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XXI Encontro

Nacional SPQ
Qumica e Inovao
11 a 13 de Junho de 2008
Faculdade de Engenharia da Universidade do Porto
XXI ENCONTRO NACIONAL DA SOCIEDADE
PORTUGUESA DE QUMICA






QUMICA E
INOVAO














Livro de Resumos



11, 12 e 13 de Junho de 2008

Faculdade de Engenharia, Universidade do Porto
ii
XXI ENCONTRO NACIONAL DA SOCIEDADE PORTUGUESA
DE QUMICA



Depsito legal n 275876/08
ISBN: 978-989-8124-03-6
Sociedade Portuguesa de Qumica




Editores: Joaquim Lus Faria
Jos Lus Figueiredo
Bruno Fernandes Machado
Edio: Sociedade Portuguesa de Qumica
Capa: Csar Sanches
DCI - Departamento de Comunicao e Imagem
FEUP
Montagem: Comisso Organizadora do XXI ENSPQ




Publicao parcialmente subsidiada pela
Fundao para a Cincia e a Tecnologia




O presente livro foi produzido a partir dos trabalhos submetidos directamente
pelos autores. Foram apenas introduzidas pequenas alteraes de edio que de
modo algum modificaram os contedos cientficos. O modelo final de impresso
foi estabelecido para o XXI Encontro Nacional da Sociedade Portuguesa de
Qumica de acordo com as normas divulgadas publicamente nos anncios do
evento. A responsabilidade dos contedos cientficos dos respectivos autores.
iii
COMISSO ORGANIZADORA LOCAL
Joaquim Lus Faria
Adrin M.T. Silva
Bruno Fernandes Machado
Cludia Gomes Silva
Filomena Gonalves
Helder Teixeira Gomes
Joo Paiva
Jos Joaquim Melo rfo
Manuel Fernando Pereira
Marcela Segundo
Nuno Loureno

COMISSO CIENTFICA
Jos Lus Figueiredo (Presidente SPQ)
Baltazar Romo de Castro (Universidade do Porto)
Fernando Rama Ribeiro (Universidade Tcnica de Lisboa)
Hugh Burrows (Universidade de Coimbra)
Irene Montenegro (Universidade do Minho)
Joo Brando (Universidade do Algarve)
Joo Crespo (Universidade Nova de Lisboa)
Joo Rocha (Universidade de Aveiro)
Jos Artur Martinho Simes (Universidade de Lisboa)
Jos Lus Costa Lima (Universidade do Porto)
Peter Carrot (Universidade de vora)


iv
COMISSO ORGANIZADORA NACIONAL
Mrio Nuno Berberan Santos (Vice-Presidente SPQ)
Paulo Ribeiro Claro (Secretrio Geral da SPQ)
Leonardo Mendes (secretariado)
Cristina Campos (secretariado)

Delegaes
Clara Magalhes, Aveiro
Joo Paulo Andr, Braga
Srgio Seixas Melo, Coimbra
Eurico Cabrita, Lisboa
Joaquim Lus Faria, Porto

Divises e Grupos
Antnio O. S. S. Rangel (Div. Qumica Analtica)
Artur Silva (Div. Qumica Orgnica)
Carlos Folhadela Simes (Div. Ensino e Divulgao da Qumica)
Clia Costa Gomes da Silva (Div. Qumica Alimentar)
Tito Trindade (Div. Qumica Inorgnica)
Isabel Moura (Div. Cincias da Vida)
Joaquim Lus Faria (Div. Catlise e Materiais Porosos e Grupo Fotoqumica)
Abel J. S. C. Vieira (Grupo Radicais Livres)
Bernardo Jerosch Herold (Grupo Histria da Qumica)
Carlos Baleizo (Grupo Qumicos Jovens)
Jos Miguel Costa Reis (Grupo Qumica Industrial)
Jos S. Cmara (Grupo Cromatografia)
Amlia Pilar Rauter (Grupo Glcidos)
Hugh D. Burrows (Grupo Colides, Polmeros e Interfaces)
Maria Lusa S e Melo (Grupo Qumica Teraputica)


v
PREFCIO
A Delegao do Porto da Sociedade Portuguesa de Qumica, em
colaborao com a Universidade do Porto atravs da Faculdade de
Engenharia da Universidade do Porto (FEUP) e do seu Departamento de
Engenharia Qumica (DEQ), e com o Laboratrio Associado, constitudo
em parceria pelo Laboratrio de Processos de Separao e Reaco (LSRE)
e pelo Laboratrio de Catlise e Materiais (LCM) convida todos os colegas
a participar no XXI ENCONTRO NACIONAL da Sociedade Portuguesa
de Qumica, que ter lugar no Porto, de 11 a 13 de Junho de 2008.
Na era actual, o desenvolvimento cientfico-tecnolgico e a inovao
constituem as pedras basilares de uma sociedade centrada na cincia e na
alta tecnologia. Ser debaixo do tema aglutinador QUMICA &
INOVAO que nos propomos discutir os novos desafios colocados pelo
avano do conhecimento cientfico em todas as suas interseces com a
Qumica - inovao na indstria qumica e no desenvolvimento de novos
produtos, novas tecnologias e novos processos; inovao no ensino da
qumica e da engenharia qumica; inovao nas interfaces da qumica com
as restantes cincias.
Tirando partido da natureza interdisciplinar da qumica organizamos um
encontro que esperamos pleno de actualidade, baseado num programa
dinmico que inclui sesses plenrias, sesses paralelas, apresentao de
posters, workshops, uma mesa redonda, lanamento de livros e a atribuio
do Prmio Ferreira da Silva e da Medalha Vicente Seabra. Vamos ainda ter
oportunidade de celebrar um Protocolo de colaborao com a nossa
congnere espanhola, Real Sociedade Espanhola de Qumica (RSEQ).
Contamos que o volume que agora segura nas suas mos d conta de
tudo isso e merea ser guardado como lembrana da sua participao!


Os editores,

Joaquim Lus Faria
Jos Lus Figueiredo
Bruno Fernandes Machado

vi
INSTITUIES ORGANIZADORAS




INSTITUIES DE APOIO

EMPRESAS PATROCINADORAS








EQUIPAMENTOS
PARA LABORATRIO
vii
PROGRAMA CIENTFICO
11 de Junho de 2008

09:00-11:15 Registo e entrega de documentao
11:15-11:45 Abertura
11:45-12:30 Plenria Ferreira da Silva
FdS Slvia M. B. Costa (Centro de Qumica Estrutural, IST, UTL)
My scientific journey: Exploring Photochemistry from
milliseconds to picoseconds
12:30-15:00 Almoo e sesso de posters
15:00-15:45 PL1 Philippe Serp (Laboratoire de Chimie de Coordination,
Toulouse, Frana)
Catalysis for and with carbon nanotubes
15:45-16:00 Assinatura do Protocolo SPQ-RSEQ
16:00-16:30 Intervalo para caf
16:30-18:30 Sesses Paralelas

Novas Fronteiras da Qumica (B032)
16:30-17:00 CC1 Carmen Freire (CICECO e Dep. Qumica, U. Aveiro)
Composite materials based on acylated cellulose fibers
17:00-17:30 CC2 Mariette M. Pereira (Dep. Qumica, U. Coimbra)
New opportunities for photodynamic therapy of cancer: A
portfolio of stable bacteriochlorins
17:30-17:45 CO1 Michael M. Caldeira (Centro de Qumica da Madeira, Dep.
Qumica, U. Madeira)
Volatile urine profile of oncologic patients by headspace solid-
phase microextraction
17:45-18-00 CO2 Lus C. Branco (REQUIMTE, Dep. Qumica, FCT, UNL)
Uso de lquidos inicos funcionalizados como novos materiais
orgnicos
18:00-18:30 CC3 V. de Zea Bermudez (Dep. Qumica, UTAD)
Auto-organizao nos materiais

viii
Inovao na Indstria Qumica (Auditrio)
16:30-17:00 CC9 Henrique Cerqueira (PETROBRAS, Rio de Janeiro, Brasil)
Efeito de metais na desativao de zelitos Y
17:00-17:15 CO11 Gonalo V.S.M. Carrera (REQUIMTE, CQFB, Dep.
Qumica, FCT, UNL)
Aprendizagem automtica com bases de dados de reaces
qumicas: estimativas de reactividade
17:15-17:30 CO12 Susana S. M. P. Vidigal (Escola Superior de Biotecnologia,
U. Catlica Portuguesa)
Sistema SIA-LOV para a determinao enzimtica de perxido
de hidrognio
17:30-18-00 CC10 M. Filipa Ribeiro (Dep. Engenharia Qumica e Biolgica,
IST)
Solues catalticas para a poluio automvel
18:00-18:30 CC11 Paulo Arajo (CUF, Qumicos de Portugal)
A inovao na indstria qumica

Inovao no Ensino da Qumica e da Engenharia Qumica
(B035 / Sala de computadores)
16:30-16:45 CO19 Hermnio Diogo (Centro de Qumica Estrutural, IST, UTL)
A microscopia qumica associada ao estudo da srie
electroqumica dos metais
16:45-17:00 CO20 Emanuel A. C. F. Reis (FCUP e Escola Bsica Integrada
com Jardim de Infncia do Couo)
A plataforma Moodle no ensino da qumica: experincias e pistas
de inovao
17:00-17:30 CC18 Slvia M. M. A. Pereira Lima (Dep. Qumica, Escola de
Cincias, U. Minho)
A qumica em projectos interdisciplinares de Engenharia e Gesto
Industrial
17:30-18:30 WS1 Carla Morais (Escola Secundria Carolina Michaelis, Porto)
Concepo e utilizao de recursos multimdia para o ensino da
Qumica
18:30 Porto de Honra
ix
12 de Junho de 2008
09:00-10:30 Sesses Paralelas

Novas Fronteiras da Qumica (Auditrio)
09:00-09:30 CC4 Joo Andr (Centro de Qumica, U. Minho)
Metal-ion-dependent biological properties of a chelator-derived
somatostatin analogue for tumour targeting
09:30-09:45 CO10 Agostinho A. Almeida (REQUIMTE, Servio de Qumica-
Fsica, FFUP)
A tcnica de ICP-MS em anlise forense
09:45-10:00 CO4 Clia T. Sousa (Dep. Fsica, FCUP e IFIMUP)
Ordered assembly of nanowires and nanotubes in porous alumina
membranes
10:00-10:15 CO5 Mariana Sardo (CICECO, Dep. Qumica, U. Aveiro)
Spectroscopic characterization of polymorphism in molecular
solids
10:15-10:30 CO6 Filipe A. Almeida Paz (CICECO, Dep. Qumica, U. Aveiro)
Functional Lanthanide-organic frameworks

Inovao na Indstria Qumica (B032)
09:00-09:15 CO13 Vera P. Santos (LCM, Dep. Engenharia Qumica, FEUP)
Oxidao total de acetato de etilo usando catalisadores de xido
de mangans
09:15-09:30 CO14 Rui C. Santos (CQB, FCUL)
ThermInfo: A chemoinformatics database system for online
properties prediction
09:30-10:00 CC12 Alrio Rodrigues (LSRE, Dep. Engenharia Qumica, FEUP)
O tringulo da inovao: Novas solues para problemas novos e
velhos
10:00-10:30 CC13 P. Selvam (National Centre for Catalysis Research,
Department of Chemistry, Indian Institute of Technology, India)
Nanoporous carbon supported platinum (Pt/NCCR-1)
electrocatalyst for methanol oxidation

Inovao no Ensino da Qumica e da Engenharia Qumica
(B035 / Laboratrio de Qumica)
09:00-09:30 CC19 Filomena Cames (CCMM, DQB, FCUL)
Cincia da medio em qumica
x
09:30-10:30 WS2 Antnio Jos Ferreira (Escola Secundria Avelar Brotero,
Coimbra)
Kit de anlise de plsticos, isso resulta...?
10:30-11:00 Intervalo para caf
11:00-11:45 PL2 Nazrio Martin (Dep. Qumica Orgnica, Facultad de
Qumica, Universidad Complutense, Madrid, Espanha)
When curves meet themselves: Donor-acceptor supramolecular
assemblies
11:45-12:30 Sesses Paralelas

Novas Fronteiras da Qumica (Auditrio)
11:45-12:15 CC5 Manuel Prieto (Centro de Qumica-Fsica Molecular, IST)
Lipid domains and lipid-protein interaction: Physical chemistry
and spectroscopy
12:15-12:30 CO7 Carlos Baleizo (Centro de Qumica-Fsica Molecular, IST)
An optical oxygen and temperature dual sensor operating under
extreme conditions

Inovao na Indstria Qumica (B032)
11:45-12:15 CC14 Lus Pais (LSRE, ESTiG, IPB)
Preparative enantioselective chromatography
12:15-12:30 CO15 Ricardo Franco (REQUIMTE, Dep. Qumica, FCT, UNL)
pH-induced adsorption of cytochrome c to acidic self-assembled
monolayers on gold surfaces and nanoparticles

Inovao no Ensino da Qumica e da Engenharia Qumica (B035)
11:45-12:15 CC20 Sebastio Feyo (Dep. Engenharia Qumica, FEUP)
The Bologna process: Qualifications frameworks in the
engineering area
12:15-12:30 CO21 M. Manuela F. Silva (Escola Secundria Fonseca
Benevides)
Qumica e biologia na cozinha: Um contributo para o ensino
experimental das cincias no ensino secundrio
12:30-15:00 Almoo e sesso de posters
15:00-15:45 PL3 Carlos Romo (Instituto de Tecnologia Qumica e Biolgica,
UNL, Portugal)
Therapy with CO: Meeting a challenge
15:45-21:00 Passeio no Porto
21:00 Jantar do Encontro/Festa Jovem
xi
13 de Junho de 2008
09:00-10:30 Sesses Paralelas

Novas Fronteiras da Qumica (B032)
09:00-09:15 CO8 Leila M. Moura (Centro de Qumica-Fsica Molecular, IST)
Nanoparticulas polimricas para reconhecimento de DNA
09:15-09:30 CO9 Ana M. Gil (CICECO, Dep. Qumica, U. Aveiro)
Metabonomics in food science: Where to now?
09:30-10:00 CC6 Iola Duarte (CICECO, Dep. Qumica, U. Aveiro)
The potential of NMR spectroscopy for assessing the metabolic
composition and activity of tumor tissues and cells
10:00-10:30 CC7 Marlene Lcio (REQUIMTE, Servio de Qumica-Fsica,
FFUP)
New look into drug-membrane interactions: Towards better
treatments

Inovao na Indstria Qumica (B035)
09:00-09:30 CC15 Armando Silvestre (CICECO e Dep. Qumica, U. Aveiro)
The Biorefinery concept: A step forward in the sustainable
production of chemicals and materials from biomass
09:30-09:45 CO16 Ana G. Cunha (CICECO e Dep. Qumica, U. Aveiro)
Bi-phobic cellulose fibers via surface modification with
perfluorinated compounds
09:45-10:00 CO17 Antnio J. Queimada (LSRE, Dep. Engenharia Qumica,
FEUP)
Phase equilibria of some phenolic compounds: Experimental and
modelling
10:00-10:30 CC16 Monica Casella (CINDECA, Facultad de Ciencias Exactas
UNLP, La Plata, Argentina)
Experimental and theoretical studies on chiral heterogeneous
catalysts for hydrogenation reactions

Inovao no Ensino da Qumica e da Engenharia Qumica
(Auditrio / Sala de computadores)
09:00-09:30 CC21 Clementina Teixeira (Centro de Qumica Estrutural, IST,
UTL)
Microscopia qumica e crescimento de cristais: Ensinar e
empreender
xii
09:30-10:30 WS3 Ricardo Silva e Manuel Silva Pinto (Colgio Internato dos
Carvalhos e Casa das Cincias, FCUP)
A aula do dia seguinte...
10:30-11:00 Intervalo para caf
11:00-11:45 PL4 John Moore (University of Wisconsin-Madison, Estados
Unidos da Amrica)
Innovation in chemical education
11:45-12:30 Sesses Paralelas

Novas Fronteiras da Qumica (B032)
11:45-12:15 CC8 M. Manuela M. Raposo (Centro de Qumica, U. Minho)
Design, sntese e caracterizao de novos sistemas heterocclicos
No Clssicos com aplicao em ptica No-Linear (ONL)
12:15-12:30 CO3 Hugh D. Burrows (Dep. Qumica, U. Coimbra)
Using nonionic surfactants to push conjugated polyelectrolytes
around

Inovao na Indstria Qumica (B035)
11:45-12:15 CC17 Goran Drazic (Joef Stefan Institute, Liubliana, Eslovnia)
Analytical electron microscopy as a powerful tool in the
development of new nanomaterials
12:15-12:30 CO18 Ana Manhita (CQE e Dep. Qumica, U. vora)
Material study of an Arraiolos tapestry from the 18
th
century

Inovao no Ensino da Qumica e da Engenharia Qumica (Auditrio)
11:45-12:15 CC22 Carlos Corra (CIQ e Dep. Qumica, FCUP)
Inovando experincias de salo
12:15-12:30 CO22 Maria Goreti Matos (Oficinas de S. Jos, Lisboa)
Com abboras, cenouras, batatas, mas...
12:30-14:30 Almoo e sesso de posters
14:30-15:30 Debate
Recursos na Web para o ensino da qumica
15:30-16:00 Medalha Vicente Seabra
MVS Manuel F R Pereira (LCM, DEQ, FEUP)
Qumica superficial de materias de carbono: aplicaes
ambientais
16:00-16:15 Fecho

xiii
NDICE
PRMIO FERREIRA DA SILVA
MY SCIENTIFIC JOURNEY: EXPLORING PHOTOCHEMISTRY FROM MILLISECONDS TO
PICOSECONDS
SILVIA M. B. COSTA............................................................................................................................. 3
MEDALHA VICENTE SEABRA
QUMICA SUPERFICIAL DE MATERIAS DE CARBONO: APLICAES AMBIENTAIS
MANUEL F R. PEREIRA ......................................................................................................................... 7
LIES PLENRIAS
CATALYSIS FOR AND WITH CARBON NANOTUBES
PHILIPPE SERP .................................................................................................................................... 11
WHEN CURVES MEET THEMSELVES: DONOR-ACCEPTOR SUPRAMOLECULAR
ASSEMBLIES
NAZARIO MARTN, LUIS SNCHEZ, EMILIO PREZ, M ANGELES HERRANZ, GUSTAVO FERNNDEZ ..... 12
THERAPY WITH CO: MEETING A CHALLENGE
CARLOS C. ROMO ............................................................................................................................ 13
INNOVATION IN CHEMICAL EDUCATION
JOHN W. MOORE ................................................................................................................................ 14
CONFERNCIAS CONVIDADAS
NOVAS FRONTEIRAS DA QUMICA
COMPOSITE MATERIALS BASED ON ACYLATED CELLULOSE FIBERS
CARMEN S. R. FREIRE ........................................................................................................................ 17
NEW OPPORTUNITIES FOR PHOTODYNAMIC THERAPY OF CANCER: A PORTFOLIO OF
STABLE BACTERIOCHLORINS
MARIETTE M. PEREIRA ...................................................................................................................... 18
AUTO-ORGANIZAO NOS MATERIAIS
V. DE ZEA BERMUDEZ ........................................................................................................................ 19
METAL-ION-DEPENDENT BIOLOGICAL PROPERTIES OF A CHELATOR-DERIVED
SOMATOSTATIN ANALOGUE FOR TUMOUR TARGETING
JOO P. ANDR .................................................................................................................................. 20
LIPID DOMAINS AND LIPID-PROTEIN INTERACTION: PHYSICAL CHEMISTRY AND
SPECTROSCOPY
LUS M. S. LOURA, ANA COUTINHO, MANUEL PRIETO ...................................................................... 21
THE POTENTIAL OF NMR SPECTROSCOPY FOR ASSESSING THE METABOLIC
COMPOSITION AND ACTIVITY OF TUMOR TISSUES AND CELLS
IOLA F. DUARTE, ANA M. GIL, BRIAN J. GOODFELLOW, LINA CARVALHO, VITOR SOUSA, JOANA B.
MELO, ISABEL M. CARREIRA ............................................................................................................. 22
NEW LOOK INTO DRUG-MEMBRANE INTERACTIONS: TOWARDS BETTER TREATMENTS
MARLENE LCIO ................................................................................................................................ 23
xiv
DESIGN, SNTESE E CARACTERIZAO DE NOVOS SISTEMAS HETEROCCLICOS NO
CLSSICOS COM APLICAO EM PTICA NO-LINEAR (ONL)
M. MANUELA M. RAPOSO, ROSA M. F. BATISTA, SUSANA P. G. COSTA ............................................ 24
INOVAO NA INDSTRIA QUMICA
EFEITO DE METAIS NA DESATIVAO DE ZELITOS Y
HENRIQUE SOARES CERQUEIRA ......................................................................................................... 25
SOLUES CATALTICAS PARA A POLUIO AUTOMVEL
M. FILIPA RIBEIRO ............................................................................................................................. 26
A INOVAO NA INDSTRIA QUMICA
PAULO A. P. ARAJO ......................................................................................................................... 27
O TRINGULO DA INOVAO: NOVAS SOLUES PARA PROBLEMAS NOVOS E VELHOS
ALIRIO E. RODRIGUES ........................................................................................................................ 28
NANOPOROUS CARBON SUPPORTED PLATINUM (PT/NCCR-1) ELECTROCATALYST FOR
METHANOL OXIDATION
P. SELVAM, B. VISWANATHAN, B. KUPPAN ....................................................................................... 29
PREPARATIVE ENANTIOSELECTIVE CHROMATOGRAPHY
LUS S. PAIS ....................................................................................................................................... 30
THE BIOREFINERY CONCEPT: A STEP FORWARD IN THE SUSTAINABLE PRODUCTION
OF CHEMICALS AND MATERIALS FROM BIOMASS
ARMANDO SILVESTRE ........................................................................................................................ 31
EXPERIMENTAL AND THEORETICAL STUDIES ON CHIRAL HETEROGENEOUS
CATALYSTS FOR HYDROGENATION REACTIONS
MNICA L. CASELLA, JOS F. RUGGERA, ANDREA B. MERLO, VIRGINIA VETERE ............................ 32
ANALYTICAL ELECTRON MICROSCOPY AS A POWERFUL TOOL IN THE
DEVELOPMENT OF NEW NANOMATERIALS
GORAN DRAZIC .................................................................................................................................. 33
INOVAO NO ENSINO DA QUMICA E DA ENGENHARIA QUMICA
A QUMICA EM PROJECTOS INTERDISCIPLINARES DE ENGENHARIA E GESTO
INDUSTRIAL
SLVIA M. M. A. PEREIRA-LIMA, RUI M. LIMA, SANDRA FERNANDES ............................................... 34
CIENCIA DA MEDIO EM QUMICA
M. FILOMENA CAMES ...................................................................................................................... 35
THE BOLOGNA PROCESS - QUALIFICATIONS FRAMEWORKS IN THE ENGINEERING
AREA
S. FEYO DE AZEVEDO ......................................................................................................................... 36
MICROSCOPIA QUMICA E CRESCIMENTO DE CRISTAIS: ENSINAR E EMPREENDER
CLEMENTINA TEIXEIRA ...................................................................................................................... 37
INOVANDO EXPERINCIAS DE SALO
CARLOS M. M. S. CORRA ................................................................................................................. 38

xv
COMUNICAES ORAIS
NOVAS FRONTEIRAS DA QUMICA
VOLATILE URINE PROFILE OF ONCOLOGIC PATIENTS BY HEADSPACE SOLID-PHASE
MICROEXTRACTION
MICHAEL M. CALDEIRA, MAFALDA ANTUNES, FERNANDO AVEIRO, SLVIA M. ROCHA, JOS S.
CMARA ............................................................................................................................................ 41
USO DE LQUIDOS INICOS FUNCIONALIZADOS COMO NOVOS MATERIAIS ORGNICOS
LUS C. BRANCO, ANDREIA ROSATELLA, CARLOS A. M. AFONSO ..................................................... 42
USING NONIONIC SURFACTANTS TO PUSH CONJUGATED POLYELECTROLYTES
AROUND
HUGH D. BURROWS, S. M. FONSECA, M. KNAAPILA, M. E. EUSBIO, R. CASTRO, S. PRADHAN, U.
SCHERF, H. VAUGHAN, A. P. MONKMAN ........................................................................................... 43
ORDERED ASSEMBLY OF NANOWIRES AND NANOTUBES IN POROUS ALUMINA
MEMBRANES
C. T. SOUSA, M. P. PROENCA, D. C. LEITAO, A. M. L. LOPES, J. VENTURA, J. G. CORREIA, A. M.
PEREIRA, J. B. SOUSA, J. P. ARAUJO ................................................................................................... 44
SPECTROSCOPIC CHARACTERIZATION OF POLYMORPHISM IN MOLECULAR SOLIDS
MARIANA SARDO, MARIELA M. NOLASCO, ANA M. AMADO, PAULO J. A RIBEIRO-CLARO .............. 45
FUNCTIONAL LANTHANIDE-ORGANIC FRAMEWORKS
FILIPE A. ALMEIDA PAZ, JOO ROCHA, LUS D. CARLOS, TITO TRINDADE ......................................... 46
AN OPTICAL OXYGEN AND TEMPERATURE DUAL SENSOR OPERATING UNDER
EXTREME CONDITIONS
CARLOS BALEIZO, STEFAN NAGL, MICHAEL SCHAFRLING, OTTO S. WOLFBEIS, MRIO N.
BERBERAN-SANTOS ........................................................................................................................... 47
NANOPARTICULAS POLIMRICAS PARA RECONHECIMENTO DE DNA
LEILA M. MOURA, TELMO PRAZERES, J. P. S. FARINHA, J. M. G.MARTINHO ..................................... 48
METABONOMICS IN FOOD SCIENCE: WHERE TO NOW?
ANA M. GIL ....................................................................................................................................... 49
A TCNICA DE ICP-MS EM ANLISE FORENSE
AGOSTINHO A. ALMEIDA, AGOSTINHO J. C. SANTOS, TERESA M. S. MAGALHES, JOANA M. F. TUNA 50
INOVAO NA INDSTRIA QUMICA
APRENDIZAGEM AUTOMTICA COM BASES DE DADOS DE REACES QUMICAS:
ESTIMATIVAS DE REACTIVIDADE
GONALO V. S. M. CARRERA, JOO AIRES-DE-SOUSA ...................................................................... 51
SISTEMA SIA-LOV PARA A DETERMINAO ENZIMTICA DE PERXIDO DE HIDROGNIO
SUSANA S. M. P. VIDIGAL, ILDIK V. TTH, ANTNIO O. S. S. RANGEL ........................................... 52
OXIDAO TOTAL DE ACETATO DE ETILO USANDO CATALISADORES DE XIDO DE
MANGANS
V. P. SANTOS, M. F. R. PEREIRA, J. J. M. RFO, J. L. FIGUEIREDO ................................................... 53
THERMINFO: A CHEMOINFORMATICS DATABASE SYSTEM FOR ONLINE PROPERTIES
PREDICTION
RUI C. SANTOS, HUGO F. M. C. MARTINIANO, JOO P. LEAL, BENEDITO J. COSTA CABRAL, JOS A.
MARTINHO SIMES ............................................................................................................................ 54
xvi
PH-INDUCED ADSORPTION OF CYTOCHROME C TO ACIDIC SELF-ASSEMBLED
MONOLAYERS ON GOLD SURFACES AND NANOPARTICLES
MARIA J. FEIO, KRISZTINA ISTVN, INS GOMES, PEDRO QUARESMA, NUNO C. SANTOS, PETER
EATON, RICARDO FRANCO ................................................................................................................. 55
BI-PHOBIC CELLULOSE FIBERS VIA SURFACE MODIFICATION WITH
PERFLUORINATED COMPOUNDS
ANA G. CUNHA, CARMEN S. R. FREIRE, ARMANDO J. D. SILVESTRE, CARLOS PASCOAL NETO,
ALESSANDRO GANDINI ...................................................................................................................... 56
PHASE EQUILIBRIA OF SOME PHENOLIC COMPOUNDS: EXPERIMENTAL AND
MODELLING
ANTNIO J. QUEIMADA, FTIMA L. MOTA, SIMO P. PINHO, EUGNIA A. MACEDO ......................... 57
MATERIAL STUDY OF AN ARRAIOLOS TAPESTRY FROM THE 18
TH
CENTURY
ANA MANHITA, VANESSA PIMENTA, HELENA VARGAS, ISABEL RIBEIRO, TERESA PACHECO, JOS
MIRO, TERESA FERREIRA, ANTNIO CANDEIAS, CRISTINA T. DA COSTA ........................................ 58
INOVAO NO ENSINO DA QUMICA E DA ENGENHARIA QUMICA
A MICROSCOPIA QUMICA ASSOCIADA AO ESTUDO DA SRIE ELECTROQUMICA DOS
METAIS
HERMNIO DIOGO, MANUEL E. MINAS DA PIEDADE, CLEMENTINA TEIXEIRA .................................... 59
A PLATAFORMA MOODLE NO ENSINO DA QUMICA: EXPERINCIAS E PISTAS DE
INOVAO
EMANUEL A. C. F. REIS ...................................................................................................................... 60
QUIMICA E BIOLOGIA NA COZINHA: UM CONTRIBUTO PARA O ENSINO
EXPERIMENTAL DAS CINCIAS NO ENSINO SECUNDRIO
M. MANUELA F. SILVA, M. NAIR ALUA, PEDRO F. GALEGO, M. CELESTE SERRA ............................. 61
COM ABBORAS, CENOURAS, BATATAS, MAS
MARIA GORETI MATOS, ANA MAFALDA SILVA, BRUNO MENDES, TIAGO FILIPE .............................. 62
COMUNICAES EM PAINEL
NOVAS FRONTEIRAS DA QUMICA
OXAZAPHOSPHOLIDINE-OXIDE, A VERSATILE ORTHO-DIRECTING GROUP
NELSON C. MARTINS, AMADEU F. BRIGAS, JIANLIANG XIAO ............................................................ 65
MATERIAIS POROSOS PARA ADSORO DE XIDO NTRICO
MOISS L. PINTO, JOO PIRES, JOO ROCHA ..................................................................................... 66
PARTIAL OXIDATION OF METHANE OVER HETEROBIMETALLIC COPPER-
LANTHANIDE OXIDES
A. FERREIRA, A. JANECO, N. PINHO, A. P. GONALVES, J. BRANCO ................................................ 67
HYDROFORMYLATION OF KAURANE DERIVATIVES: MECHANISTIC STUDIES
ANDREIA F. PEIXOTO, MARISELA REYES, RICARDO R. CONTRERAS, EDUARDO N. DOS SANTOS, J.
CARLES BAYN, MARIETTE M. PEREIRA ........................................................................................... 68
OZONIZAO CATALTICA DE COMPOSTOS ORGNICOS MODELO EM SOLUO
AQUOSA
PATRCIA C. C. FARIA, JOS J. M. RFO, MANUEL F. R. PEREIRA ................................................... 69
REDUO CATALTICA COM HIDROGNIO DE NITRATOS E NITRITOS EM GUA
OLVIA SALOM G. P. SOARES, JOS J. M. RFO, MANUEL F. R. PEREIRA ...................................... 70
xvii
NEW HETEROGENEOUS CHIRAL VANADIUM(V) SALEN CATALYSTS FOR THE
STRECKER REACTION
M. ALEXANDRA ESTEVES, JOO C. OLIVEIRA, A. MARGARIDA GUERREIRO, CLIA SANTOS, CARLOS
BALEIZO .......................................................................................................................................... 71
AMINE-FUNCTIONALISED SILICA NANOPARTICLES AS SUPPORTS FOR [M(ACAC)
2
]
CATALYSTS
JOS F. SILVA, CLARA PEREIRA, SUSANA L. H. REBELO, ANA P. CARVALHO, JOO PIRES, CRISTINA
FREIRE ............................................................................................................................................... 72
NEW Rh/CHIRAL MONOPHOSPHITE CATALYST IN HYDROFORMYLATION OF STYRENE
DERIVATIVES
RUI M. B. CARRILHO, ARTUR R. ABREU, PAULA S. S. LACERDA, MARIA JOS S. M. MORENO,
MARIETTE M. PEREIRA, JOAN C. BAYN ........................................................................................... 73
Ni-Cu RANEY-TYPE CATALYSTS FOR CO
X
-FREE HYDROGEN PRODUCTION VIA
METHANE CRACKING
A. F. CUNHA, J. J. M. RFO, J. L. FIGUEIREDO ................................................................................. 74
DESENVOLVIMENTO DE CARVES ACTIVADOS A PARTIR DE PRECURSORES
NATURAIS
JOO M. VALENTE NABAIS, PETER J. M. CARROTT, MANUELA L. RIBEIRO CARROTT, JOS A. F. L.
GOMES ............................................................................................................................................... 75
CARACTERIZAO E ESTABILIDADE ESTRUTURAL DE TITANOSSILICATOS
MESOPOROSOS
J. VALRIO, C. GALACHO, M. M. L. RIBEIRO CARROTT, P. J. M. CARROTT ....................................... 76
ADSORO DE O-DICLOROBENZENO EM CARBONIZADOS DE P DE CORTIA
ANA S. MESTRE, MARTA ANDRADE, JOO PIRES, ANA P. CARVALHO .............................................. 77
ACTIVAO DE CAROOS DE PSSEGO COM K
2
CO
3

ANA S. BEXIGA, ANA S. MESTRE, ISABEL M. FONSECA, ANA P. CARVALHO..................................... 78
SNTESE DE 2,2-BIS-BINOL QUIRAIS: AVALIAO CATALTICA NA ALQUILAO DE
ALDEDOS
ARTUR R. ABREU, MARIETTE M. PEREIRA, ERMELINDA EUSBIO, MRIO T. S. ROSADO, J. CARLES
BAYON ............................................................................................................................................... 79
IMOBILIZAO DE COMPLEXOS DE MOLIBDNIO(II) EM MCM-41 E SUA APLICAO
EM CATLISE
MARTA S. SARAIVA, MARIA JOS CALHORDA CARLA D. NUNES ...................................................... 80
ESTERIFICAO DE CIDO PALMTICO A BIODIESEL NA PRESENA DE POLMEROS
COM GRUPOS CIDO SULFNICO
CATARINA S. CAETANO, ANA M. RAMOS, ISABEL M. FONSECA, JOAQUIM VITAL, JOS E.
CASTANHEIRO .................................................................................................................................... 81
ADSORO DE CORANTES EM MATERIAIS DE CARBONO MESOPOROSOS
MODIFICADOS
J. P. S. SOUSA, C. A. ORGE, F. GONALVES, C. FREIRE, J. L. FIGUEIREDO, M. F. R. PEREIRA, J. J. M.
RFO ............................................................................................................................................... 82
INFLUNCIA DE CLCIO E SDIO NA ACTIVAO QUMICA DE LENHINA COM CIDO
FOSFRICO
PAULO A. M. MOURO, PETER J. M. CARROTT, MANUELA RIBEIRO CARROTT, RITA I. L. S. LOPES ..... 83
SNTESE E APLICAO EM OZONIZAO CATALTICA DE MATERIAIS DE CARBONO
MESOPOROSOS
C. A. ORGE, J. P. S. SOUSA, F. GONALVES, P. C. C. FARIA, C. FREIRE, J. J. M. RFO, M. F. R. PEREIRA . 84
xviii
COVALENT SIDEWALL FUNCTIONALIZATION OF CARBON NANOTUBES BY
METALLOPORPHYRINS THROUGH 1,3-DIPOLAR CYCLOADDITION
D. TEIXEIRA, S. L. H. REBELO, F. GONALVES, A. M. G. SILVA, M. F. R. PEREIRA, J. J. M. RFO, C.
FEIRE.................................................................................................................................................. 85
FUNCIONALIZAO DE SLICA GEL COM 2-AMINO-1,3,4-TIADIAZOL E Mo(II)
MARIA VASCONCELLOS DIAS, NEWTON L. DIAS FILHO, PAULA FERREIRA, CARLA D. NUNES, MARIA
JOS CALHORDA, FTIMA C. M. PORTUGAL, JOS M. F. NOGUEIRA ................................................. 86
PREPARAO DE XIDOS METLICOS POR EXOTEMPLATING EM MATERIAIS DE
CARBONO
S. S. T. BASTOS, F. GONALVES, V. P. SANTOS, J. J. M. RFO, M. F. R. PEREIRA, J. L. FIGUEIREDO ... 87
ACETOXILAO DE GLICEROL COM HETEROPOLICIDOS IMOBILIZADOS EM
ZELITO Y
PATRCIA FERREIRA, ANA M. RAMOS, ISABEL M. FONSECA, JOAQUIM M. VITAL, JOS E.
CASTANHEIRO .................................................................................................................................... 88
TITANIUM DIOXIDE SUPPORTED Pt CATALYSTS FOR CINNAMALDEHYDE
HYDROGENATION
BRUNO F. MACHADO, HELDER T. GOMES, JOAQUIM L. FARIA .......................................................... 89
PHOTODEPOSITION OF Pt NANOPARTICLES ON Ce-Ti-O
ADRIN M. T. SILVA, BRUNO F. MACHADO, HELDER T. GOMES, JOS L. FIGUEIREDO, GORAN
DRAZIC, JOAQUIM L. FARIA ............................................................................................................... 90
SYNTHESIS, CHARACTERIZATION AND CATALYTIC APPLICATION OF A CHIRAL
MENTHYLDIMETHYLTIN MOLYBDATE
MARTA ABRANTES, ANABELA A. VALENTE, MARTYN PILLINGER, CARLOS C. ROMO, ISABEL S.
GONALVES ....................................................................................................................................... 91
GOLD NANOPARTICLES ON CERIA SUPPORTS FOR THE OXIDATION OF CARBON
MONOXIDE
S. A. C. CARABINEIRO, A. M. T. SILVA, G. DRAZIC, J. L. FIGUEIREDO .............................................. 92
PREPARATION OF HIGHLY MESOPOROUS CARBON CATALYSTS FOR WET OXIDATION
OF ANILINE
PURNAKALA V. SAMANT, HELDER T. GOMES, JOS L. FIGUEIREDO, JOAQUIM L. FARIA ................... 93
UNUSUAL POLARITY AND SURFACE POTENTIAL PROPERTIES IN BINARY MIXED
LIPID BILAYERS ACCESSED WITH PYRENE BASED FLUOROPHORES
JORGE MARTINS, DALILA ARRAIS, MIGUEL MANUEL ........................................................................ 94
SURFACE MODIFICATION OF MAGNETIC NANOPARTICLES
ANA S. CARDOSO, ANA C. A. ROQUE ................................................................................................ 95
ADSORPTION OF PROTEINS ON MAGNETIC NANOPARTICLES
VERA CASTRO, ANA S. PINA, ANA S. CARDOSO, ABID HUSSAIN, ANA C. A. ROQUE......................... 96
MAPEAMENTO DE INTERACES ENTRE CADEIAS LATERAIS DE PARES DE AMINOCIDOS
MIGUEL M. DE SOUSA, CRISTIAN MUNTEANU, ALEXANDRE L. MAGALHES .................................... 97
MONITORIZAO DE EFLUXO DE POTSSIO E FOSFATO DE CLULAS BACTERIANAS
(LISTERIA INNOCUA)
M. TERESA S. O. B. FERREIRA, HELENA I. S. TEIXEIRA, ILDIK V. TTH, FRANCISCO M. CAMPOS,
JOS A. COUTO, TIMOTHY A. HOGG, ANTNIO O. S. S. RANGEL ....................................................... 98
WHEY PROTEIN ISOLATE - CHITOSAN INTERACTIONS: A CALORIMETRIC AND
SPECTROSCOPIC STUDY
HILIA K. S. DE SOUZA, GUANGYUE BAI, MARGARIDA BASTOS, MARIA DO PILAR GONALVES ...... 99
xix
DEGRADAO TERMOXIDATIVA DE COPOLMEROS E MISTURAS BASE DE EVA
ISABEL G. MOURA, GABRIELA BOTELHO, ANA V. MACHADO ......................................................... 100
SELF-AGGREGATION OF MODIFIED DEXTRINS AND THEIR INTERACTIONS WITH
SURFACTANTS
G. BAI, C. GONALVES, F. M. GAMA, M. BASTOS ........................................................................... 101
CARACTERIZAO TRMICA DE MEMBRANAS DE ACETATO DE CELULOSE/PANI
DANIEL A. CERQUEIRA, ARTUR J. M. VALENTE, GUIMES R. FILHO, ALFONSO JIMNEZ .................. 102
PREPARATION AND CHARACTERISATION OF LAYER-BY-LAYER ASSEMBLED
COMPOSITES FROM [Ni(SALEN)]-TYPE COMPLEX WITH CARBON NANOTUBES
SNIA PATRCIO, ANA S. SILVA, COSME MOURA, CRISTINA FREIRE, A. ROBERT HILLMAN ............ 103
THE BULK OXYPROPYLATION OF CHITIN AND CHITOSAN AND THE
CHARACTERIZATION OF THE POLYOLS
S. FERNANDES, C. S. R. FREIRE, C. PASCOAL NETO, A. GANDINI .................................................... 104
[Ni(SALEN)]-BASED POLYMERS BEARING CROWN ETHER SUBSTITUENTS
J. TEDIM, S. J. GURMAN, C. FREIRE, A. R. HILLMAN ........................................................................ 105
STUDIES ON THE DEPOSITION OF CHROMIUM FROM CHROMIUM (III) DES USING
MICROELECTRODE
ELISABETE S. FERREIRA, C. M. PEREIRA, FERNANDO SILVA............................................................ 106
AFM CHARACTERIZATION OF THE ORGANIZED MOLECULAR FILMS
E. J. PEREIRA, C. CARREIRA, C. M. PEREIRA, F. SILVA .................................................................... 107
PREPARATION OF NANOCOMPOSITES VIA RAFT POLYMERIZATION IN MINIEMULSION
SUSANA PEIXOTO, PENKA I. GIRGINOVA, MANUEL A. MARTINS, TITO TRINDADE, ANA BARROS-
TIMMONS ......................................................................................................................................... 108
THERMOREVERSIBLE MATERIALS BASED ON THE DIELS-ALDER REACTION OF
FURAN MONOMERS
DORA COELHO, ALESSANDRO GANDINI, ARMANDO SILVESTRE ...................................................... 109
SNTESE E CARACTERIZAO DE NANOPARTCULAS HBRIDAS COM NCLEO DE
SLICA E COROA POLIMRICA
TNIA R. RIBEIRO, J. P. FARINHA .................................................................................................... 110
CHARACTERIZATION OF MICELLAR AGGREGATES OF POLY(DCA-B-DEA)
AMPHIPHILIC COPOLYMERS IN WATER
GEMA MARCELO, TELMO J. V. PRAZERES, J. P. S. FARINHA, J. M. G. MARTINHO ........................... 111
CHIRAL SEPARATION OF PROFEN ENANTIOMERS BY PREPARATIVE LIQUID
CHROMATOGRAPHY
ANTNIO E. RIBEIRO, NUNO S. GRAA, LUS S. PAIS, ALRIO E. RODRIGUES ................................. 112
EXTRACO ADSORTIVA EM BARRA (BAE) NOVAS APLICAES PARA ANLISE DE
OPICEOS
ALEXANDRA F. P. GONALVES, NUNO R. NENG, ANA S. MESTRE, ANA P. CARVALHO, JOS M. F.
NOGUEIRA ........................................................................................................................................ 113
FLUORESCENCE QUENCHING OF A FLUORENE-PHENYLENE COPOLYMER BY
NITROAROMATICS
NGELA C. P. ALMEIDA, H. D. BURROWS, S. M. FONSECA, L. MARQUES, A. T. DE ALMEIDA,
RICARDO MALLAVIA ....................................................................................................................... 114

xx
TRANSFERNCIA DE ENERGIA ENTRE UM POLMERO CONJUGADO CATINICO E
PORFIRINAS ANINICAS
SARA M. A. PINTO, HUGH D. BURROWS, MARIETTE M. PEREIRA, SOFIA M. FONSECA, RICARDO
MALLAVIA ....................................................................................................................................... 115
SYNTHESIS AND CHARACTERIZATION OF PORPHYRIN MODIFIED INORGANIC
MATERIALS AS SENSITIZERS IN PHOTODEGRADATIVE PROCESSES
M. SILVA, M. E. AZENHA, M. M. PEREIRA, H. D. BURROWS, M. SARAKHA ..................................... 116
FLUORESCENCE PROPERTIES OF FULLERENE C
70
IN IMIDAZOLIUM IONIC LIQUIDS
SOFIA MARTINS, PAULO FORTE, PEDRO GIS, CARLOS A. M. AFONSO, CARLOS BALEIZO, MRIO N.
BERBERAN-SANTOS ......................................................................................................................... 117
PHOTOCATALYTIC OXIDATION OF CLOFIBRIC ACID WITH NANOCRYSTALLINE TiO
2

CLUDIA G. SILVA, JOAQUIM L. FARIA ........................................................................................... 118
CYCLIC VOLTAMMETRIC ANALYSIS OF 2-STYRYLCHROMONES
ANA GOMES, EDUARDA FERNANDES, M. BEATRIZ Q. GARCIA, ARTUR M. S. SILVA, DIANA C. G. A.
PINTO, CLEMENTINA M. M. SANTOS, JOS A. S. CAVALEIRO, JOS L. F. C. LIMA ........................... 119
POLIMORFISMO E REACTIVIDADE DA GABAPENTINA
VNIA ANDR, M. TERESA DUARTE, M. FTIMA MINAS DA PIEDADE ............................................ 120
APLICAO DO MODELO DE ARRHENIUS NA PREVISO DO TEMPO DE VIDA TIL DE
GEOTXTEIS
JOS R. CARNEIRO, PAULO J. ALMEIDA, MARIA L. LOPES ............................................................... 121
IDENTIFICATION AND DISCRIMINATION OF PHARMACEUTICAL RELEVANT
BACTERIA BY INTRINSIC FLUORESCENCE
ANA G. ALMEIDA, CARLA S. COUTINHO, LUS MEIRINHOS-SOARES, JOO A. LOPES...................... 122
ELECTROCHEMICAL CARACTERIZATION OF CHOLINE CHLORIDE BASED DEEP
EUTETIC SOLVENTS
MARTA FIGUEIREDO, ANA MARTINS, FERNANDO SILVA ................................................................. 123
THERMORESPONSIVE DEXTRAN AND CHITOSAN HYDROGELS AS DRUG DELIVERY
SYSTEMS
ANTONIO LOPES, JOS F. ALMEIDA, PAULA FERREIRA, ARMANDO ALCOBIA, MARIA H. GIL ......... 124
THE ACETYLCHOLINESTERASE INHIBITION AND ANTIOXIDANT PROPERTIES OF FENNEL
MARIA EDUARDA M. ARAJO, CARLA PROENA, MRIO NETO, TERESA DUARTE, MARIA LUISA M.
SERRALHEIRO .................................................................................................................................. 125
STUDIES ON SONLO PROPERTIES OF HALF-SANDWICH COMPLEXES USING TD-DFT
CALCULATIONS
TIAGO SILVA, A. J. P. CARVALHO, PAULO J. MENDES ..................................................................... 126
SOLID-LIQUID EQUILIBRIA OF SOME PHARMACEUTICAL COMPOUNDS
FTIMA L. MOTA, ANTNIO J. QUEIMADA, SIMO P. PINHO, EUGNIA A. MACEDO ....................... 127
MULTIPUMPING AND MULTICOMMUTATED REVERSED-FLOW SYSTEMS FOR THE
DETERMINATION OF TRIMIPRAMINE
JOO A. V. PRIOR, DAVID S. M. RIBEIRO, JOO L. M. SANTOS, JOS L. F. C. LIMA ........................ 128
SPECTROPHOTOMETRIC DETERMINATION OF INDAPAMIDE IN A MULTI-PUMPING
FLOW SYSTEM
DAVID S. M. RIBEIRO, JOO A. V. PRIOR, JOO A. LOPES, JOO L. M. SANTOS, JOS L. F. C. LIMA ... 129
INTERACTION OF ENROFLOXACIN WITH OUTER MEMBRANE PROTEIN C (OMPC)
ISABEL SOUSA, HELGE WEINGART, MATHIAS WINTHERHALTER, PAULA GAMEIRO ........................ 130
xxi
VOLTAMMETRIC BIOELECTRONIC TONGUE FOR THE DETERMINATION OF PHENOLIC
COMPOUNDS
GEORGINA M. S. ALVES, ADLIO A. S. C. MACHADO, JLIA M. C. S. MAGALHES ........................ 131
FRIEDEL-CRAFTS ACYLATION OF HETEROAROMATIC COMPOUNDS OVER ZEOLITES
AMADEU F. BRIGAS, BRUNA C. S. SANTOS, VASCO F. D. LVARO, ERIC G. DEROUANE ................. 132
SYNTHESIS AND CHARACTERIZATION OF NOVEL OCTAHEDRAL [FeH(DPPE)
2
(NCR)]
[PF
6
] COMPOUNDS
ANTNIO P. S. TEIXEIRA, ANA FALCO, VNIA F. PAIS, M. PAULA ROBALO, M. HELENA GARCIA 133
SUPRAMOLECULAR CONTROL OF A SOLID STATE [2+2] CYCLOADDITION IN
CARBOXY-SUBSTITUTED TETRATHIAFULVALENE DERIVATIVES
M. TERESA DUARTE, VNIA ANDR, CLAUDIA C. D. SIMO, MARTA MAS-TORRENT, JAUME
VECIANA, CONCEPCI ROVIRA ........................................................................................................ 134
PREPARATION, CHARACTERISATION AND APPLICATION OF ACTIVATED CARBONS
PREPARED FROM DIFFERENT POLYMERS
ISABEL P. P. CANSADO, M. R. CARROTT, P. J. M. CARROTT, F. GONALVES ................................... 135
MERCURY IN SALT MARSHES ECOSYSTEMS: HALIMIONE PORTULACOIDES AS
BIOMONITOR
M. VLEGA, A. I. LILLEB, I. CAADOR M. E. PEREIRA, A. C. DUARTE, M. A. PARDAL ................. 136
REMOO DE BENZO(GHI)PERILENO UTILIZANDO CASCA DE AMNDOA COMO
ADSORVENTE
SOFIA L. SILVA, DIONZIA J. M. CORNLIO, A. ALVES, L. SANTOS .................................................. 137
AVALIAO DA CAPACIDADE DE COMPLEXAO DO CALIX[2]FURANO[2]PIRROL
ATRAVS DE CLCULOS COMPUTACIONAIS
CLUDIA A. TEIXEIRA DOS SANTOS, SHEILA M. F. DOS SANTOS AGUIAR, ALEXANDRE L.
MAGALHES .................................................................................................................................... 138
PREPARATION AND CHARACTERISATION OF NANOSTRUCTURED CARBON AND
SILICA BASED MATERIALS FOR TEXTILE APPLICATIONS
I. ROCHA, T. GALVO, A. G. GONALVES, H. GASPAR, H. ALVES, C. PEREIRA, F. GONALVES, B.
JARRAIS, A. RIBEIRO, A. CARNEIRO, J. MORGADO, M. F. R. PEREIRA, C. FREIRE ............................ 139
NOVO MTODO DE ANLISE DE COMPOSTOS ORGNICOS VOLTEIS (COVS) POR
SPME-GC/MS
VERA HOMEM, RITA ARAJO, JOS LUS MOREIRA, LCIA SANTOS, ARMINDA ALVES .................. 140
METODOLOGIA DE ANLISE DE PESTICIDAS AGRCOLAS POR SPE-LC/MS
RITA ARAJO, VERA HOMEM, LCIA SANTOS, ARMINDA ALVES .................................................... 141
METODOLOGIA DE SCREENING DE CLOROALCANOS C
10-13
E TER
PENTABROMODIFENLICO EM GUAS POR SPME-GC/MS
E. RIBEIRO, JOS LUS MOREIRA, L. SANTOS, A. ALVES .................................................................. 142
DETERMINAO ESPECTROFOTOMTRICA DE NITRATOS EM DIFERENTES TIPOS DE
ALFACE
ANA I. SANTOS, SANDRA FLIX, CRISTINA M. R. R. OLIVEIRA ........................................................ 143
DESIDRATAO DA CEBOLA: INFLUNCIA DAS VARIVEIS DO PROCESSO SOBRE O
PRODUTO FINAL
ANA C. DIAS, MARIA JOO BARROCA, RAQUEL P. F. GUIN ........................................................... 144
CARACTERIZAO QUMICA DO PIMENTO DESIDRATADO POR DIFERENTES
MTODOS
DULCE H. M. COSTA, MARIA JOO BARROCA, RAQUEL P. F. GUIN ............................................... 145
xxii
EVALUATION OF THE ANTIOXIDANT CAPACITY OF EDIBLE WILD MUSHROOMS BY
CYCLIC VOLTAMMETRY
SORAIA FALCO, LILLIAN BARROS, ISABEL C. F. R. FERREIRA, CRISTINA FREIRE, MIGUEL VILAS-
BOAS ................................................................................................................................................ 146
DETERMINAO DO TEOR DE PECTINAS EM DIFERENTES FRUTOS E BEBIDAS
MANUELA M. MOREIRA, LUS F. GUIDO, JOS M. CRUZ, AQUILES A. BARROS ............................... 147
VITAMIN E IN COFFEE BEANS: DEVELOPMENT AND VALIDATION OF A MICRO-
EXTRACTION METHOD
RITA C. ALVES, SUSANA CASAL, BEATRIZ OLIVEIRA ...................................................................... 148
CHEMICAL COMPOSITION AND ANTIOXIDANT ACTIVITY OF FROZEN, DRIED AND
COOKED WILD EDIBLE MUSHROOMS
LILLIAN BARROS, PAULA BAPTISTA, DANIELA M. CORREIA, JORGE S MORAIS, ISABEL C. F. R.
FERREIRA ......................................................................................................................................... 149
EFEITO ANTIPROLIFERATIVO DE FLAVONIDES PRESENTES EM BEBIDAS NUMA
LINHA CELULAR DE CANCRO HUMANO
DANIEL O. CARVALHO, AQUILES A. BARROS, ALEXANDRE DO CARMO, JOS M. CRUZ, LUS F.
GUIDO .............................................................................................................................................. 150
DETERMINATION OF PESTICIDES IN IRRIGATION WATER USING SPE AND GC-ECD
JOS A. N. S. FERREIRA, VALENTINA F. DOMINGUES, NUNO F. C. B. MATEUS, CRISTINA F. DELERUE-
MATOS. ............................................................................................................................................ 151
QUANTIFICATION OF ETHYL ESTERS AND ACETATES IN WINES USING SOLVENTLESS
TECHNIQUES: SBSE AND SPME
ROSA M. PERESTRELO, JOS S. CMARA, JOS M. NOGUEIRA ........................................................ 152
ANALYSIS OF VOLATILES IN COMMERCICAL OLIVE OIL USING LLE/GC-MS AND HS-
SPME/GC-MS
ROSA M. PERESTRELO, CATARINA G. LUS, MICHAEL M. CALDEIRA, JOS C. MARQUES, JOS S.
CMARA .......................................................................................................................................... 153
VOLATILES CHARACTERIZATION OF ANNONA CHERIMOLA MILL. CULTIVARS USING
HS-SPME/GC-MS
LISETH FERREIRA, ROSA M. PERESTRELO, JOS S. CMARA ........................................................... 154
OPTIMIZATION OF MATRIX SOLID PHASE DISPERSION EXTRACTION FOR THE
ANALYSIS OF ISOFLAVONES IN TRIFOLIUM PRATENSE
TATIANA VISNEVSCHI-NECRASOV, SARA C. CUNHA, EUGNIA NUNES, M. BEATRIZ OLIVEIRA ..... 155
DETECTION OF SOYBEAN DNA IN COMMERCIALLY AVAILABLE VEGETABLE OILS
JOANA COSTA, ISABEL MAFRA, JOANA ROCHA, JOANA S. AMARAL, M. BEATRIZ P.P. OLIVEIRA ... 156
QUALITY CONTROL OF FRANKFURT SAUSAGES BY BIOMOLECULAR TECHNIQUES
SNIA SOARES, JOANA S. AMARAL, ISABEL MAFRA, M. BEATRIZ P. P. OLIVEIRA .......................... 157
VALIDATION OF A MSPD METHOD TO ANALYSE ACRYLAMIDE IN FOODSTUFFS BY
GC-MS
CRISTINA M. D. SOARES, JOS O. FERNANDES ................................................................................ 158
DETERMINAO DE AZOTO AMONIACAL EM ALFACES POR DIFERENTES MTODOS
MARTA DUARTE, CRISTINA M. R. R. OLIVEIRA, SANDRA FLIX ..................................................... 159
MOLECULAR MOBILITY AND PHYSICAL AGING ON THE AMORPHOUS PHASE OF
GLUCOSE
JOAQUIM J. MOURA-RAMOS, HERMNIO P. DIOGO ........................................................................... 160
xxiii
OCCURRENCE OF OCHRATOXIN A IN WHEAT BREAD FROM CENTRAL ZONE OF
PORTUGAL: WINTER 2007
SOFIA C. DUARTE, ANA C. TANELLO, CELESTE M. LINO, ANGELINA PENA ..................................... 161
EXTRACO DE ANTIOXIDANTES EM BRCOLOS ATRAVS DE ULTRASSONS
NAIR ALUA, ANABELA RAYMUNDO, M. CELESTE SERRA ................................................................ 162
SINGLE INTERFACE FLOW ANALYSIS LIQUID-LIQUID EXTRACTION. PRELIMINARY
STUDIES
CRISTINA I. C. SILVESTRE, JOO L. M. SANTOS, JOS L. F. C. LIMA ................................................ 163
A SPECIATION METHOD FOR THE DETERMINATION OF THE HYDROXYL CONTENT IN
HYDROXYAPATITE
RICARDO G. SIMES, ANTNIO C. L. CONCEIO, MANUEL E. MINAS DA PIEDADE ....................... 164
SISTEMA DE FLUXO COM CLULA DE PERCURSO OPTICO LONGO PARA A
DETERMINAO DE FERRO EM GUAS
RICARDO N. M. J. PSCOA, ILDIK V. TTH, ANTNIO O. S. S. RANGEL ........................................ 165
UNVEILING CHEMICAL AND PHYSICAL INFORMATION FROM CHEMOMETRICS
MODELS
MAFALDA C. SARRAGUA, ADRIANO FACHINI, JOO A. LOPES ...................................................... 166
DETERMINAO DE DIVERSOS PARMETROS EM GUAS POR ANLISE POR
INJECO SEQUENCIAL
RAQUEL B. R. MESQUITA, ANTNIO O. S. S. RANGEL ..................................................................... 167
DURABILIDADE DE GEOSSINTTICOS EXPOSTOS A AGENTES QUMICOS PROJECTO
GEOCHEM
JOS R. CARNEIRO, PAULO J. ALMEIDA, MARIA L. LOPES ............................................................... 168
MONITORIZAO DE MACRONUTRIENTES EM AMOSTRAS AMBIENTAIS USANDO
ANLISE POR MULTI-SERINGA
M. INS G. S. ALMEIDA, MARCELA A. SEGUNDO, JOS L. F. C. LIMA, ANTNIO O. S. S. RANGEL .. 169
SOLID-PHASE EXTRACTION USING BEAD INJECTION IN LAB-ON-VALVE FORMAT
HUGO M. OLIVEIRA, MARCELA A. SEGUNDO, JOS L. F. C. LIMA, MANUEL MIR, VICTOR CERD ... 170
ESTUDO DA FOTO-DEGRADAO DE GEOTXTEIS DE POLIPROPILENO POR FTIR
INS M. VALENTE , PAULO J. ALMEIDA , JOS R. CARNEIRO , MARIA L. LOPES ............................. 171
DETERMINATION OF COMPOUNDS WITH PHARMACEUTICAL INTEREST BY
OXIDATION REACTIONS USING A SIA SYSTEM
MARIETA L. C. PASSOS, M. LCIA M. F. S. SARAIVA, JOS L. F. C. LIMA ....................................... 172
SISTEMAS DE EXTRACO COM MEMBRANA DESCARTVEL: DETERMINAO DE
ACETALDEDO
J.P. PACHECO, J. A. RODRIGUES A. A. BARROS ............................................................................... 173
DESENVOLVIMENTO DE UM SISTEMA MULTI-COMUTADO PARA A DETERMINAO
DE SO
2
LIVRE E TOTAL
SARA M. OLIVEIRA, TERESA I. M. S. LOPES, ILDIK V. TTH, ANTNIO O.S.S. RANGEL ............... 174
AUTOMATIC FLOW METHODOLOGY FOR METHANOL DETERMINATION IN BIODIESEL
ANDR R. T. S. ARAUJO, M. LCIA M. F. S. SARAIVA, JOS L. F. C. LIMA, M. GRAAS A. KORN .. 175
ADVANCES IN SBSE: NEW POLYURETHANE FOAMS FOR DETERMINATION OF POLAR
POLLUTANTS
FTIMA C. M. PORTUGAL, MOISS L. PINTO, JOO PIRES, J. M. F. NOGUEIRA ................................... 176
xxiv
MICROGRAVIMETRIC QCM AND AFM STUDIES OF THIN FILMS FOR DNA BIOSENSORS
APPLICATIONS
J. F. BORGES, C. M. PEREIRA, A. F. SILVA ....................................................................................... 177
ANLISE DE SISTEMAS COMPLEXOS
J. COSTA PEREIRA, JOANA R. CRUZ OLIVEIRA ................................................................................. 178
ASSEMBLIES OF GOLD NANOPARTICLES PREPARED BY USING SUGARS AS REDUCING
AGENTS
C. P. ARIEIRA, C. M. PEREIRA, A. F. SILVA ...................................................................................... 179
CRITICAL SURVEY ON METHODS FOR IN VITRO EVALUATION OF ANTIOXIDANT
PROPERTIES
MARCELA A. SEGUNDO, LUS M. MAGALHES, SALETTE REIS, JOS L. F. C. LIMA ........................ 180
SISTEMAS DE ANLISE EM FLUXO COM INTERFACE NICA
JOO L.M. SANTOS, C. SILVESTRE, JOS L. F. C. LIMA ................................................................... 181
DETERMINAO DE IO CLORETO EM VINHOS NUM SISTEMA DE FLUXO BASEADO
EM MULTISERINGA
J. RODRIGO SANTOS, MARCELA A. SEGUNDO, JOS L. F. C. LIMA, MAURO KORN .......................... 182
CROMATOGRAFIA INICA DE GUAS DO MAR E DE OUTRAS SOLUES SALINAS
NATASA GROS, FILOMENA CAMES, CRISTINA M. R. R. OLIVEIRA ................................................. 183
MULTI-PUMPING FLOW SYSTEM FOR PHENYLGLYOXYLIC ACID DETERMINATION IN
URINE
KARINE L. MARQUES, JOO L.M. SANTOS, JOS L. F. C. LIMA ....................................................... 184
SENSOR FOR AMPEROMETRIC DETERMINATION OF AMMONIA IN SEAWATER
C. PEIXE, C. M. PEREIRA, F. SILVA, M-T BORGES ........................................................................... 185
ELECTRONIC TONGUE FOR QUALITATIVE AND QUANTITATIVE ANALYSIS OF DRINKS
JLIA M. C. S. MAGALHES, CLAUDIA SILVA, ADLIO A. S. C. MACHADO .................................... 186
DETERMINATION OF VANADIUM (V) IN WATER SAMPLES BY SEQUENTIAL INJECTION
ANALYSIS
ELIANA S. SILVA, PAULA C. A. G. PINTO, M. LCIA M. F. S. SARAIVA, JOS L. F. C. LIMA ............ 187
SISTEMAS DE FLUXO CONTNUO BASEADOS EM NOVOS CONCEITOS DE GESTO DE
FLUDOS
MARTA F. T. RIBEIRO, JOO L. M. SANTOS, JOS L. F. C. LIMA ...................................................... 188
DETERMINAO DE METAIS PESADOS EM COSMTICOS
MANUEL MATOS, SOFIA P. M. GONALVES, SUSANA I. E. SILVA, NELSON A. F. SILVA, HUGO F. A.
SILVA ............................................................................................................................................... 189
PRODUO DE PADRES PARA ANLISE DE METAIS PESADOS EM AEROSSIS
PRO M. P. PEDROSO, HUGO F.A. SILVA, SANDRINA OLIVEIRA, PAULA CANTINHO, CRISTINA
OLIVEIRA, FILOMENA CAMES, MANUEL MATOS ........................................................................... 190
DEVELOPMENT OF A HPLC-DAD METHODOLOGY FOR ANTIBIOTICS SCREENING IN
WASTEWATERS
SALOM TEIXEIRA, CRISTINA DELERUE-MATOS, ARMINDA ALVES
,
LCIA SANTOS ....................... 191
DETERMINAO DA DISTNCIA DE DISPARO DE ARMAS DE FOGO ATRAVS DA
ANLISE DOS RESDUOS NA SUPERFCIE DE IMPACTO
JOANA M. F. TUNA, AGOSTINHO A. ALMEIDA, AGOSTINHO J. C. SANTOS, TERESA M. S. MAGALHES,
MARISA C. F. SILVA, SNIA M. MARTINS ........................................................................................ 192
xxv
RUBDIO VS POTSSIO NO HUMOR VTREO COMO PARMETRO ANALTICO PARA
ESTIMAR O TEMPO DECORRIDO APS A MORTE
CATARINA A. S. CHAVES, AGOSTINHO A. ALMEIDA, M. HELENA A. T. ANDRADE, AGOSTINHO J. C.
SANTOS, TERESA M. S. MAGALHES, SOFIA M. L. M. FRAZO, DANIELA P. MONTEIRO, SUSANA F.
CRUZ ................................................................................................................................................ 193
IRON (II) OPTRODE BASED ON THIONINE IMMOBILIZED ON A SOL-GEL NET
JOANA A. E. CARVALHIDO, ALBERTO N. ARAJO, M. CONCEIO B. S. M. MONTENEGRO ............ 194
MTODO MULTIRESDUO PARA ANLISE DE PESTICIDAS AGRCOLAS EM GUAS POR
EXTRACO EM FASE SLIDA COM DETECO POR GC-MS
JOS LUS MOREIRA, MARIA DE FTIMA FERREIRA, SERAFIM PEREIRA, ARMINDA ALVES ............. 195
CARACTERIZAO DOS LENHOSULFONATOS OBTIDOS A PARTIR DO LICOR DE
COZIMENTO AO SULFITO CIDO DO EUCALYPTUS GLOBULUS
ANA P. S. MARQUES, D. V. EVTUGUIN, A. PRATES .......................................................................... 196
SNTESE E CARACTERIZAO DE COMPLEXOS ORGANOMETLICOS COM
HETEROCICLOS - IV
J. L. FERREIRA DA SILVA, A. ROMO DIAS, A. P. FERREIRA, P. T GOMES, M. M. SALEMA ............. 197
METAL-NSAID COORDINATION: STUDY OF INTERACTIONS BETWEEN IBUPROFEN
AND BIOLOGICALLY ACTIVE METALS
ELISABETE OLIVEIRA, TIAGO SILVA, LUZ FERNANDES, HUGO SANTOS, TERESA AVILS, JOS LUIS
CAPELO, CARLOS LODEIRO .............................................................................................................. 198
SYNTHESIS OF COORDINATION COMPOUNDS WITH 2-MERCAPTONICOTINIC ACID
AND 1,10-PHENANTHROLINE
PENKA I. GIRGINOVA, LUS CUNHA-SILVA, FILIPE A. A. PAZ, HELENA I. S. NOGUEIRA, JOO ROCHA,
VTOR AMARAL, TITO TRINDADE .................................................................................................... 199
CHARACTERIZATION OF BIONANOPROBES FROM CYTOCHROME C/ GOLD
NANOPARTICLES COMPLEXES
INS GOMES, NUNO C. SANTOS, LUS M. A. OLIVEIRA, ALEXANDRE QUINTAS, PETER EATON,
RICARDO FRANCO ............................................................................................................................ 200
STUDY OF THE EFFECT OF THE R GROUP IN CC BOND RUPTURE PROMOTED BY CUCL
IN CAMPHOR ALKYNES
M. FERNANDA N. N. CARVALHO, TIAGO A. FERNANDES, RUDOLF HERRMANN .............................. 201
NEW RHENIUM (III) COMPLEXES BEARING WATER SOLUBLE LIGANDS
GONALO J. O. C. LOPES, PIOTR SMOLESKI, ELISABETE C. B. A. ALEGRIA, LUSA M. D. R. S.
MARTINS, ARMANDO J. L. POMBEIRO .............................................................................................. 202
SYNTHESIS OF ZnO/POLY-{TRANS-[RuCl
2
(VPY)
4
]/STY} NANOCOMPOSITES
KAREN SEGALA, ROSILENE L. DUTRA, CSAR V. FRANCO, ANGELA S. PEREIRA, MANUEL A.
MARTINS, PROTIMA RAUWEL, TITO TRINDADE ............................................................................... 203
SNTESE E CARACTERIZAO DE COMPLEXOS DE FERRO(II) E RUTNIO(II) COM
LIGANDOS NITRILO E ACETILETO: POTENCIAIS FIOS MOLECULARES?
V. PACHECO, S. SOARES, M. P. ROBALO, M. FTIMA M. PIEDADE .................................................. 204
INFLUENCE OF THE PREPARATION METHOD IN FINAL PRODUCTS OF THE SERIES
CO
X
Fe
3-X
O
4
(X = 1; 2)
TERESA FERREIRA, M. HELENA MENDONA, FERNANDA M.A. COSTA ........................................... 205
ANISOTROPIC GOLD NANOPARTICLES: A CONTROLLED APPROACH TO OBTAIN
NANOTRIANGLES
MARIA ADELAIDE MIRANDA, PATRCIA A. CARVALHO, PETER EATON, BALTAZAR DE CASTRO,
EULLIA PEREIRA ............................................................................................................................ 206
xxvi
UV-Vis-NEAR-IR AND EPR STUDIES OF METAL COMPLEXES OF 15-MEMBERED
MACROCYCLES
N. TORRES, M. F. CABRAL, J. COSTA, R. DELGADO ......................................................................... 207
N-ALKYLOXYSULFAMOYLPHENYLPORPHYRINS: SYNTHESIS AND PHOTODYNAMIC
EFFECT AGAINST COLON CARCINOMA CELLS
A. C. SERRA, NELSON A. M. PEREIRA, M. PINEIRO, A. M. DA. ROCHA GONALVES, M. ABRANTES,
M. LARANJO, A. C. SANTOS, M. F. BOTELHO ................................................................................... 208
FUNCTIONAL DESYMMETRIZATION OF 1,3-DIOXIMES FOR THE OBTENTION OF 1,2,3-
TRISUBSTITUTED CARBOCYCLES
VALDEMAR B. C. FIGUEIRA, ARANTXA G. ESQU, SUNDARESAN PRABHAKAR, ANA M. LOBO ...... 209
ESTUDO QUMICO DA BULNESIA SARMIENTOI
SNIA C. NABAIS, JESUS M. RODILLA, CARLA GAIOLAS, ARLINDO GOMES, LCIA SILVA ............. 210
SYNTHESIS OF NEW PUSH-PULL (OLIGO)THIENYL-BENZOXAZOLES AS EFFICIENT NLO
CHROMOPHORES
ROSA M. F. BATISTA, SUSANA P. G. COSTA, MICHAEL BELSLEY, M. MANUELA M. RAPOSO .......... 211
SYNTHESIS OF SULFONAMIDE HALOGENATED PORPHYRINS AND K
OW
EVALUATION
CARLOS J. P. MONTEIRO, MARIETTE M. PEREIRA, SARA M. A. PINTO, ANA V. C. SIMES, GONALO
F. F. S, LUS G. ARNAUT, SEBASTIO J. FORMOSINHO, SRGIO SIMES ........................................ 212
SNTESE DE NOVOS IMIDAZOLIL[1,2,4]TRIAZOLES
SANDRA M. NOBRE, A. SOFIA VILA-CH, ALICE M. DIAS, M. F. PROENA .................................... 213
CALIX[4]ARENE -BASED POLYMERS: HOMO AND COPOLYMERIZATION WITH
CARBAZOLE DERIVATIVES
PATRCIA D. BARATA, ALEXANDRA I. COSTA, JOS V. PRATA ........................................................ 214
SYNTHESIS OF SINGLE BRIDGED DOUBLE CALIX[4]ARENES
ALEXANDRA I. COSTA, JOS V. PRATA ............................................................................................ 215
COMPLEXAO DE IES LANTANDEOS POR DERIVADOS HOMOOXACALIXARENOS
CONTENDO O GRUPO CARBONILO
PAULA M. MARCOS, JOS R. ASCENSO, MANUEL A. P. SEGURADO ................................................. 216
NEW HYDROXYPYRIMIDINONE-SULFONAMIDES AS BI-TARGET LIGANDS FOR
ENZYME INHIBITION
M. ALEXANDRA ESTEVES, OSVALDO ORTET, ANABELA CAPELO, SRGIO M. MARQUES, CLAUDIU
SUPURAN, M. AMLIA SANTOS ........................................................................................................ 217
o,o-DIALKYL GLYCINES DIPEPTIDES OBTAINED FROM UGI REACTION PRODUCTS
ANA MARIA F. SILVA, SLVIA M. M. A. PEREIRA-LIMA ................................................................... 218
REACTIVITY OF C-VINYL-1H-PYRROLES
MARIA I. L. SOARES, SUSANA M. M. LOPES, TERESA M. V. D. PINHO E MELO ...................................... 219
SNTESE DE DERIVADOS DIPEPTDICOS DE FRMACOS CONTENDO O GRUPO AMIDA
JOANA MATOS, PAULA GOMES ........................................................................................................ 220
ELECTROCHEMICAL EVALUATION OF THE REDOX-PROPERTIES OF DIARYLAMINES
IN THE 2,3-DIMETHYLBENZO[B]THIOPHENE SERIES
SORAIA FALCO, RUI M. V. ABREU, ISABEL C. F. R. FERREIRA, MIGUEL VILAS-BOAS, MARIA-JOO
R. P. QUEIROZ .................................................................................................................................. 221
DOCKING STUDIES OF INDOMETHACIN DERIVATIVES IN CYCLOOXYGENASE-2
BINDING SITE
ANA M. D. RAMOS, A. GIL SANTOS, EURICO J. CABRITA, MARIA M. B. MARQUES ......................... 222
xxvii
SYNTHESIS AND CHARACTERIZATION OF A PGN MONOMER WITH BIOLOGICAL
INTEREST
LUSA R. CARVALHO, SRGIO R. FILIPE, M. M. PEREIRA, MARIA M. B. MARQUES ........................ 223
SYNTHESIS OF AN INDOLE LIBRARY AND EVALUATION OF ITS IN VITRO
ANTIOXIDANT ACTIVITY
MNICA S. ESTEVO, ANA GOMES, EDUARDA FERNANDES, LUSA P. FERREIRA, MARIA M. B.
MARQUES......................................................................................................................................... 224
AVALIAO DA INTERACO DO IBUPROFENO E DA INDOMETACINA COM MODELOS
MEMBRANARES
DIANA GASPAR, KERSTIN WAGNER, GERALD BREZESINSKI, JOS L. F. C. LIMA, MARLENE LCIO,
SALETTE REIS .................................................................................................................................. 225
ESTUDO DA ACTIVIDADE E INIBIO DA FOSFOLPASE A2 POR ACO DO
MELOXICAM
SALETTE REIS, DIANA GASPAR, M. LCIA M. F. S. SARAIVA, JOS L. F. C. LIMA, MARLENE LCIO .. 226
INTERACTION OF NSAIDS WITH DMPC LIPOSOMES: STUDIES OF PARTITION,
LOCATION AND MEMBRANE FLUIDITY
CLUDIA NUNES, DIANA GASPAR, KATARZYNA GOBSKA, MICHA WINIEWSKI, JOS L. F. C.
LIMA, SALETTE REIS, MARLENE LCIO ........................................................................................... 227
INTRAMOLECULAR HYDROGEN BONDING IN 4-AMINO-3,5-DI-PIRYDYL-4H-1,2,4-
TRIAZOLE CRYSTALS
JOANA A. SILVA, CLUDIA T. ARRANJA, ANA F. P. V. FERREIRA, NUNO D. MARTINS, MANUELA R.
SILVA, ANA MATOS BEJA, ABLIO J. F. N. SOBRAL.......................................................................... 228
CRYSTAL STRUCUTRE CHARACTERIZATION OF ETHYL 3,5-DIMETHYL-1H-PYRROLE-2-
CARBOXYLATE
CLUDIA T. ARRANJA, JOANA A. SILVA, ANA F. P. V. FERREIRA, MANUELA R. SILVA, ANA MATOS
BEJA, ABLIO J. F. N. SOBRAL .......................................................................................................... 229
NEW INDAZOLE AND CONDENSED PYRAZOLE BISPHOSPHONATES
FTIMA C. TEIXEIRA, CARLA LUCAS, INS F. ANTUNES, M. JOO M. CURTO, M. NEVES, M. TERESA
DUARTE, VNIA ANDR .................................................................................................................. 230
ESTUDO TERMOQUMICO DE DERIVADOS DO NITROTIOFENO
ANA FILIPA L. O. M. SANTOS, MANUEL A. V. RIBEIRO DA SILVA ................................................... 231
TERMOQUMICA DOS COMPOSTOS 5-BROMOINDOLE E 5-BROMOINDOLINA
JOANA I. T. A. CABRAL, MANUEL A. V. RIBEIRO DA SILVA ............................................................. 232
CHEMICAL CALIBRATION OF ISOTHERMAL TITRATION CALORIMETERS: A TEST
REACTION AT 308.15 K
R. ADO, G. BAI, R. SASSONIA, W. LOH, M. BASTOS ...................................................................... 233
APPLICATION OF GENETIC ALGORITHMS IN CHEMISTRY: FROM FITTING THE
POTENTIAL ENERGY TO THE STUDY OF CLUSTERS
JORGE M. C. MARQUES, FRANCISCO B. PEREIRA ............................................................................. 234
METASTABLE ZONE WIDTH FOR THE CRYSTALLIZATION OF NICOTINIC ACID FROM
WATER
ELSA M. GONALVES, MANUEL E. MINAS DA PIEDADE .................................................................. 235
ESTUDO TERMOQUMICO DE ALGUNS DERIVADOS DO FURANO
LUSA M. P. F. AMARAL, MANUEL A. V. RIBEIRO DA SILVA ........................................................... 236
THERMOCHEMISTRY OF DIHYDROXYBENZOIC ACID ISOMERS
MARIANA VIDINHA, MARIA D. M. C. RIBEIRO DA SILVA, MANUEL J. S. MONTE ..................................... 237
xxviii
FIRST HYPERPOLARIZABILITY OF SOME NICKEL-ACETYLIDE COMPLEXES: A DFT
STUDY
ANA BARROCAS, PAULO J. MENDES, A. J. P. CARVALHO ................................................................ 238
MONOCYCLOPENTADIENYLRUTHENIUM COMPLEXES FOR SECOND-ORDER NLO
PURPOSES
PAULO J. MENDES, M.H. GARCIA, M. P. ROBALO ............................................................................ 239
ROTATIONAL MOTION OF FULLERENE C
70
DERIVATIVES FROM FLUORESCENCE
ANISOTROPY MEASUREMENTS
FILIPE MENEZES, ALEXANDER A. FEDOROV, CARLOS BALEIZO, MRIO N. BERBERAN-SANTOS ...... 240
ENERGETICS OF THE FORMATION OF CALCIUM PHOSPHATE NANOPARTICLES
MIROSLAV LESKIV, ANA L. C. LAGOA, HENNING URCH, JANINE SCHWIERTZ, MANUEL E. MINAS DA
PIEDADE, MATTHIAS EPPLE ............................................................................................................. 241
CH BOND DISSOCIATION ENTHALPIES IN NORBORNANE
PAULO M. NUNES, SLVIA G. ESTCIO, GUSTAVO T. LOPES, BENEDITO J. COSTA CABRAL, RUI M.
BORGES DOS SANTOS, JOS A. MARTINHO SIMES ......................................................................... 242
THERMODYNAMIC STUDY OF ANTITUBERCULOSTATIC DRUGS
ALFA U. S, GUANGYUE BAI, FILIPA ABRUNHOSA MARGARIDA BASTOS ....................................... 243
THE ELECTRICAL DOUBLE LAYER AT THE BMIMPF
6
IONIC LIQUID/SOLID ELECTRODE
INTERFACE
CRISTIANA GOMES, ANA MARTINS, FERNANDO SILVA .................................................................... 244
CALCULATING CONVENTIONAL STRAIN ENERGIES IN PARENT MOLECULES AND
THEIR RADICALS
RUI M. BORGES DOS SANTOS, FILIPE AGAPITO, PAULO M. NUNES, BENEDITO J. COSTA CABRAL, JOS
A. MARTINHO SIMES ..................................................................................................................... 245
TRANS CINNAMIC ACID DERIVATIVES INCLUDED IN CYCLODEXTRINS: A RAMAN
SPECTROSCOPIC STUDY
MARIELA M. NOLASCO, ANA M. AMADO, PAULO A. RIBEIRO-CLARO ............................................ 246
A QSAR STUDY OF ANTITUBERCULAR THIOBENZANILIDE DERIVATIVES: PREDICTION
OF LIPOPHILICITY
SUSANA M. BORGES, JOO MANSO, CRISTINA VENTURA, SUSANA SANTOS, FILOMENA MARTINS . 247
THE INFLUENCE OF AROMATIC SUBSTITUENTS ON THE SOLVOLYSIS OF TERTIARY
ALKYL HALIDES: A GRUNWALD-WINSTEIN ANALYSIS
MARINA REIS, LUS MOREIRA, RUBEN LEITO, FILOMENA MARTINS ............................................. 248
TRENDS IN CH BOND DISSOCIATION ENTHALPIES: DELOCALIZATION,
CONJUGATION, AND STRAIN
FILIPE AGAPITO, PAULO M. NUNES, BENEDITO J. COSTA CABRAL, RUI M. BORGES DOS SANTOS, JOS
A. MARTINHO SIMES ..................................................................................................................... 249
ENERGETIC AND CONFORMATIONAL CHANGES OF CYP3A4 FOLLOWING CO
HOMOLYSIS
ANA FRANGOLHO, PAULO M. NUNES, VTOR H. TEIXEIRA, PAULO J. MARTEL, LUS F. M. ROSA,
GUILHERME N. M. FERREIRA, RUI M. BORGES DOS SANTOS ........................................................... 250
ION SPECIFIC EFFECTS IN THE LIQUID-LIQUID PHASE EQUILIBRIA BETWEEN WATER
AND IONIC LIQUIDS
MARA G. FREIRE, PEDRO J. CARVALHO, LUS M. N. B. F. SANTOS, LUS P. N. REBELO, J. A. P.
COUTINHO, I. M. MARRUCHO .......................................................................................................... 251
xxix
SURFACE TENSION MEASUREMENTS OF HYDROPHILIC IONIC LIQUIDS AQUEOUS
SOLUTIONS
MARA G. FREIRE, JOO A. P. COUTINHO, JOS N. CANONGIA LOPES, LUS P. N. REBELO, ISABEL M.
MARRUCHO ...................................................................................................................................... 252
THEORETICAL STUDY OF THE HOOH (X,
1
A) POTENTIAL ENERGY SURFACE
DANIELA V. COELHO, JOO BRANDO ............................................................................................ 253
HO
2
POTENTIAL ENERGY SURFACE WITH SPECTROSCOPIC ACCURACY: DMBE IV-M
JOO BRANDO, JONATHAN TENNYSON, CAROLINA M. A. RIO ...................................................... 254
STRUCTURE EFFECTS ON THE INTERACTION OF PHENOLIC ACIDS WITH DNA
JOANA VITORINO, M. J. SOTTOMAYOR ............................................................................................ 255
ESTUDO TERMOQUMICO, EXPERIMENTAL E TERICO, DE ALGUMAS HIDROXI-
TETRALONAS
CLARA C. S. SOUSA, M. AGOSTINHA R. MATOS, VICTOR M. F. MORAIS ......................................... 256
IMPORTANCE OF GLUCOSE FOR HUMAN NEUTROPHILS OXIDATIVE BURST IN VITRO
MARISA FREITAS, GRAA PORTO, JOS L. F. C. LIMA, EDUARDA FERNANDES........................................ 257
REDUCTASES DE LEVEDURAS - BIOMARCADORES DE STRESS PELO VANDIO E
ISOPROTURO
SARA GONALVES, MARTA CANDEIAS, ANA CONIM, TNIA ROSADO, ISABEL ALVES-PEREIRA, RUI
FERREIRA ......................................................................................................................................... 258
ANTIOXIDANT ACTIVITY OF PORTUGUESE HONEY SAMPLES
EDMUR AIRES, ISABEL C. F. R. FERREIRA, LETCIA M. ESTEVINHO ................................................. 259
ANTIOXIDANT ACTIVITY OF NON STEROIDAL ANTI-INFLAMATORY DRUGS
ANTIPIRYNE AND DERIVATIVES
ABEL VIEIRA, PEDRO SANTOS, ALEXANDRA ANTUNES, JOO NORONHA, EDUARDA FERNANDES ...... 260
INOVAO NA INDSTRIA QUMICA
HETEROGENEIZAO DE COMPLEXOS DE COORDENAO DE ALPHA DIIMINAS DE
NIQUEL PARA A POLIMERIZAO DE ETILENO
INS MATOS, ISABEL FONSECA, ANA M. BOTELHO DO REGO, M. A. N. D. A. LEMOS, AUGUSTE
FERNANDES, RITA CATALO, FRANCISCO LEMOS, MARIA M. MARQUES ........................................ 261
OXIDAO SELECTIVA DE GLICEROL CATALISADA POR METAIS NOBRES EM
CARVO ACTIVADO
E. G. RODRIGUES, O. S. G. P. SOARES, S. A. C. CARABINEIRO, F. GONALVES, M. F. R. PEREIRA, J. L.
FIGUEIREDO, J. J. M. RFO ............................................................................................................ 262
DEGRADAO FOTO-OXIDATIVA DO TERPOLMERO ACRILONITRILO-BUTADIENO-
ESTIRENO
RAQUEL M. SANTOS, GABRIELA L. BOTELHO, ANA V. MACHADO, JORGE S. CONDUTO ................. 263
SPECTRAL AND PHOTOPHYSICAL STUDIES OF SUBSTITUTED INDIGO DER. IN THEIR
LEUCO FORMS
RAQUEL RONDO, J. SEIXAS DE MELO, M. J. MELO, G. VOSS ......................................................... 264
APPLICATION OF BIOPOLYMER AGAR TO GREEN PACKAGING AND COATING
ANA M. M.SOUSA, RONALD D. VILLANUEVA, LOIC HILLIOU, MARIA P. GONALVES .................... 265
GOLD ON MAGNETITE NANOPARTICLES: GROWTH TO A CORE-SHELL SYSTEM
PEDRO QUARESMA, PETER EATON, RICARDO FRANCO, PATRCIA CARVALHO, JOO PEDRO ARAUJO,
PEDRO BAPTISTA, EULLIA PEREIRA ............................................................................................... 266
xxx
MORDANT ION INFLUENCE IN COLOUR HUE AND PHOTODEGRADATION OF WOOL
DYED FIBERS
VANESSA PIMENTA, ANA MANHITA, HELENA VARGAS, ISABEL RIBEIRO, TERESA PACHECO, JOS
MIRO, CRISTINA T. DA COSTA, ANTNIO CANDEIAS, TERESA FERREIRA ...................................... 267
TEORES DE VITAMINA E EM DIFERENTES VARIEDADES DE CASTANEA SATIVA
JOO C. M. BARREIRA, RITA C. ALVES, SUSANA CASAL, ISABEL C. F. R. FERREIRA, JOS ALBERTO
PEREIRA, M. BEATRIZ P. P. OLIVEIRA .............................................................................................. 268
IMPROVED CHROMATOGRAPHIC METHODOLOGIES FOR FOOD CONTROL MARKERS
OF QUALITY
ELVIRA M. GASPAR, JOO F. LOPES, ANA F. LUCENA ..................................................................... 269
MDULO DE EXTRACO SEM MEMBRANA: APLICAO ANLISE DE SO
2
EM VINHO
M. F. ANUNCIAO, J. P. PACHECO, J. A. RODRIGUES, A. A. BARROS ............................................. 270
DETERMINATION OF H
2
O
2
BY FLOW INJECTION ANALYSIS BASED ON TITANIUM
PEROXIDE COMPLEX
JOANA RIBEIRO, MARCELA A. SEGUNDO, SALETTE REIS, JOS L. F. C. LIMA.................................. 271
SINGLE-STANDARD CALIBRATION IN SIA ANALYTICAL SYSTEMS
LEONEL G. C. SOARES, RUI A.S. LAPA ............................................................................................ 272
TECNOLOGIA CAD/CAM APLICADA AO DESENVOLVIMENTO DE SISTEMAS DE FLUXO
EUNICE R. G. O. RODRIGUES, M. GABRIELA T. C. RIBEIRO, RUI A. S. LAPA ............................................ 273
BENZOYLDIAZENIDO-Re(III) AND OXO-Re(V) COMPLEXES BEARING N,N- AND N,O-
TYPE LIGANDS
ARLINDA FURTADO, CATARINA TRAVASSOS, ALEXANDER M. KIRILLOV, M. FTIMA C. GUEDES DA
SILVA, LUSA M.D.R.S. MARTINS, ELISABETE C.B.A. ALEGRIA, ARMANDO J.L. POMBEIRO .......... 274
SILVER NANOWIRES: PHOTOCATALYTIC SYNTHESIS AND CHARACTERIZATION
INS V. OSRIO, ADELAIDE MIRANDA, PATRCIA A. CARVALHO, EULLIA PEREIRA...................... 275
CHIRAL JACOBSEN COMPLEXES IMMOBILISED IN PILLARED CLAYS
HELENA ALVES, JOO PIRES, MARTA ANDRADE, ANA P. CARVALHO, CLARA PEREIRA, SUSANA L. H.
REBELO, CRISTINA FREIRE ............................................................................................................... 276
ESTUDO TERMOQUMICO DOS TRS ISMEROS DO MONOCLORONITROBENZENO
ANA I. M. C. LOBO FERREIRA, ANA R. G. MORENO, MANUEL A. V. RIBEIRO DA SILVA ................. 277
INOVAO NO ENSINO DA QUMICA E DA ENGENHARIA QUMICA
INVESTIGAO NOS ENSINOS SUPERIOR-SECUNDRIO: UMA EXPERINCIA EM
QUMICA INORGNICA
A. PONTINHA, V. PACHECO, L. MARTINS ......................................................................................... 278
ESTRELA VERDE: UMA MTRICA DE VERDURA
M. G. T. C. RIBEIRO, D. A. COSTA, B. FARIA, A. NEVES, A. A. S. C. MACHADO ............................. 279
TEATRO CIENTFICO: ALGUNS DADOS SOBRE O IMPACTO DA PEA OXIGNIO NOS
ALUNOS
CLUDIA C. SARAIVA, M. JOO MONTE, J. C. PAIVA ...................................................................... 280
A AVENTURA, O MISTRIO E A QUMICA
MARTA PINHEIRO, JOO P. LEAL ..................................................................................................... 281
TCNICAS ANALITICAS APLICADAS AO ESTUDO DE PIGMENTOS DO SCULO XIX E
SUA CONTRIBUIO PARA O ENSINO
MARIA F. ANTNIO, F. M. COSTA .................................................................................................... 282
xxxi
CONTEXTUALIZAO CURRICULAR EM TABELAS PERIDICAS DIGITAIS
FLORA M. B. FERREIRA, JOO C. PAIVA .......................................................................................... 283
CONTRIBUIES DA FILOSOFIA DA QUMICA PARA UMA DIDTICA DA QUMICA
MARCOS ANTONIO PINTO RIBEIRO, TATIANA GONALVES SARDINHA, HYRLAM SOUZA FERREIRA ... 284
PORTUGUESE PARTICIPATION IN CROSSNET: EQUILIBRACTION - THE NATIONAL
PROJECT
SUSANA FONSECA, JOO PAIVA, ANTNIO FERREIRA, JOO VALE ................................................. 285
BIOCOMBUSTVEIS
SNIA J. ROCHA, DIOGO A. M. M. G. ROCHA, FREDERICO A. R. B. JUNQUEIRA, JOO A. S. SARAIVA,
MAFALDA P. S. RAMOS, RICARDO S. BESSA, RUI P. C. CARVALHO ................................................. 286
PROTOCOLOS EXPERIMENTAIS YOUTUBE
MANUEL MATOS, MARGARIDA PORTUGAL, SRGIO P. COSTA, HUGO F.A. SIVA, NELSON A.F. SILVA,
PEDRO L. GALEGO, ALDA M. CARMO, ALICE R. CATARINO, ISABEL B. GODINHO, NAIR N. ALUA,
CELESTE M. SERRA .......................................................................................................................... 287
MICROSCOPIA QUMICA E CRISTAIS: UMA REVOLUO CULTURAL EM CURSO
CLEMENTINA TEIXEIRA .................................................................................................................... 288
O MODELO DA ESFERA RGIDA EM FOLHA DE CLCULO: DA TETRA
NONACOORDENAO
MRIO VALENTE, HELENA MOREIRA .............................................................................................. 289
DA FLORESTA FOLHA DE PAPEL EXPLORANDO O PROCESSO DO PONTO DE VISTA
PEDAGGICO
PATRCIA FIAL, JORGE PINHEIRO, ARLINDO GOMES, LCIA SILVA, ................................................. 290
A FILOSOFIA DA QUMICA, O DISCURSO QUMICO E A EDUCAO QUMICA
DUARTE COSTA PEREIRA ................................................................................................................. 291
TEORIA CONSTRUCTAL PARA O ENSINO DA QUMICA E DA ENGENHARIA QUMICA
LUS M. P. HORTA ............................................................................................................................ 292
NOMENCLATURA DOS ELEMENTOS QUMICOS
M. CLARA F. MAGALHES, JOS A. L. COSTA, ROBERTO B. FARIA, M. HELENA GARCIA, RUI T.
HENRIQUES, BERNARDO J. HEROLD, ADLIO A. S. C. MACHADO, JOAQUIM MARALO, OSVALDO A.
SERRA .............................................................................................................................................. 293
CRIAO DE AULAS MULTIMDIA: O DOCENTE SOZINHO OU COM A AJUDA DE UM
INFORMTICO
MARIA F. SIMES, MARIA ISABEL ISMAEL, JOO L. BELO............................................................... 294
A CONSTRUO DO CUBO
JAIME F. B. PUNA, BRULIO S. BAPTISTA ........................................................................................ 295
CONSTRUO E EXPLORAO DIDCTICA DE CALORMETROS
JOS A. L. COSTA, GUIDA M. M. BASTOS, M. CLARA F. MAGALHES ............................................ 296
OPTIMIZAO DE UM MTODO DE HPLC PARA DETERMINAO DE ADITIVOS
ALIMENTARES
ELSA PEREIRA, CELESTE SERRA, LUSA OLIVEIRA, ELSA VASCO .................................................... 297
A QUMICA ANALTICA, NAS PGINAS DE O INSTITUTO, NA SEGUNDA METADE DO
SCULO XIX
ANTNIO J. F. LEONARDO, DCIO R. MARTINS, CARLOS FIOLHAIS ................................................. 298

xxxii
INNOVATION IN COOKING CHEMISTRY HAS A DECISIVE ROLE
PAULINA MATA, JOANA MOURA, MARGARIDA GUERREIRO, CATARINA PRISTA, MARIA LOUREIRO
DIAS ................................................................................................................................................. 299
DESENVOLVIMENTO DE UM LABORATRIO REMOTO COM APLICAO NO ENSINO
DA QUMICA
M. GABRIELA T. C. RIBEIRO, EUNICE R. G. O RODRIGUES, RUI A. S. LAPA............................................. 300
MEDIO DA DENSIDADE DE LQUIDOS UTILIZANDO O MTODO DO PICNMETRO
ELSA BATISTA, NELSON ALMEIDA, EDUARDA FILIPE ...................................................................... 301
FERRAMENTA WEB PARA O CLCULO DE ESTADOS VIBRACIONAIS EM TEMPO REAL
JOO P. M. POIARES, SRGIO P. J. RODRIGUES, JORGE M. C. MARQUES ......................................... 302
SOLUES PADRO PARA REFRACTMETROS, INSTRUMENTO DE MEDIO DO TEOR
DE ACARES DOS MOSTOS DE UVAS
MARIA DO CU FERREIRA, ANDREIA FURTADO, OLIVIER PELLEGRINO ........................................... 303
BOMBAS FOTNICAS DE PROTES: A LUZ COMO UM CIDO
LUS G. ARNAUT, M. PINEIRO, RUI NUNES ...................................................................................... 304
KUROMANIN: EFFECTS OF SOLVENT COMPOSITION ON PROTONATION-
DEPROTONATION & ON COLOUR
I. B. COUTINHO, J. C. LIMA, A. L. MAANITA .................................................................................. 305
2-PHENYL-1-PYRROLINE AND ITS CATALYTIC DEHYDROGENATION TO 2-
PHENYLPYRROLE
CLUDIA A. FIGUEIRA, CLARA S. B. GOMES, SNIA A. CARABINEIRO, M. TERESA DUARTE, PEDRO T.
GOMES ............................................................................................................................................. 306
PRODUCTION OF BIODIESEL USING HETEROGENEOUS ACID CATALYSTS
MARIA J. SAMPAIO, HELDER T. GOMES ........................................................................................... 307
CARBON SUPPORTED COBALT CATALYST FOR ALCOHOL OXIDATION WITH
MOLECULAR OXYGEN
JUNJIANG ZHU, JOS L. FIGUEIREDO, JOAQUIM L. FARIA ................................................................ 308
PREPARATION OF FAUJASITE MEMBRANES
ANDREIA F. G. MACHADO, ZHI LIN, TITO TRINDADE, MIGUEL TEIXEIRA, ADLIO MENDES, MIGUEL
MADEIRA, JOS SOUSA .................................................................................................................... 309
WORKSHOPS
CONCEPO E UTILIZAO DE RECURSOS MULTIMDIA PARA O ENSINO DA
QUMICA
CARLA MORAIS ................................................................................................................................ 313
KIT DE ANLISE DE PLSTICOS. ISSO RESULTA...?
ANTNIO J. M. A. FERREIRA ............................................................................................................ 314
"A AULA DO DIA SEGUINTE..."
RICARDO SILVA, MANUEL SILVA PINTO .......................................................................................... 315
NDICE DE AUTORES 319






PRMIO
FERREIRA DA SILVA


MY SCIENTIFIC JOURNEY: EXPLORING
PHOTOCHEMISTRY FROM MILLISECONDS TO
PICOSECONDS

Slvia Marlia de Brito Costa*
Centro de Qumica Estrutural, Complexo 1, Instituto Superior Tcnico, Universidade
Tcnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
*sbcosta@mail.ist.utl.pt

Important primary photochemical processes such as electron transfer, energy
transfer, proton transfer, dissociation and isomerization reveal interesting
dynamic aspects concerning the behaviour of simple molecules, molecular
aggregates and supramolecules.
Over the last thirty five years, the focus of research in Molecular
Photochemistry, in the Group I have been directing in CQE, has centred in
photoinduced electron transfer processes, progressing from intermolecular or
intramolecular systems in solution, to molecular aggregates micelles, reverse
micelles, vesicles and Langmuir Blodgett films. In these systems a
photochemical or photophysical reporter (fluorescent or phosphorescent probe)
was always incorporated. More recently, complex supramolecular systems
linking non-covalently some porphyrin dyes to dendrimers and proteins have
been investigated.
Some examples will be reviewed with emphasis on spectroscopic and kinetic
aspects. These studies were carried out with equipment acquired throughout the
years and installed in our Laboratory in CQE, covering the temporal range from
milliseconds to picoseconds.


3





MEDALHA
VICENTE SEABRA


QUMICA SUPERFICIAL DE MATERIAS DE CARBONO:
APLICAES AMBIENTAIS

Manuel F. R. Pereira*
Labortorio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
*fpereira@fe.up.pt

A utilizao em catlise e adsoro de materiais de carbono, desde os
tradicionais carves activados at aos nanotubos de carbono passando pelos
materiais mesoporosos como os xerogis e as rplicas de carbono, tem tido um
crescimento exponencial. Uma das razes para este facto reside na possibilidade
de se controlar a sua qumica superficial de forma a optimizar o seu desempenho
em aplicaes especficas.
Nesta apresentao far-se- uma breve introduo sobre a problemtica da
qumica superficial dos materiais de carbono, nomeadamente sobre os mtodos
de modificao e de caracterizao, sendo posteriormente apresentados dois
exemplos da utilizao destes materiais em aplicaes ambientais: como
adsorventes de compostos orgnicos em solues aquosas e como catalisadores
na ozonizao de poluentes orgnicos.


7




LIES
PLENRIAS


CATALYSIS FOR AND WITH CARBON NANOTUBES

Philippe Serp*
Laboratoire de Chimie de Coordination UPR CNRS 8241, composante ENSIACET, 118
Route de Narbonne 31077 Toulouse, France
*Philippe.Serp@ensiacet.fr

Carbon nanotubes [1] are macromolecular-scale tubes of graphitic carbon
with outstanding properties. Since their discovery more than a decade ago, they
have held scientists and engineers in captive fascination, seated on the verge of
enormous breakthroughs in areas such as materials science, electronics, and
medicine, to name but a few. The selective production of these nanomaterials is
currently a strategic topic, since recently major chemical companies have
launched projects around carbon nanotubes.
In the first part of this talk, we will particularly focus on the importance of
catalysts and catalytic processes for the selective and massive production of
carbon nanotubes, which have allow CNTs to be already produced on a small
industrial scale [2, 3].
In the second part of the talk, will be presented recent results obtained in our
laboratory concerning the use of this wonder material for catalytic applications
[4, 5].

[1] M. Monthioux, P. Serp, E. Flahaut, C. Laurent, A. Peigney, M. Razafinimanana, W.
Bacsa, J.-M. Broto. Springer Handbook of Nanotechnology Second revised and
extended Edition B. Bhushan (ed.), Springer-Verlag, Heidelberg, Germany (2007) 43.
[2] R. Philippe, A. Moranais, M. Corrias, B. Caussat, Y. Kihn, P. Kalck, D. Plee, P.
Gaillard, D. Bernard, P. Serp, Chem. Vap. Deposition 13 (2007) 447.
[3] E. Lamouroux, P. Serp, P. Kalck, Catal. Rev. Sc. & Eng. 49 (2007) 341.
[4] P. Serp, M. Corrias, P. Kalck, Appl. Catal. A: Gen. 253 (2003) 337.
[5] H. Vu, F. Gonalves, R. Philippe, E. Lamouroux, M. Corrias, Y. Kihn, D. Plee, P.
Kalck, P. Serp, J. Catal. 240 (2006) 18.


11


WHEN CURVES MEET THEMSELVES: DONOR-
ACCEPTOR SUPRAMOLECULAR ASSEMBLIES

Nazario Martn*, Luis Snchez, Emilio Prez, M Angeles Herranz,
Gustavo Fernndez
Departamento de Qumica Orgnica, Facultad de Qumica, Universidad Complutense, E-
28040 Madrid, Spain
*nazmar@quim.ucm.es; Tel.: (+34) 913 944 227

The combination of supramolecular and electronic reciprocity between
exTTF as strong electron donor systems and Fullerenes as well-known electron
acceptors suggest that this novel host-guest system is a good candidate to be
utilized in the self-organization of electroactive materials. Considering these
principles, we have prepared a series of novel electroactive TTF-type derivatives
as supramolecular receptors for fullerenes and CNTs. Several bowl and belt-
shaped fullerene receptors based on this concave-convex complementarity
principle have already been reported.
.
Herein, we report novel electroactive TTF-
type receptors as supramolecular partners for fullerenes. Firstly, we describe the
first exTTF-based receptor for fullerene, based on a synthetically straightforward
tweezer-like design.

Despite its structural simplicity, our receptor associates
fullerene efficiently in both chlorobenzene and CHCl
3
/CS
2
mixtures (K
assoc
> 10
3

M
-1
). Moreover, it shows a unique solvent-controlled positive homotropic
cooperative binding behavior. Other related supramolecular assemblies endowed
with exTTF concave geometry and covex fullerene surfaces will be also
presented. In addition, we report the synthesis, X-ray, spectroscopic,
electrochemical and theoretical characterization of a new family of -extended
TTF derivatives as bowl-shaped electroactive monotopic receptors for fullerenes.
Single wall carbon nanotubes (SWCNs) have also been interacted with
electron donor exTTFs through covalent and supramolecular linkage and
photoinduced electron transfer processes were observed.

[1] E.M. Prez, L. Snchez, G. Fernndez, N. Martn, J. Am. Chem. Soc. 128 (2006) 7172.
[2] E.M. Prez, M. Sierra, L. Snchez, M.R. Torres, R. Viruela, P.M. Viruela, E. Ort, N.
Martn, Angew. Chem. Int. Ed. 46 (2007) 1847.
[3] M.A. Herranz, Ch. Ehli, S. Campidelli, M. Gutierrez, G.L. Hug, K. Ohkubo, S.
Fukuzumi, M. Prato, N. Martn, Dirk M. Guldi, J. Am. Chem. Soc., 130 (2008) 66.
[4] E.M. Prez, M. Sierra, L. Snchez, M.R. Torres, N. Martn, Angew. Chem. Int. Ed. 47
(2008) 1094.
12


THERAPY WITH CO: MEETING A CHALLENGE

Carlos C. Romo
a,b
*
a
Instituto de Tecnologia Qumica e Biolgica da Universidade Nova de Lisboa, Av. da
Repblica, EAN, 2780-157, Oeiras, Portugal
b
Alfama Lda, Taguspark, ncleo central 267, 2740-122, Porto Salvo, Portugal
*ccr@alfama.com.pt

The role of carbon monoxide (CO) in Biology is still vastly undisclosed.
Recognized as a toxin since Antiquity and used as a tool in biological work since
the XIXth century (C. Bernard, O. Warburg), CO gained a new importance in
Biology after the discovery that it is endogenously produced in healthy and
diseased patients as a result of the catabolism of heme [1]. Curiosity driven
research on the role of such a toxin in the organism led to the discovery of some
of its fundamental biological properties, namely its action as a mediator similar
to NO and its anti-inflammatory properties only recognized in 2000. The number
of studies grew very rapidly based on administration of CO to rodents by
inhalation. Although the beneficial therapeutic effects of inhaled CO have been
amply demonstrated, they require complex procedures for application in humans
and, most importantly, seem to require amounts of CO that are close to toxic
levels. Furthermore, distribution of CO in the organism via its transport by
hemoglobin is necessarily a non-selective process. To improve selectivity of CO
therapy the use of molecules capable of carrying CO and delivering it only in the
diseased tissues is a better alternative and one that will guarantee lower doses of
CO in the blood and, therefore, less toxicity. This approach led to the research on
CO Releasing Molecules (CORM) which was pioneered independently by
Motterlini (who coined the term) [2] and by Alfama [3].
This lecture will describe the evolution of this fast growing field of
therapeutic development and present the state-of-the-art of its research.

[1] T. Sjstrand, Scand. J. Clin. Lab. Invest. 1 (1949) 201.
[2] S.W. Ryter, J. Alam, A.M. Choi, Physiol Rev 86 (2006) 583-650
[3] R.A. Motterlini, B.E. Mann, WO 02/092075 A2 and patents and applications
therefrom.
[4] W. Haas, C. Romo, B. Royo, A. C. Fernandes, I. Gonalves, WO 03/066067 A2 and
patents and applications therefrom.

13


INNOVATION IN CHEMICAL EDUCATION

John W. Moore*
W. T. Lippincott Professor of Chemistry, University of Wisconsin-Madison, 1101
University Avenue Madison, WI 53706-1396 USA.
*jwmoore@chem.wisc.edu

Many positive innovations are possible in secondary (high school) and
postsecondary (university) chemistry education using computers, the World
Wide Web, and social networking (Web 2.0) to link students and faculty with
each other and with chemistry content. I will describe my personal experiences
with many such innovations in courses I have taught at the first-year university
level. These include Web-based tutorials on chemistry, biomolecules, and
laboratory techniques; digitized videos showing chemical reactions and other
chemical phenomena; and an interactive periodic table that provides a broad
range of information about each element (including videos of its reactions, 3-D
models of its crystal structure, and descriptive information about its properties)
and allows for community participation through a wiki. The materials described
are all available through the Chemical Education Digital Library and the Journal
of Chemical Education Web Software.


14




COMUNICAES
CONVIDADAS


COMPOSITE MATERIALS BASED ON ACYLATED
CELLULOSE FIBERS

Carmen S. R. Freire*
Department of Chemistry and CICECO, Campus de Santiago, University of Aveiro, 3810-
193 Aveiro, Portugal
*cfreire@ua.pt

The remarkable properties of cellulose, the most abundant naturally available
polymer, and of its derivatives, have been exploited for centuries and new potential
applications for this ubiquitous renewable resource are still being sought, mainly in
response to the predicted dwindling of fossil resources, associated with the
increasing interest in the development of biodegradable materials based on
renewable resources. One of these ongoing investigations concerns the use of
cellulose fibers as reinforcing elements in composite materials based on polymeric
matrices [1]. The major problems faced by researchers in this field are mostly
related with the highly polar surface of the cellulose fibers, which causes (i) a very
low interfacial compatibility with non-polar matrices like polyolefins, (ii) moisture
uptake, and (iii) inter-fiber aggregation by hydrogen bonding. Numerous strategies
have been explored to overcome these drawbacks, which include both physical and
chemical approaches [1]. The acylation of cellulose fibers with fatty acids
constitutes an interesting way to prepare reinforcing elements for composites with
common thermoplastic matrices, such as polyethylene, as well as to produce
biodegradable plastics with appropriate matrices.
As part of a wider research programme on the surface chemical modification
of cellulose fibres [2-5] for the preparation of new materials (composites, special
papers, etc), we have been studying the preparation and characterization of
composite materials based on acylated cellulose fibers. In this study, two
thermoplastic matrices (polyethylene and a biodegradable polyester) and
cellulose fibers modified with different fatty acids (C6, C12, C18 and C22) were
used in the preparation of various composite materials. Parameters such as the
degree of substitution (DS), and the fibre/matrix ratio were also examined.
The present communication will provide the characterization of the ensuing
composite materials by different techniques, such as DMA, DSC, mechanical
tests, SEM and water uptake determinations. These results will then enable to
establish structure/properties relationships on the basis of both the matrix and the
type of fiber modification and to assess potential applications for the materials.
[1] M.N.Belgacem; A. Gandini Comp. Interf. 12 (2005) 41.
[2] C.S.R. Freire, A.J.D. Silvestre, C. Pascoal Neto, M.N. Belgacem, A. Gandini, J. Appl.
Polym. Sci., 100 (2006) 1093.
[3] C.S.R. Freire; A.J.D. Silvestre; C. Pascoal Neto; A. Gandini; P. Fardim; B. Holmbom
J. Colloid Interf. Sci. 301 (2006) 205.
[4] A.G. Cunha, C.S.R. Freire, A.J.D. Silvestre, C. Pascoal Neto, A. Gandini, E. Orblin,
P. Fardim, Biomacromolecules, 8 (2007) 1347.
[5] A.G. Cunha, C.S.R. Freire, A.J.D. Silvestre, C. Pascoal Neto, A. Gandini, E. Orblin,
P. Fardim, Langmuir 23 (2007) 10801.
17


F ig ure 1
0
0,2
0,4
0,6
300 450 600 750
Abs
nm
NEW OPPORTUNITIES FOR PHOTODYNAMIC
THERAPY OF CANCER: A PORTFOLIO OF STABLE
BACTERIOCHLORINS

Mariette M. Pereira*
Departamento de Qumica, Universidade de Coimbra, 3004-535 Coimbra, Portugal
*mmpereira@qui.uc.pt

Photodynamic therapy (PDT) is a promising treatment modality for several
diseases, being cancer the most relevant. In photodynamic therapy, O
2
, light and a
photosensitizer drug are used in combination. In the past 20 years a large number of
books, reviews and patents have been published based on the development of
sensitizers with ideal properties (stability, red wavelength absorption, non-toxic,
preferential accumulation in tumour cells, formation of oxygen citotoxyc species
and easy elimination from the body). The tetrapyrrolic macrocycles have been
paradigmatic compounds on this field [1]. Photofrin was the first sensitizer used in
PDT and in 1961-1983 dominated the field (first generation). Synthetic chlorins
(Foscan) made their way to PDT in the eighties (second generation), but
bacteriochlorins are recognized as the compounds with best potential for PDT (third
generation). Unfortunately they are
generally difficult to synthesise and
unstable. Herein we present an easy, clean
and green synthetic approach for the
synthesis of a portfolio of halogenated
sulphonamide meso-aryl bacteriochlorins
[2]. The new bacteriochlorins present: i)
High absorbance in the phototherapeutic
window (
max
=749 nm, with c10
5
M
-1

cm
-1
), Figure 1; ii) High photostability, even in aerated aqueous solutions at pH 2;
iii) Low fluorescence quantum yield, u
F
=0.008; iv) High triplet quantum yields; v)
Long triplet lifetimes in deaerated solution (t
T
>100 s), but short in the presence of
oxygen (t
T
=300 ns); vi) High singlet oxygen quantum yields (u
A
>0.5).
The in vitro phototoxicity in breast, colon, prostate, lung and melanoma cell
lines, and their in vivo photodynamic action in melanoma and colon tumours
implanted in mice will be presented.
The photophysical and photochemical properties of these amphiphilic
halogenated bacteriochlorins, together with their efficient synthesis, stability,
controlled solubility in water and biological properties, make this new class of
molecules nearly ideal photosensitizers for PDT.
Ackowledgements: Bluepharma, PRODEP, Eixo Prioritrio I, Medida 1.5; Cmara de
Coimbra.
[1] J.M. Dabrowski, M.M. Pereira, L.G. Arnaut, C.J.P. Monteiro, A.F. Peixoto, A.
Karocki, K. Urbanska, G. Stochel, Photochem. Photobiol. 83 (2007) 897.
[2] M.M. Pereira, L.G. Arnaut, S.J. Formosinho, C.J.P. Monteiro WO Pat. 053707, 2006.
18


AUTO-ORGANIZAO NOS MATERIAIS

V. de Zea Bermudez*
Departamento de Qumica, Universidade de Trs-os-Montes e Alto Douro, 5001-801 Vila
Real, Portugal
*vbermude@utad.pt

Em termos genricos, a auto-organizao um processo no qual a
organizao interna de um sistema aumenta do ponto de vista da complexidade
[1] sem ser dirigido ou guiado por uma fonte exterior. Tipicamente os sistemas
auto-organizados apresentam estrutura hierrquica [2] e exibem propriedades
emergentes [3]. Existem numerosos exemplos de processos de auto-organizao
em polmeros, cristais lquidos, colides e hbridos orgnicos/inorgnicos que se
traduziram na formao de impressionantes estruturas tridimensionais regulares e
organizadas hierarquicamente [4,5].
A auto-organizao nos materiais deve ser entendida como um processo
espontneo de organizao de blocos de construo ("building blocks", BBs)
com dimenses superiores aos da escala subnanomtrica da maioria das
molculas [6]. Os BBs podem ser preparados a partir de materiais orgnicos,
inorgnicos, polimricos e hbridos.
A qumica da auto-organizao nos materiais transcende a qumica de auto-
organizao supramolecular de J. M. Lehn. Os BBs e suas associaes no se
encontram restringidos pela escala de tamanho e no esto limitados a foras de
ligao clssicas, podendo tambm incluir foras capilares, coloidais, elsticas,
magnticas, entre outras.
Para o desenvolvimento da rea dos materiais auto-organizados contribuiram
as lies retiradas da biomineralizao por Pieter Harting, Ernst Haeckel e
DArcy Wentworth Thompson. O advento dos slidos porosos teve lugar em
1938 graas a Richard Barrer, pai dos zelitos [7]. Seguiram-se as intervenes
notveis de Charles Kresge e Edith M. Flanigen, bem como o desenvolvimento
das redes metalo-orgnicas, cuja expanso tem sido extraordinria.
Vrios mtodos, envolvendo [8] ou no [9] a incorporao de um molde
externo, possibilitam a produo de materiais organizados.

[1] N. Goldenfeld, L.P. Kadanoff, Science 284 (1999) 87
[2] P.W. Anderson, Science 177 (1972) 4047
[3] R.B. Laughlin, D. Pines, Proc. Nat. Acad. Sci. 97 (2000) 28.
[4] K. Vall, P. Belleville, F. Pereira, C. Sanchez, Nature Mater. 5 (2006) 107
[5] A. Von Blaaderen, Nature, 439 (2006) 545
[6] G.A. Ozin, A.C. Arsenault, Nanochemistry. A Chemical Approach to Nanomaterials,
RSC Publishing, 2006
[7] R. Barrer, Proc. Royal Soc. London. Series A, 167 (1938) 392
[8] S. Mann, S.L. Burkett, S.A. Davis, C.E. Fowler, N.H. Mendelson, S.D. Sims, D.
Walsh, N.T. Whilton, Chem. Mater. 9 (1997) 2300
[9] J.J. E. Moreau, L. Vellutini, M. Wong Chi Man, C. Bied, J.-L. Bantignies, P.
Dieudonn, J.-L. Sauvajol, J. Amer. Chem. Soc. 123 (2001) 7957
19


METAL-ION-DEPENDENT BIOLOGICAL PROPERTIES
OF A CHELATOR-DERIVED SOMATOSTATIN
ANALOGUE FOR TUMOUR TARGETING

Axel Heppeler
a
, Joo P. Andr
b
*, Ingeborg Buschmann
a
, Xuejuan
Wang
a
, Jean-Claude Reubi
c
, Michael Hennig
d
, Thomas A. Kaden
e
,
Helmut R. Maecke
a

a
Division of Radiological Chemistry, University Hospital of Basel, 4031 Basel Switzerland
b
Centro de Qumica, Campus de Gualtar, Universidade do Minho 4710-057 Braga, Portugal
c
Division of Cell Biology and Experimental Cancer Research, Institute of Pathology,
University of Berne, Murtenstrasse 31, 3010 Berne, Switzerland
d
F. Hoffman-La Roche Ltd, Pharma Research, X-ray Crystallography, CH-4070 Basel,
Switzerland
e
Institute of Inorganic Chemistry, University of Basel, Spitalstrasse 51, 4056 Basel,
Switzerland
*jandre@quimica.uminho.pt

Somatostatin-based radioligands have been shown to have sensitive imaging
properties for neuroendocrine tumours and their metastases. The potential of
[
55
Co(dotatoc)] (dotatoc=4,7,10-tricarboxymethyl-1,4,7,10-tetraazacyclododecane-
1-ylacetyl-d-Phe-(Cys-Tyr-dTrp-Lys-Thr-Cys) threoninol (disulfide bond)) as a
new radiopharmaceutical agent for PET has been evaluated.
57
Co was used as a
surrogate of the positron emitter
55
Co and the pharmacokinetics of [
57
Co-(dotatoc)]
were investigated by using two nude mouse models. The somatostatin receptor
subtype (sst1sst5) affinity profile of [
nat
Co(dotatoc)] on membranes transfected
with human somatostatin receptor subtypes was assessed by using
autoradiographic methods. These studies revealed that [
57
Co-(dotatoc)] is an sst2-
specific radiopeptide which presents the highest affinity ever found for the sst2
receptor subtype.
The rate of internalisation into the AR4-2J cell line also was the highest
found for any somatostatin-based radiopeptide. Biodistribution studies,
performed in nude mice bearing an AR4-2J tumour or a transfected HEKsst2
cell-based tumour, showed high and specific uptake in the tumour and in other
sst-receptor-expressing tissues, which reflects the high receptor binding affinity
and the high rate of internalisation.
The pharmacologic differences between [
57
Co(dotatoc)] and [
67
Ga-(dotatoc)]
are discussed in terms of the structural parameters found for the chelate models
[Co
II
(dota)]
2_
and [Ga
III
(dota)]
_
whose X-ray structures have been determined.
Both chelates show six-fold coordination in pseudooctahedral arrangements.
20


LIPID DOMAINS AND LIPID-PROTEIN INTERACTION:
PHYSICAL CHEMISTRY AND SPECTROSCOPY

Lus M. S. Loura
a,b
, Ana Coutinho
c,d
, Manuel Prieto
d
*
a
Faculdade de Farmcia, Universidade de Coimbra, Rua do Norte, 3000-295, Coimbra
b
Centro de Qumica de vora, Rua Romo Ramalho, 59, 7000-671, vora
c
DEQB, Faculdade de Cincias, Universidade de Lisboa, R. Ernesto de Vasconcelos,
1749-016, Lisboa
d
Centro de Qumica-Fsica Molecular-IST, Av. Rovisco Pais,1049-001, Lisboa
*manuel.prieto@ist.utl.pt

The biological membrane is a very complex system, constituted by a large
number of different types of lipids and proteins, organized in a quasi-
bidimensional geometry, the bilayer. Although direct studies at the cellular level
are carried out, model systems with a more restricted number of components
(lipids or proteins) are frequently used, since they allow a very detailed
biophysical description of the system.
Physical chemistry and spectroscopic approaches in the area of membrane
biophysics will be presented. The lipids self-segregate into domains in the
membrane (phase separation), and thermodynamic descriptions (phase diagrams)
are used in their characterization. Also, membrane proteins select specific types
of lipids to their vicinity (the so-called annular region), or they can disrupt the
bilayer structure inducing strong morphological alterations.
Fluorescence spectroscopy is invaluable in biophysics and life sciences,
among other reasons due to its high sensitivity. The application of time-resolved
methodologies in the framework of quantitative modeling, allows a detailed
structural and dynamic characterization of the biological membrane. Among
these, from FRET (Frster resonance energy transfer), which is a distance
dependent photophysical interaction, information about the system topology can
be obtained.
Recent publications [1-6], describe specific biophysical studies of the
research team.

[1] A. Coutinho et al. Biophys. J. (2008) 240.
[2] L. Loura, et al., Biochim. Biophys. Acta (2008) (review article, in press).
[3] R. de Almeida et al. Chem. Phys. Lipids (2008) (review article, in press).
[4] L. Loura et al., in Annual Reviews in Fluorescence, Springer, N. Y. (2008) (review
article, in press).
[5] L. Loura et al., in Membrane-active peptides: methods and results on structure and
function, International University Line, La Jolla (CA, USA) (2008) (review article,
in press).
[6] L. Loura, M. Prieto, Protein Peptide Lett. (2008) (review article, in press).
21


THE POTENTIAL OF NMR SPECTROSCOPY FOR
ASSESSING THE METABOLIC COMPOSITION AND
ACTIVITY OF TUMOR TISSUES AND CELLS

Iola F. Duarte
a
*, Ana M. Gil
a
, Brian J. Goodfellow
a
, Lina Carvalho
b
,
Vitor Sousa
b
, Joana B. Melo
c
, Isabel M. Carreira
c

a
CICECO, Departamento de Qumica, Campus Universitrio de Santiago, Universidade
de Aveiro, 3810-193 Aveiro, Portugal
b
Instituto de Anatomia Patolgica, Faculdade de Medicina, Universidade de Coimbra,
3001-401 Coimbra, Portugal
c
Laboratrio de Citogentica, Faculdade de Medicina, Universidade de Coimbra, 3001-
401 Coimbra, Portugal
*ioladuarte@ua.pt

The ability to detect and follow metabolic changes in tumours is of
paramount importance for investigating their altered cellular metabolism and for
finding new targets for therapy. Nuclear Magnetic Resonance (NMR)
spectroscopy is a particularly powerful tool for generating metabolic profiles of
complex biological samples and unveiling biomarkers for a specific condition or
disease [1-3]. In this work, we have applied High Resolution Magic Angle
Spinning (HRMAS) NMR to the analysis of intact pieces of lung tumoural and
normal adjacent tissue, in order to characterize and compare their composition.
The
1
H NMR profiles obtained show great complexity and a high degree of
signal overlap resulting from the many compounds present. Based on a range of
one-dimensional (1D) and two-dimensional (2D) NMR experiments, about thirty
of these compounds, including amino acids, organic acids, choline metabolites,
nucleosides and lipids, could be identified. As expected, this composition was
found to differ between tumoural and non-tumoural tissue and, also, between
tumours of different histological types. Changes in small metabolites, such as
creatine and lactate, and in cell membrane constituents (lipids, choline
compounds and myo-inositol) were found to dominate the biochemistry of the
tumours analysed.
HRMAS NMR is also shown to be very useful for obtaining well-resolved
spectra from intact cultured cells. In particular, the composition of endometrial
primary cell lines obtained from tumours and normal tissue was characterised,
and the response of these cells to different degrees of radiation exposure was
assessed.

[1] M. Coen, E. Holmes, J.C. Lindon, J.K. Nicholson, Chem. Res. Toxicol. 21 (2008) 9.
[2] I.F. Duarte, E.G. Stanley, E. Holmes, J.C. Lindon, A.M. Gil, H. Tang, R. Ferdinand,
C.G. McKee, J.K. Nicholson, H.V. Melendez, N. Heaton, G.M. Murphy, Anal. Chem.
77 (2005) 5570.
[3] I.F. Duarte, B.J. Goodfellow, A. Barros, J.G. Jones, C. Barosa, L. Diogo, P. Garcia,
A.M. Gil, NMR Biomed. 20 (2007) 40.
22


NEW LOOK INTO DRUG-MEMBRANE INTERACTIONS:
TOWARDS BETTER TREATMENTS

Marlene Lcio*
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-30 Porto, Portugal
*mlucio@ff.up.pt

Non-steroidal anti-inflammatory drugs (NSAID) are one of the worlds most
prescribed groups of drugs for acute and chronic inflammatory diseases, and
their continuous use is associated with severe gastrointestinal toxicity. The study
of membrane changes upon the interaction with NSAID molecules aimed to
elucidate the molecular mechanisms underlying the biological actions of these
drugs which may prove valuable in reducing their gastrointestinal side-effects.
Most NSAID are weakly acidic, lipid-soluble compounds. Since the cell
membranes on the stomach wall contain lipids for protection against strong
acids, they offer little resistance to the lipid-soluble NSAID. Therefore, the focus
of the work presented has been placed on the effects of NSAID on membranes,
and specifically the ability of these drugs to bind to surface-active phospholipids,
as well as their effect on the lipid dynamic properties of membrane models, once
the results may elucidate about the effects of these drugs compromising the
integrity of gastric mucosal barrier.
In order to identify and isolate the effect of different membrane parameters on
the interaction of NSAID, the biomimicry of the bilayer lipid membrane was
achieved by the use of membrane models (liposomes and monolayers). The
effects on membrane biophysical properties elicited by the drugs under study
were evaluated by fluorescence techniques and differential scanning calorimetry
(DSC). The effects in symmetry and in the long and short-range organisation of
bilayers; in the molecular packing of the bilayers as well as in the chain
conformation of the molecules upon the interaction of the bilayers with NSAID
were also investigated by small and wide angle X-ray scattering (SAXS and
WAXS). Besides the studies in bilayers systems, models consisting of
phospholipids spread at the airwater interface as Langmuir monolayers were
used to obtain additional information on the structure of the penetrated monolayer
by the drug by synchrotron X-ray experiments at grazing incidence (GIXD).
Results provide evidence that the NSAID studied have destabilizing effects,
especially in the lipid gel phase, with a possible increase of the bilayers
wettability which could be transposed to a similar effect in the stomachs mucus
phospholipid gel layer with the development of gastric erosions.

Acknowledgements: Partial financial support for this work was provided by FCT (Lisbon),
through the contract PTDC/SAU-FCF/67718/2006

[1] M. Lcio, S. Reis, J.L.F.C. Lima, F. Bringezu, G. Brezezinski. Langmuir 24 (2008) 4132.
23


Figure 1. Sistemas
heterocclicos para ONL.
DESIGN, SNTESE E CARACTERIZAO DE NOVOS
SISTEMAS HETEROCCLICOS NO CLSSICOS COM
APLICAO EM PTICA NO-LINEAR (ONL)

M. Manuela M. Raposo*, Rosa M. F. Batista, Susana P. G. Costa
Centro de Qumica, Universidade do Minho, Campus de Gualtar 4710-057 Braga,
Portugal
*mfox@quimica.uminho.pt

O design e a sntese de compostos heterocclicos com propriedades de no-
lineariedade ptica (ONL) tem atrado recentemente a ateno de muitos
investigadores devido s suas potenciais aplicaes no processamento e
armazenamento de informao, em comunicaes
pticas, etc. Recentemente desenvolvemos nos
nossos laboratrios a sntese de novos crmoforos
heterocclicos no clssicos com vrias
aplicaes na rea dos materiais pticos. Estes
compostos so constitudos por heterociclos ricos
em electres (pirris [1-3] ou (oligo)tiofenos [4-
6]) que funcionam simultaneamente como ponte
t-conjugada e como grupo dador de electres,
enquanto que heterociclos deficientes em
electres (benzotiazoles, benzimidazoles, fenantrolinas) ou antraquinonas
funcionam como grupos aceitadores de electres. O estudo da estabilidade
trmica e das propriedades pticas (lineares e no-lineares) destes novos
materiais revelaram a sua maior eficincia comparativamente a crmoforos
orgnicos clssicos.
Nesta comunicao ser apresentado o trabalho desenvolvido nos ltimos
anos nos nossos laboratrios, dando nfase aos resultados mais recentes que
incluem a sntese e a caracterizao de ariltienil- e (oligo)tienil- benz-X-azoles,
fenantrolinas e antraquinonas, Figura 1, como sondas de solvatocromismo e
como materiais com aplicao em ptica no-linear.

Agradece-se Universidade do Minho e Fundao para a Cincia e Tecnologia (Projecto
PTDC/QUI/66250/2006 e Bolsa SFRH/BD/36396/2007 a R.MF. Batista) o apoio financeiro.

[1] M.M.M. Raposo, A.M.R.C. Sousa, P. Cardoso, E. Matos Gomes, M. Belsley, G.
Kirsch, A.M.C. Fonseca. Org. Lett. 8 (2006) 3681 e referncias citadas.
[2] R.M.F. Batista, S.P.G. Costa, E.L. Malheiro, M. Belsley, M.M.M. Raposo.
Tetrahedron 63 (2007) 4258.
[3] R.M.F. Batista, S.P.G. Costa, M. Belsley, M.M.M. Raposo. Tetrahedron 63 (2007) 9842.
[4] R.M.F. Batista, S.P.G. Costa, M.M.M. Raposo. Tetrahedron Lett. 45 (2004) 2825.
[5] S.P.G. Costa, R.M.F. Batista, P. Cardoso, M. Belsey, M.M.M. Raposo. Eur. J. Org.
Chem. 17 (2006) 3938.
[6] J. Pina, J. Seixas de Melo, H.D. Burrows, R.M.F. Batista, S.P.G. Costa, M.M.M.
Raposo. J. Phys. Chem. A 111 (2007) 8574.
Ponte t
A D
Ponte t = (oligo)tiofeno, pirrole
D = H, OH, O-alquil, N,N-(alquil)
2
A = benz-X-azole, fenantrolina,
antraquinona
24


EFEITO DE METAIS NA DESATIVAO
DE ZELITOS Y

Henrique Soares Cerqueira*
PETROBRAS/AB-PQF/COMPERJ Av. Rio Branco, 1/ 20 Andar, 20090-907 Centro, Rio
de Janeiro
*henriquecerqueira@petrobras.com.br

Este trabalho discute o efeito dos metais Ni, V, Ca e Fe tipicamente
encontrados nos gasleos empregados como carga no processo de craqueamento
cataltico (FCC), na desativao hidrotrmica de zelitos Y.
Na presena de vapor, o V o principal responsvel pela reduo na rea
superficial da zelita; quando elementos terra-rara esto presentes, o Ni aumenta
o efeito do V. Anlises de temperatura programada de reduo (TPR) sugerem
que uma maior mobilidade das espcies de vandio devido a uma interao entre
Ni e elementos terra-rara. A adio de Fe ou Ca ao catalisador contendo Ni e V
resulta em uma diminuio na formao de coque e aumenta a relao
olefina/parafina durante o craqueamento de molcula modelo.

25


SOLUES CATALTICAS PARA A POLUIO
AUTOMVEL

M. Filipa Ribeiro*
Departamento de Engenharia Qumica e Biolgica, Instituto Superior Tcnico, Av.
Rovisco Pais, 1049-001 Lisboa
*filipa.ribeiro@ist.utl.pt

A catlise tem sido definida como uma tecnologia vital para melhorar a
qualidade de vida e do ambiente, pois tem contribudo ao longo dos ltimos anos
para fornecer solues para muitas das preocupaes ambientais. Por exemplo, o
controlo das emisses dos automveis considerado actualmente como a mais
moderna e segunda maior aplicao da catlise heterognea. Os catalisadores dos
automveis a gasolina, normalmente designados por catalisadores de trs-vias,
eficientes na reduo simultnea de CO, NOx e hidrocarbonetos, comearam a
ser desenvolvidos nos anos setenta, mas a sua introduo massiva no mercado
europeu s ocorreu a partir de 1990, em simultneo com a introduo da
legislao ambiental, a qual tem sido actualizada regularmente e sempre
definindo nveis cada vez mais baixos para as emisses dos principais poluentes.
Actualmente existe um enorme interesse em promover o uso de automveis
com motores (GDI) de injeco directa a gasolina (motores de combusto pobre)
ou a diesel, uma vez que estes motores apresentam grande eficincia energtica,
com menores consumos de combustvel que os motores convencionais de
gasolina e menores quantidades de CO
2
libertadas. Contudo, com este tipo de
motores, os catalisadores de trs vias no so efectivos na reduo dos NOx, e
para reduzir as emisses para os nveis regulamentados pelas normas ambientais,
necessrio desenvolver catalisadores activos na reduo dos NOx em presena
de excesso de oxignio. H vrios anos que este problema est a ser estudado, e
j foram implementadas nos automveis com injeco directa a gasolina e
combusto pobre, algumas solues que recorrem ao armazenamento prvio dos
NOx (tecnologia NSR) e posteriormente promovem a sua reduo cataltica. O
processo mais directo e eficiente para remover os NOx em atmosferas oxidantes
atravs da decomposio directa dos NOx ou da reduo cataltica selectiva
(RCS) dos NOx com hidrocarbonetos ou com amonaco (ou ureia). No caso dos
veculos pesados a diesel, para que possam cumprir com a legislao definida
pelo Euro 4 (2005) e Euro 5 (2009) os fabricantes tm estado a desenvolver
sistemas catalticos capazes de utilizar a RCS com ureia como processo de
reduo dos NOx.


26


A INOVAO NA INDSTRIA QUMICA

Paulo A. P. Arajo*
CUF, Qumicos de Portugal, S.A., Quinta da Indstria, 3860-680 Estarreja, Portugal
*paulo.araujo@cuf-qi.pt

As empresas e em particular as da Indstria Qumica, tm duas estratgias
principais para acrescentar valor s suas organizaes: Fuses & Aquisies
(F&A) e Inovao (I).
Ao contrrio das F&A, a Inovao tem um desenvolvimento endgeno, uma
dinmica mais longa e os activos incorpreos (patentes,) constituem uma parte
importante do capital criado. A intangibilidade e o tempo, constituem barreiras
ao investimento na Inovao e a sua valorao por parte dos accionistas,
refugiando-se em alternativas de retorno mais rpido e seguro.
A intensidade da despesa em Inovao na Indstria Qumica considerada
mdia (2-5 % - despesa inovao/volume de vendas) em relao a outras
indstrias. A abordagem, prioridades e preocupaes so no entanto diferentes
conforme o sector qumico em que a empresa se encontra.
Estatsticas recentes revelam diferenas interessantes entre o sector dos
produtos qumicos de base e de especialidades qumicas. O sector dos produtos
qumicos de base tem uma menor intensidade na despesa em Inovao (2,5%) e
as suas preocupaes centram-se na reduo de custos e o aumento da
flexibilidade da produo. Estas empresas revelam uma focalizao da sua
actividade no processo qumico ao contrrio das especialidades qumicas que
apostam no produto. As empresas de especialidades qumicas tm um
investimento mdio em Inovao de 3,5 % e as suas preocupaes so por ordem
decrescente: a conquista de novos mercados, melhoria da qualidade do produto,
alargar a gama de produtos e a substituio de produtos em declnio.
Para alm do binmio Processo-Produto, as empresas qumicas tem
acentuado o seu esforo de Inovao na Proteco Ambiental, Sade e
Segurana. Este esforo inferior nas empresas de produtos qumicos de base,
apesar dos 10 mais produzidos, serem responsveis na indstria qumica por
mais de 90% do consumo energtico primrio e 80% das emisses de gases com
efeito de estufa.
O modelo de gesto da Inovao que evoluiu nos anos 60-70 para os
laboratrios centralizados e progressivamente para a formao de redes em que
ganharam importncia o outsourcing e as parcerias, tambm ser analisado. A
globalizao e a deslocalizao de centros de Inovao para os pases emergentes
merecero uma referncia, no constituindo actualmente uma preocupao para a
Indstria Qumica.
Finalmente ser feita uma reflexo sobre os factores de sucesso da Inovao,
de que destaco especialmente para este congresso, a temtica da formao
universitria de base Qumico/Engenheiro Qumico.

27


O TRINGULO DA INOVAO: NOVAS SOLUES
PARA PROBLEMAS NOVOS E VELHOS

Alirio E. Rodrigues*
Laboratrio de Processos de Separao e Reaco (LSRE), Laboratrio Associado
LSRE/LCM, Departamento de Engenharia Qumica, Faculdade de Engenharia da
Universidade do Porto, Rua Dr Roberto Frias 4200-265 Porto, Portugal
*arodrig@fe.up.pt

O desenvolvimento de processos e produtos em Engenharia Qumica
combina cincia e tecnologia em ordem no fixada. Apresento dois exemplos:
cromatografia de perfuso para separao de protenas e tecnologia de leito
mvel simulado (SMB) para separaes
quirais em que os detentores do know-how
de fabrico de adsorventes convencionais e de
operao de unidades petroqumicas com
SMB foram ultrapassados por spin-offs que
se tornaram leaders escala global. Os
pequenos podem vencer os grandes... Nestes
dois exemplos h necessidade de cincia
(desenho de adsorventes-MATERIAIS) e
tecnologia de SMB. Um equipamento
verstil FlexSMB para uso da tecnologia em
modos no convencionais de operao foi
desenvolvido no LSRE (PRODUTO).
Problemas velhos podem ser interesantes
quando se quer abanar o presente para
formatar o futuro [1]. Um exemplo o da
separao propano/propileno feita actualmente
por destilao criognica que altamente
consumidora de energia. A procura de
tecnologias alternativas (PSA/VSA e SMB-
PROCESSOS) tem sido objecto de estudo no
LSRE [2]. A separao em fase gasosa pode
ser mesmo desenhada a partir da escala
molecular (simulao MOLECULAR) at ao
processo [3].
Estes casos revelam que:
Engenharia Qumica= M2P2E
(M = Molecular, Materials; P = Processes, Products)
[1] A.E.Rodrigues, Shaking the present.Shaping the future. http://lsre.fe.up.pt
[2] A.E.Rodrigues, Development of propane/propene separations: from molecular
simmulation to processes, Eng Foundation Conference, Costa Rica, 2008.
[3] A.E. Rodrigues et al. French patent 2.903.981, application No 06 06827, 24/07/2006),
PCT WO 2008/012410 A!
28


2 4 6 8
c
b

a

2u (degree)


I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
20 40 60 80
(
2
2
2
)
(
3
1
1
)
(
2
2
0
) (
2
0
0
)



(
1
1
1
)
Fig. 1. XRD patterns of: (a) MCM-
41; (b) MCM-41-sucrose composite;
(c) NCCR-1. Inset XRD pattern of
Pt/NCCR-1
NANOPOROUS CARBON SUPPORTED PLATINUM
(Pt/NCCR-1) ELECTROCATALYST FOR METHANOL
OXIDATION

P. Selvam*, B. Viswanathan, B. Kuppan
National Centre for Catalysis Research, Department of Chemistry, Indian Institute of
Technology-Madras, Chennai 600 036, India
*selvam@iitm.ac.in, fax: + 91-44-2257-4202/0509

For the first time, we have prepared a nanoporous carbon, designated as NCCR-
1, using MCM-41 as the hard (silica) template and sucrose as the carbon precursor
[1, 2]. The high dispersion of platinum on NCCR-1 carbon gives rise to promising
electrocatalytic activity for methanol oxidation. In this study, 20 wt. % Pt was
loaded on NCCR-1 using H
2
PtCl
6
. The loaded sample was then ultrasonicated
followed by heating at 343 K under nitrogen
atmosphere. Subsequently, paraformaldehyde
and sodium carbonate solution was added slowly,
which was then stirred for 3 h at 343 K. The
sample was filtered, washed with distilled water,
and dried in a vacuum at 358 K for 20 h. The
catalyst thus obtained is denoted as Pt/NCCR-1.
The electrochemical oxidation of methanol
over Pt/NCCR-1 was studied by cyclic
voltammetry at room temperature. The working
electrode was fabricated using 20 mg Pt/NCCR-1
by dispersing in 0.5 ml water under
ultrasonication for 20 min. A part (10 l) of this
suspension was then coated on glassy carbon
(GC) disk and dried at 348 K. Finally 5 l of 5
wt% Nafion was coated so as to anchor the
catalyst onto the GC disk and then dried at room temperature.
The electrochemical measurements performed in 1 M H
2
SO
4
+ 1 M CH
3
OH
indicate that 20 % Pt/NCCR-1 catalyst exhibit excellent activity (I
f,p
= 176 mA/cm
2
)
as compared to the commercial 20 % Pt/Vulcan Carbon [3] (If,p = 78 mA/cm2) for
methanol oxidation. Furthermore, the chronoamperometry measurement performed
in 1 M H
2
SO
4
+ 1 M CH
3
OH at + 0.7 V vs. Ag/AgCl saturated KCl for 3 h showed
excellent stability with < 8% degradation of electrocatalytic activity. In addition,
unlike many other Pt supported carbon catalysts [4, 5], Pt/NCCR-1 catalyst does not
get poisoned by carbon monoxide. Thus, the Pt/NCCR-1 show promise as electrode
material for the methanol fuel cell application.
[1] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J. S. Beck, Nature 359 (1992) 710.
[2] R. Ryoo, S.H. Joo, S. Jun, J. Phys. Chem. B 103 (1999) 7743.
[3] V. Raghuveer, A. Manthiram, J. Electrochem. Soc. 152 (2005) A1510.
[4] W. Wei, C. Jieming, C. Yu, L. Tianhong, Chinese J. Catal. 28 (2007) 17.
[5] T. Meiyalagan, B. Viswanathan, J. Power Sources 175 (2008) 789.
29


PREPARATIVE ENANTIOSELECTIVE
CHROMATOGRAPHY

Lus S. Pais*
Laboratory of Separation and Reaction Engineering, School of Technology and
Management, Bragana Polytechnic Institute, Campus de Santa Apolnia, Apartado
1134, 5301-857 Bragana, Portugal
*pais@ipb.pt

In the last years, preparative chiral chromatography has become a more and
more important separation process for the purification of pharmaceuticals and
other added-value products. One reason chromatography is preferred is that the
process allows both high yields and purities of both enantiomers. On the other
hand, this technique is applicable to a wide variety of racemic mixtures, since
chromatographic stationary phases for enantiomer separation are now available.
The optimization of preparative liquid chromatography and simulated
moving bed (SMB) processes for enantioseparation depends on the choice of the
proper stationary phase-mobile phase combination. In this choice, a high
resolution (or selectivity) of enantiomers should not be the only goal to be
aimed, as it is frequently followed at analytical scale. Other objectives, such as,
to obtain high solubility of enantiomers and low retention times should also be
taken into account.
The optimization of chiral separations is frequently a complex task that
requires, at a preparative scale, a careful selection of its operating conditions. In
the case of binary or multicomponent mixtures, an additional complexity results
from the competition between the different components in the interaction with
the stationary phase. Therefore, one of the first steps of the preliminary study of
a chromatographic separation process is the determination of the equilibrium
competitive adsorption isotherms of the two enantiomers that will contribute to
explain the retention mechanism and allow the prediction of the production rate
recoveries and separation costs. Additionally, solubility of the racemate,
selectivity and retention times are separation parameters very sensitive to
changes in mobile phase composition. In fact, the use of continuous separation
processes, such as SMB technology, has achieved high throughputs when high
feed concentrations and short cycle times were applied.
This lecture will present the experimental and simulation tools for the
optimization of preparative enantioseparation chromatographic processes,
including simulated moving bed operation. Experimental results will be shown to
illustrate that different conclusions can be obtained at analytical and preparative
scales and depending on the enantiomer system in study.

30


THE BIOREFINERY CONCEPT: A STEP FORWARD IN
THE SUSTAINABLE PRODUCTION OF CHEMICALS AND
MATERIALS FROM BIOMASS

Armando Silvestre*
CICECO and Chemistry Department, University of Aveiro, 3810-193Aveiro, Portugal
*armsil@ua.pt

Due to the inevitable dwindling of fossil recourses in the coming half century
humankind faces the tremendous challenge of finding alternative sources of
fuels, chemicals and materials to fulfil society needs. Biomass looks as one of
the most logical alternatives to fossil resources, giving rise to a new model of
sustainable development, known as the bio-economy.
Biomass conversion will take place in the so called biorefineries [1], a model
of industry where, similarly to oil refineries, biomass is converted into fuels,
energy, chemicals and materials. Among the different types of biorefineries, the
so called Lignocellulosics-feedstock (LCF) biorefinery might have the
conditions to become the most successful for several reasons such as the nature
of the feedstock, the fact that they can be developed based on existing pulp mills
and finally, that there will be no competition with food production. Additionally,
carbohydrates will be the key starting materials in the large scale production of
chemicals and materials [2].
This presentation will give a general overview of the biorefinery concept and
on the approaches to convert biomass into chemicals and materials illustrated
with some examples of the research being developed at the University of Aveiro,
notably in the exploitation of high value wood extractives from pulp industries
and on the preparation of new materials based on the heterogeneous
functionalization of cellulosic fibers.

[1] B. Kamm, M. Kamm, P.R. Gruber, S. Kromus, Biorefinery systems - An Overview,
In Biorefineries-Industrial Processes and Products, Kamm B., Gruber P.R. and
Kamm M. (Eds.), Wiley-VCH, Weinheim (2006) 3.
[2] A. Corma, S. Iborra, A. Velty, Chem. Rev. 107 (2007) 2411.
31


EXPERIMENTAL AND THEORETICAL STUDIES ON
CHIRAL HETEROGENEOUS CATALYSTS FOR
HYDROGENATION REACTIONS

Mnica L. Casella*, Jos F. Ruggera, Andrea B. Merlo, Virginia
Vetere
CINDECA (Facultad de Ciencias Exactas, UNLP CCT La Plata, CONICET), calle 47
N 257 1900 La Plata, Argentina
*casella@quimica.unlp.edu.ar

The preparation of pure chemical compounds has been one of the most rapid
growing areas in chemistry over the last decades with heterogeneous catalysis
being recognised as providing new possibilities. In this contribution, two
different strategies are studied to obtain enantioselectivity through heterogeneous
catalysis: the use of a chiral species to modify a solid surface and the grafting of
a chiral organotin compound on a metallic catalyst (via Surface Organometallic
Chemistry on Metals techniques, SOMC/M). Both types of systems are applied
to enantioselective hydrogenation reactions.
In the SOMC/M approximation, the modelization of organotin precursor
compounds of general formula Men-Sn-R
3
(R = achiral fragment) that could be
employed for the obtention of enantioselective heterogeneous catalysts, was
studied. To do so, molecular modelling, both at the level of Mechanics and
Molecular Dynamics and Density Functional Theory (DFT), was used. It can be
concluded that, the probability that the Menthyl group, the only one that possesses
a chiral center, could remain anchored to the superficial phase, is higher than the
probability that only the fragments denominated R1, R2, and R3 (all of them
achiral) could remain on the surface, in agreement with experimental results.

Table 1. Binding energies for Sn-C bonds (kCal /mol).
Molecule Binding energy (kcal/mol)
Sn-C(Men) Sn-C(R1) Sn-C(R2) Sn-C(R3)
Men-Sn-(iso-Bu)
3
42.20 42.16 42.13 41.04

The hydrogenation of ethyl pyruvate was studied using (S)-(+)-1-aminoindan
and (R)-(-)-1-aminoindan as chiral modifiers of a Pt/SiO
2
catalyst, using two
different solvents (toluene and acetic acid), in order to analyze their influence on
the reaction. The approach employed to explain the experimental results,
consisted of the molecular modeling of the transition states. In acetic acid, it was
observed an inversion in the sense of the enantiomeric excess (ee%), which was
corroborated by means of the molecular modeling of the transition complexes
formed between modifier and substrate. The origin of the sense of the ee% seems
to be given by the relative abundance of the chiral modifier/substrate complex.
32


ANALYTICAL ELECTRON MICROSCOPY AS A
POWERFUL TOOL IN THE DEVELOPMENT OF NEW
NANOMATERIALS

Goran Drazic*
Joef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
*goran.drazic@ijs.si

Analytical Electron Microscopy (AEM) is a powerful tool for microstructural
investigations of nanostructured materials. Dedicated field-emission gun
instruments enable study of nanosized volumes using various methods, such as
high resolution transmission electron microscopy (HRTEM), hig-resolution Z-
contrast (STEM/HAADF) imaging, different techniques of electron diffraction
(SAED, CBED, nanodiffraction), X-ray energy dispersive spectroscopy (XEDS)
and electron energy loss spectroscopy (EELS).
In the work the main stress will be on AEM study of nanoparticles,
determination of their size, morphology, chemical and structural composition,
orientation, etc.
Study of the nucleation and crystallization of nanosized particles from
amorphous phase, analysis of light elements in small volumes with complicated
geometries, determination of atomic clusters of secondary element in
monocrystals, investigation of self-assembly of quantum dots in an amorphous
matrix are examples that will be presented and discussed in the work.
Determination of the crystallinity is in many cases quite complicated and
ambiguous. The boundary between amorphous and crystalline phase in certain
materials is very broad and smeared. Amount, crystallite size and shape and
defectiveness of the crystal structure of nanoparticles (clusters, embryos, nuclei,
precipitates, nanowires, nanorods, etc.) could be in usual cases determined using
classical approaches (bright-field, dark-field experiments, selected area electron
diffraction, HRTEM). In specific cases novel approaches should be used to
extract the useful information from the sample. Such approaches are the use of
chemical composition fluctuations in nano-regions for the determination of the
presence of nanoclusters, the comparison of calculated and experimental electron
diffraction patterns in the determination of the degree of crystallinity, and the use
of non-standard geometries for absorption correction procedures during the
chemical composition determination using X-ray energy dispersive spectroscopy.
Beside theoretical limits, such as resolution, lowest detection limit, etc.,
which are connected with the physics of the processes and instrumental
conditions, aberrations, etc. there are many practical limits of the methods used
due to a structure, geometry and chemistry of the real samples. Many problems
in analytical electron microscopy are associated with the sample preparation,
such as deterioration of a crystal structure, altering of chemical composition, and
the formation of a contamination layer. In the work these issues will be
addressed and commented.
33


A QUMICA EM PROJECTOS INTERDISCIPLINARES DE
ENGENHARIA E GESTO INDUSTRIAL

Slvia M. M. A. Pereira-Lima
a
*, Rui M. Lima
b
, Sandra Fernandes
b

a
Departamento de Qumica, Escola de Cincias, Universidade do Minho, Campus de
Gualtar, 4710-057 Braga
b
Departamento de Produo e Sistemas, Escola de Engenharia, Universidade do Minho,
Campus de Azurm, 4800-058 Guimares
*silviap@quimica.uminho.pt

Quando iniciei a minha actividade como docente de Qumica na
Universidade do Minho, j l vo 17 anos, as metodologias de ensino e
aprendizagem utilizadas eram as do tempo dos meus avs. Nessa poca, inovar
era sinnimo de utilizao de novas tecnologias mas, no essencial, as aulas
continuavam a funcionar no esquema tradicional. A responsabilidade do ensino
ministrado estava centrada no professor e os alunos limitavam-se a ser
espectadores dentro de uma sala de aula.
A Declarao de Bolonha veio alterar o panorama da educao superior
europeia incentivando a alterao das metodologias de ensino e aprendizagem
centradas do professor para metodologias activas com a aprendizagem centrada
nos alunos. Em 2004, quando as universidades portuguesas ainda no tinham
comeado a adequar os seus cursos no mbito do Processo de Bolonha, j a
Reitoria da Universidade do Minho apoiava projectos-piloto que fomentavam a
aplicao de novas metodologias de ensino que estavam a emergir ao nvel
internacional. Um desses projectos foi a aplicao da metodologia de Ensino por
Projecto - PLE (Project led education)

no, ento Curso de Engenharia e Gesto
Industrial, agora Mestrado Integrado em Engenharia e Gesto Industrial [1, 2].
Este sistema de ensino para alm de fomentar a integrao dos contedos
programticos das unidades curriculares num projecto interdisciplinar elaborado
num perodo de um semestre, visa tambm o desenvolvimento de competncias
transversais como capacidade de trabalho em equipa, capacidade de
comunicao oral e escrita e desenvolvimento de pensamento crtico.
Nesta comunicao ser feita uma breve apresentao sobre a forma como a
metodologia PLE foi implementada neste curso, seguida por uma descrio
detalhada das alteraes que foram efectuadas ao nvel das metodologias de
ensino da qumica (ajuste do programa ao projecto, negociao de critrios de
avaliao, entre outras) referindo tambm algumas percepo sobre os resultados
destas alteraes e a opinio de alguns alunos sobre este processo.

[1] a) P.C. Powell. European Journal of Engineering Education, 29 (2004) 221; b) P.C.
Powell, W. Weenk. Project-Led Engineering Education, Lemma (2003).
[2] a) R.M. Lima, D. Carvalho, M.A. Flores, N.v. Hattum-Janssen. European Journal of
Engineering Education, 32 (2007) 337; b) S.Fernandes, M.A. Flores, R.M. Lima.
Proceedings of ICECE 2007 International Conference on Engineering and Computer
Education, C.R. Brito, M.M. Ciampi (Eds.), Monguagu, Brasil (2007) 422.
34


CINCIA DA MEDIO EM QUMICA

M. Filomena Cames*
CCMMDQBFCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa, Portugal
*fcamoes@fc.ul.pt

Os valores de resultados de medies qumicas, particularmente de carcter
analtico, representam cada vez mais um papel fulcral na troca de informao
sobre composio e outras propriedades fsicas e qumicas de sistemas materiais,
sejam eles do foro alimentar, ambiental, clnico, comercial, ou outro. Da
resultou a crescente necessidade de estabelecer regras e procedimentos para que
os resultados sejam comparveis, com o consequente estabelecimento, num
encontro em Paris a 14 de Outobro de 1999, entre directores dos institutos
metrolgicos nacionais (NMI) de 33 Estados Membros da Conveno do Metro e
representantes de duas organizaes internacionais de padres nacionais de
medio, de um Acordo de Reconhecimento Mtuo (MRA) de certificados de
calibrao e medio emitidos pelos institutos metrolgicos nacionais, num
esquema transparente e compreensivo para dar aos utilizadores informao
quantitativa credvel sobre a comparabilidade dos servios metrolgicos
nacionais e para fornecer uma base tcnica para um acordo mais amplo
negociado para o comrcio internacional e questes de regulamentao. Se a
Metrologia Fsica era j uma cincia de larga implementao, tal no acontecia
com a Metrologia Qumica, com toda uma variedade e complexidade de etapas
dos procedimentos analticos com caractersticas absolutamente especficas.
Houve, portanto a necessidade de desenvolver um conjunto de requisitos de
gesto e tcnicos para o desempenho dos laboratrios, definindo uma linguagem
comum e procedimentos comuns, e de evidenciar a relevncia da melhoria da
qualidade das medies, pois nada se sobrepe evidncia experimental para
substanciar uma afirmao de competncia. O reconhecimento da importncia da
Metrologia nas sociedades modernas que utilizam medies em tecnologia, em
trocas comerciais, no estabelecimento de regulamentos, levou a que, em
particular a Comisso Europeia, com cerca de 40% das Directivas Europeias
envolvendo medies, a promova. Com o objectivo da construo de uma slida
infraestrutura de medies qumicas, so vrias as aces, em vrias frentes,
visando a formao dos executantes de medies que se projectam para fora do
laboratrio, atravessam fronteiras, so usadas em contextos legais, de agentes de
ensino de profissionais destas reas e de auditores tcnicos. Pertencem a este
conjunto, e sero alvo de apresentao, os programas de formao TrainMiC e
AcadeMiC e mais recentemente a atribuio de uma Euromaster Label em
Cincia da Medio em Qumica.

35


THE BOLOGNA PROCESS QUALIFICATIONS
FRAMEWORKS IN THE ENGINEERING AREA

S. Feyo de Azevedo*
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto
*sfeyo@fe.up.pt

The Bologna Process has to be understood as one of the major components of
a model for European development, in the historical background of progress in
science and technology, of societal and political changes that took place on the
last quarter of the 20
th
Century. The commitment is to develop a competitive
economy based on a knowledge society, a model for growth and jobs. This
requires increasing mobility and trans-national co-operation. Such can only be
based on TRUST, which is only achieved with readable national qualification
frameworks and degree systems and with transparent quality assurance systems.
The Bologna Process should thus be seen on a dual environment of related and
complementary, but different, academic and political issues.
In the lecture I shall identify and examine the background and objectives
of this immense reform, which involves some 16 million students in well
over 5000 institutions of 46 countries, with special emphasis on the role that
the development of National Qualifications Frameworks, compatible with
European Guidelines, and the creation of the European Register will have in
the expected and desired outcomes.
I shall in particular comment the tremendous effort that indeed is being made
by governments, academia and professional societies to respond to these
challenges of reform. Also I shall highlight why I wrote back in 2002 [1] that the
Bologna Process is an unloosable opportunity for the reform and progress of
the Portuguese Higher Education System.
Technical Education, more specifically engineering education, can for sure
benefit from the reforms that are being enforced.
In the lecture I shall further comment and give my views on some specific
implications of the Bologna Process in changing methods and curricula in the
engineering area, indeed on how the Bologna Process may be seen as even
linked to changing paradigms of Engineering Education.
In practical terms, two major questions of the exercise are: (i) what role and
distinction of education at the tertiary stage (University education)? (ii) what
should be the structure and the core content of engineering curricula for the
different qualifications recognized in the engineering profession (as set in the
European Directive for Recognition of Professional Qualifications)? What, what
depth, when, how, which teaching aids?
[1] S. Feyo de Azevedo, Notas para Reflexo sobre o Tema Bolonha - Oportunidade
Imperdvel para a reforma do sistema do ensino superior, XIV Congress of Ordem
dos Engenheiros - Engineers Portugal, Coimbra, full paper in CD-ROM, 27-29 June,
2002 (available in www.fe.up.pt/~sfeyo)
36


MICROSCOPIA QUMICA E CRESCIMENTO DE
CRISTAIS: ENSINAR E EMPREENDER

Clementina Teixeira*
Centro de Qumica Estrutural, Instituto Superior Tcnico, Universidade Tcnica de
Lisboa, Av. Rovisco Pais 1049-001 Lisboa
*clementina@ist.utl.pt

Na sociedade contempornea a componente educativa deve cada vez mais
incluir actividades ligadas investigao. No basta promover o ensino de forma
repetitiva, embora eficiente: tambm necessrio que a par da aquisio de
competncias seja estimulada a criatividade, introduzindo cada vez mais a
cultura de projecto. Porm, para que as ideias reunidas neste processo
frutifiquem e sejam motor de desenvolvimento, necessrio que se estabelea a
cadeia de valor das quais elas so o primeiro elo: cada vez mais necessria a
sua insero na comunidade e a sua ligao a outros centros de cultura e de
criao de riqueza onde essas competncias se desenvolvam.
nesta perspectiva que se apresentam os dois projectos que do o ttulo a
esta comunicao, e que tm dado provas no terreno, envolvendo Escolas,
Universidades, Museus e tambm Empresas. O crescimento de cristais por
nucleao heterognea (na presena de suportes rugosos) tem sido explorado em
todas essas vertentes, desde 1994. Mais recentemente, a Microscopia Qumica,
permitindo a observao de cristais e filmagem de reaces ao microscpio,
revitaliza a Qumica reciclando conhecimentos (Qumica Descritiva, Marcha
Geral de Anlise, Qumica Analtica, etc.), promove o ensino de forma
motivadora e sustentvel a todos os nveis de aprendizagem, e ao mesmo tempo
permite empreender, fomentando a ligao da comunidade educativa a empresas
que possam utilizar os padres obtidos na comercializao dos seus produtos.











Figura 1. Microscopia Qumica. Estudo da cristalizao: gelo seco (CO
2
) coberto de cristais
dendrticos de H
2
O. Combinao de motivos para comercializao.

[1] C.Teixeira, Qumica, Boletim da Sociedade Portuguesa de Qumica 107 (2007) 41.
[2] Financiamento FCT e Projecto Cincia Viva, CV/VI/ID976.

37


INOVANDO EXPERINCIAS DE SALO

Carlos M. M. S. Corra*
Centro de Investigao em Qumica da Universidade do Porto (CIQ), Departamento de
Qumica da Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre,
687, 4169-007, Porto
*ccorrea@fc.up.pt

Se uma imagem vale mais que mil palavras,
uma experincia vale mais que mil imagens.

Desde h muito que os cientistas acompanhavam as suas palestras e
comunicaes com experincias geralmente espetaculares, ficando clebres
algumas apresentaes, nomeadamente a da pilha feita por Volta, as
demonstraes de Michael Faraday e William Bragg na Royal Institution, as
palestras de George Porter na BBC e muitas outras.
As demonstraes do tipo "Qumica Mgica" so geralmente realizadas fra
da sala de aula e destinam-se, muitas vezes, ao pblico em geral. Outras
demonstraes, a que chammos h alguns anos Experincias de Salo, podem
realizar-se na sala de aula e so sempre acompanhadas de uma explicao do
fenmeno, juntando o agradvel ao til, sob o ponto de vista qumico.
Desde h alguns anos que os professores tem acesso a tecnologias baratas,
comeando pelo retroprojector, para realizar experincias em escala reduzida
(mas visveis em toda a sala). A projeco de experincias de Qumica em
cpsulas de Petri e gobls bem conhecida, embora o retroprojector se possa
adaptar para projeces laterais.
Sero apresentadas algumas experincias utilizando o equipamento
actualmente existente em praticamente todas as escolas: PC e projector de vdeo,
uma webcmara e uma mquina fotogrfica digital, estas de preo muito
acessvel.
A utilizao destes novos recursos tecnolgicos j realizada por muitos
professores, poupando reagentes, reduzindo a contaminao ambiental e
aumentando a segurana.



38




COMUNICAES
ORAIS


VOLATILE URINE PROFILE OF ONCOLOGIC PATIENTS
BY HEADSPACE SOLID-PHASE MICROEXTRACTION

Michael M. Caldeira
a
, Mafalda Antunes
b
, Fernando Aveiro
b
, Slvia
M. Rocha
c
, Jos S. Cmara
a
*
a
Centro de Qumica da Madeira, Departamento de Qumica, Universidade da Madeira,
Campus da Penteada, 9000-390 Funchal, Portugal
b
Centro Hospitalar do Funchal
c
Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro, Portugal
*jsc@uma.pt

Volatile organic compounds (VOCs), such as aldehydes, alkanes and
methylated alkanes [1] are apparent markers of oxidative stress, which are the
toxic effects of reactive oxygen species comprising oxygen free radicals and
hydrogen peroxide. Reactive oxygen species are constantly produced in the
mitochondria and leak into the cytoplasm where they cause peroxidative damage
to proteins, polyunsaturated fatty acids, and DNA. Peroxidative changes to DNA
bases may be carcinogenic, and oxidative stress appears to be increased in some
cancers, although the evidence for a causal role is lacking [2].
Various methods have been applied in recent years for the discovery of
biomarker patterns of major human diseases, especially for various types of
cancer. Sample preparation remains one of the most time consuming, error prone
aspects of analytical chemistry, so much so that it is increasingly being
recognized as an important area of specialization in this field. In this experiment,
the applicability of solid phase microextraction (SPME) coupled to mass
spectrometry based on quadrupole detection (GC/
q
MS) to isolate/preconcentrate
and analyse aldehydes, alkanes and aromatic hydrocarbons in human biological
fluids has been studied. The experiments were organized in two steps: i) the
SPME experimental parameters were optimized; ii) the proposed methodology
was applied to 36 human biological fluids (urine), 11 of which were from
oncologic patients and the other 25 of which were from controlled healthy
persons. The healthy (members of the general blood donors who had no history
of cancer or any other chronic disease) and oncologic volunteers were recruited
in local Hospital. The application of the developed analytical methodology
allowed the obtaining several tens compounds in both control and oncologic
group, in a wide variety of chemical compounds pertaining to several different
chemical families. Finally, multivariate analysis, were applied to the data set
obtained from the patients and the control group, in order to establish the volatile
biomarker profile associated to the oncologic pathologies.

[1] C. Deng, X. Zhang, N. Li, Journal of Chromatography B, 808 (2004) 269.
[2] P.J. OBrien, A.G. Siraki, N. Shangari, Critical Reviews in Toxicology, 35 (2005) 609.
41


N N
N
R
R
R
R
X
R = n-hexil
aniao quiral ou
aquiral
X
USO DE LQUIDOS INICOS FUNCIONALIZADOS COMO
NOVOS MATERIAIS ORGNICOS

Lus C. Branco
a
*, Andreia Rosatella
b
, Carlos A. M. Afonso
b

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias e Tecnologia da
Universidade Nova de Lisboa, Quinta da Torre, 2829-516 Caparica, Portugal
b
CQFM, Departamento de Engenharia Qumica e Biolgica, Instituto Superior Tcnico,
Av. Rovisco Pais, 1049-001 Lisboa, Portugal
*lbranco@dq.fct.unl.pt

Durante a ltima dcada os Lquidos Inicos (LIs) tm emergido como uma
nova classe ambientalmente benfica e alternativa aos solventes orgnicos clssicos
[1], principalmente devido s suas propriedades peculiares tais como a reduzida
presso de vapor, elevada estabilidade trmica e condutividade inica, larga janela
electroqumica, insolubilidade em CO
2
supercrtico (scCO
2
) e dissoluo de uma
larga gama de molculas orgnicas, inorgnicas e complexos de metais de transio.
As propriedades fsicas e estruturais dos Lquidos Inicos esto geralmente
dependentes do tipo de seleco e combinao das estruturas de catio e anio. As
aplicaes dos LIs inserem-se actualmente em diferentes reas cientficas [2],
destacando-se o seu uso como meio reciclvel para processos qumicos (incluindo
reaces de catlise qumica e biocatlise); no transporte selectivo utilizando
membranas lquidas suportadas e mais recentemente no seu uso como
nanomateriais. Nos ltimos anos tem sido possvel desenvolver novos lquidos
inicos funcionalizados nomeadamente baseados nos caties imidazlio [mim][3] e
guanidnio [dmg][4] combinados com diferentes anies quirais e aquirais. Nesta
comunicao salienta-se o uso de Lquidos Inicos do tipo
guanidnio [dmg] quando combinados com:
-anies orgnicos aquirais: permitindo aplicaes
em processos de dissoluo, extraco e partio de
compostos de interesse biolgico ou farmacutico.
-anies orgnicos quirais permitindo aplicaes em
processos de catlise assimtrica como meio reaccional
quiral e reciclvel [5].
Agradecimentos: Fundao para a Cincia e Tecnologia e FEDER (Ref.
SFRH/BPD/24969/2005 e PTDC/QUI/70902/2006) pelo suporte financeiro.
[1] R.D. Rogers, K.R. Seddon, (Eds); Ionic Liquids: Industrial Applications for Green
Chemistry; ACS Symposium Series 818, ACS, Washington DC, 2002.
[2] a) C.A.M. Afonso, L.C. Branco, N.R. Candeias, P.M.P. Gois, N.M.T. Loureno,
N.M.M. Mateus, J.N. Rosa, Chem. Comm, 2007, 2669. b) L.C. Branco, J.G. Crespo,
C.A.M. Afonso, Angew. Chem., Int. Ed. 41 (2002) 2771.
[3] L.C. Branco, J.N. Rosa, J.J.M. Ramos, C.A.M. Afonso, Chem. Eur. J. 8 (2002) 3671.
[4] N.M.M. Mateus, L.C. Branco, N.M.T. Loureno, C.A.M. Afonso, Green Chem. 5
(2003) 347.
[5] L. C. Branco, P. M. P.Gois, N. M. T. Loureno, V. B. Kurteva, C. A. M. Afonso;
Chem. Comm. 2006, 2371.
42


Figure 1. Structures of 2T
and C
12
E
4

USING NONIONIC SURFACTANTS TO PUSH
CONJUGATED POLYELECTROLYTES AROUND

Hugh D. Burrows
a
*, S. M. Fonseca
a
, M. Knaapila
b
, M. E. Eusbio
a
,
R. Castro
a
, S. Pradhan
c
, U. Scherf
c
, H. Vaughan
d
, A. P. Monkman
d

a
Departamento de Qumica, Universidade de Coimbra, Portugal
b
MAX-lab, Lund University, Sweden
c
Makromolekulare Chemie, Bergische Universitt Wuppertal, Germany
d
Department of Physics, University of Durham, UK
*burrows@ci.uc.pt

Conjugated polymers are an important group of materials, with applications
ranging from light emitting devices, photovoltaic cells to chemical or biological
sensors. Recently, much of the activity in this area has focussed on conjugated
polyelectrolytes. Their aqueous solubility favours
processing from solution using methodologies
such as ink-jet printing, and may also facilitate
self-assembly. Fluorene based systems are
excellent candidates for many of these
applications because of their blue emission, high
fluorescence quantum yield and possibility of
modification to make them good charge carriers
[1]. Although they tend to cluster in water, we
have shown that it is possible to obtain
homogeneous solutions having isolated conjugated polymer chains by using non-
ionic oxyethylene based surfactants, C
m
E
n
[2]. These form cylindrical micelles,
which grow upon increasing surfactant concentration to give long, wormlike
structures. In addition to micellar solutions, non-ionic surfactants form a wide
variety of liquid crystalline phases with water [3]. The anisotropic lamellar L
o

phase is of particular interest as it is likely to lead to polarised fluorescence. We
report a study of the conjugated polyelectrolyte poly[9,9-bis(4-
sulfonylbutoxyphenyl)fluorene-co-2,2-bithiophene] (2T) self aligned in the L
o

phase of the C
12
E
4
/water system. Structural details will be given based on small
angle X-ray scattering and thermomicroscopy measurements. In addition, results
will be presented on polarised emission, and suggestions given of potential
applications.

[1] U. Scherf, E.J.W. List, Adv. Mater. 14 (2002) 477.
[2] H.D. Burrows, M.J. Tapia, S.M. Fonseca, S. Pradhan, U. Scherf, C.L. Silva, A.A.C.C.
Pais, A.J.M. Valente, K. Schillen, Langmuir, submitted for publication.
[3] K. Holmberg, B. Jnsson, B. Kronberg, B. Lindman Surfactants and Polymers in
Aqueous Solution, Wiley, Chichester, 2
nd
Edn., 2003.
2T
S
O O
NaO3S SO3Na
n
S
2T
S
O O
NaO
3
S SO
3
Na
n
S
CH
3
(CH
2
)
11
(OCH
2
CH
2
)
4
OH

43


ORDERED ASSEMBLY OF NANOWIRES AND
NANOTUBES IN POROUS ALUMINA MEMBRANES

C. T. Sousa
a
*, M. P. Proena
a
, D. C. Leito
a
, A. M. L. Lopes
a
, J.
Ventura
a
, J. G. Correia
b
, A. M. Pereira
a
, J. B. Sousa
a
, J. P. Araujo
a

a
Departamento de Fsica and IFIMUP, Rua do Campo Alegre 687, 4169-007 Porto, Portugal
b
ITN, Estrada Nacional n10, Sacavm, Portugal
*celiasousa@fc.up.pt

Nanoporous alumina membranes are an
easy-made product that has attracted much
interest in these last years in nanoscience and
nanotechnology, being used as templates for
well ordered growth of nanowires, nanotubes,
nanorods and nanodots. The research devoted
to this field is pushed by the potential
applications offered by such structures in
several areas, ranging from spintronics to
nanomedicine. While in the former area, these
nanomaterials appear as key components for
applications in nanoscale electronics, optics
and sensors, in the latter they can be used for biomedical applications such as
drug delivery and bioseparations, profiting from the fact that inner voids can be
filled with species, ranging in size from large proteins to small molecules.
In this work we used nanoporous alumina membranes to produce different
nanostructures: silica nanotubes [1] and perovskite manganites (nanotubes and
nanowires) [2] via the sol-gel method and magnetic nanowires with pulsed
electrodeposition [3]. These templates can be easily fabricated using adequate
anodization conditions and the pore size and interpore distance easily varied.
Furthermore, their use for growth of nanotubes and nanowires has enormous
advantages: the possibility to build a net of aligned and ordered nanostructures,
the chance to fill or functionalize their surface and the ability to control the
dimensions required. Using these methods, not only can we control the length of
the nanotubes and nanowires, but we can also control their diameter and
thickness, allowing us to vary these characteristics along their surface.
We will present the implementation of the sol-gel and pulsed
electrodeposition methods using nanoporous alumina membranes allowing the
achievement of high quality nanotubes and nanowires of oxides and magnetic
materials, varying template characteristics such as pore and interpore sizes in
order to optimize these systems.
[1] D.T. Mitchell, S.B. Lee, L. Trofin, N. Li, T.K. Nevanen, H. Soderlund, C.R.Martin, J.
Am. Chem. Soc. 124 (2002) 11864.
[2] P. Levy, A.G. Leyva, H.E. Troiani, R.D. Snchez, Appl. Phys. Lett. 83 (2003) 5247.
[3] K. Pirota, M. Hernndez-Vlez, D.Navas, A. Zhakuv and M.Vzquez, Adv. Funct.
Mater. 14 (2004) 266.

Figure 1 SEM image of silica
nanotubes obtained by sol-gel.
44


SPECTROSCOPIC CHARACTERIZATION OF
POLYMORPHISM IN MOLECULAR SOLIDS

Mariana Sardo
a
*, Mariela M. Nolasco
a
, Ana M. Amado
b
, Paulo J. A.
Ribeiro-Claro
a

a
University of Aveiro, Chemistry Department, CICECO, P-3810-193 Aveiro, Portugal
b
Qumica-Fsica Molecular,Chemistry Department, P-3004-535 Coimbra, Portugal
*msardo@ua.pt

Polymorphism in molecular solids presents a challenge for both structural
studies and practical applications. In fact, the polymorphic behavior of drugs is a
major concern of the pharmaceutical industry, since different polymorphs can
exhibit different biopharmaceutical properties [1].
The PiMM approach (Pairs in Molecular Materials) provides a new
methodology to the computational modelling of a solid in terms of the sum of
molecular pairs present in the structure, with a significant reduction of the
computational effort required. The basis of the concept is that the intermolecular
interactions in the crystal promote perturbations to the isolated molecule
spectrum, and these perturbations are additive.
The proposed methodology
provides an answer to the current
demand for a reliable assignment of the
vibrational spectra and allows the
prediction of the most probable
structure for unknown materials from
the experimental spectra. This new
approach has already been shown to
allow a reliable and complete
vibrational assignment of interacting
molecules in the crystalline form [2].
The present work illustrates the
application of the basic methodology to
a particular vibrational spectroscopy
problem: polymorphism and hydrogen
bonding in pharmaceutical active
compounds. The PiMM approach is
applied to the complete assignment of
the Raman and infrared vibrational spectra of room temperature forms of
pharmaceutical substances like caffeine, theobromine, theophylline and
nitrofurantoin (NF).

[1] G. Fini, J. Raman Spectrosc. 35 (2004) 335.
[2] M. Nolasco, A. M. Amado, P.J.A. Ribeiro-Claro, ChemPhysChem 7 (2006) 2150.
Figure 1. Calculated and experimental
Raman spectra of NF polymorph o.
45


FUNCTIONAL LANTHANIDE-ORGANIC FRAMEWORKS

Filipe A. Almeida Paz
a
*, Joo Rocha
a
, Lus D. Carlos
b
, Tito Trindade
a

a
University of Aveiro, CICECO, Department of Chemistry, 3810-193 Aveiro, Portugal
b
University of Aveiro, CICECO, Department of Physics, 3810-193 Aveiro, Portugal
*filipe.paz@ua.pt

Since the beginning of the 90s that the synthesis of novel metal-organic
frameworks (MOFs) has been a worldwide topical area of research, steaming
from the unusual structural architectures achieved by the combination of organic
ligands with metallic centres. We have been focusing our research efforts in the
use of lanthanide centres with organic linkers based on polyphosphonic acids to
isolate, under mild hydrothermal conditions, large quantities of phase-pure
photoluminescent hybrid materials.
Layered materials belonging to the families formulated as
[Ln(H
3
NMP)]1.5(H
2
O) [Ln = La, Pr, Nd, Sm and Eu] and [Ln(H
2
CMP)]H
2
O
[Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er] [where H
3
NMP
3-
and
H
2
CMP
3-
are residues of nitrilotris(methylenephosphonic acid) and N-
(carboxymethyl)iminodi(methylphosphonic acid), respectively] have been
systematically isolated as microcrystalline powders [1]. High-resolution X-ray
data (powder and also micro-crystal for the latter family of materials),
photoluminescent studies and solid-state NMR techniques have been used in
tandem to unveil the structural details of these functional compounds. Besides
the intrinsic photoluminescent properties, these materials, in particular the latter
family, are also acid catalysts in the conversion of D-xylose into furfural.
Etidronic acid (H
5
hedp) contains two phosphonic acid groups and a central
hydroxyl group. Under hydrothermal conditions, the reaction with lanthanide
centres leads to a rich diversity of networks: layered orthorhombic
[Eu(H
2
hedp)(H
2
O)
2
]H
2
O, layered monoclinic [Ln(H
2
hedp)(H
2
O)]3H
2
O (Ln =
Y, Tb), and also framework-type Na
4
[Ln
2
(hedp)
2
(H
2
O)
2
]nH
2
O (Ln = La, Ce,
Nd, Eu, Gd, Tb, Er) materials [2]. Remarkably, and observed for the first time in
functional MOF materials, these networks are completely inconvertable: under
typical hydrothermal conditions, the HCl treatment of the frameworks materials
produces single-crystals of the layered monoclinic phase; in turn, when the
layered orthorhombic network is treated with NaCl, single-crystals of the
original framework material are instead isolated.

Acknowledgements: This research was supported by Fundao para a Cincia e a
Tecnologia under the project POCI-PPCDT/QUI/58377/2004.

[1] L. Cunha-Silva, L. Mafra, D. Ananias, L. D. Carlos, J. Rocha, F. A. Almeida Paz.
Chem. Mat. 19 (2007), 3527.
[2] F. N. Shi, L. Cunha-Silva, R. A. S Ferreira, L. Mafra, T. Trindade, L. D. Carlos, F.
A. Almeida Paz, J. Rocha. J. Am. Chem. Soc. 130 (2008) 150.
46


AN OPTICAL OXYGEN AND TEMPERATURE DUAL
SENSOR OPERATING UNDER EXTREME CONDITIONS

Carlos Baleizo
a,b
*, Stefan Nagl
b
, Michael Schafrling
b
, Otto S.
Wolfbeis
b
, Mrio N. Berberan-Santos
a

a
Centro de Qumica-Fsica Molecular, Instituto Superior Tcnico, 1049-001 Lisboa,
Portugal
b
Institute of Analytical Chemistry, Chemo- and Biosensors, University of Regensburg,
93040 Regensburg, Germany
*carlos.baleizao@ist.utl.pt

Oxygen, being essential for life, is an immensely important chemical species.
Determination of low oxygen levels is required in many different areas, like
biotechnology, aerospace research, food packaged, chemical industry, etc. A
possibility for trace oxygen sensing is an oxygen sensor based on the thermally
activated delayed fluorescence (TADF) [1] effect displayed by C
70
, leading to an
extremely efficient quenching of the intensity and lifetime of TADF.[2]
However, all known fluorescence-based oxygen sensors suffer from
interference by temperature. This interference can be corrected using a second
sensor dedicated to temperature measurement. Most of the oxygen-temperature
dual sensors reported so far exhibit operation conditions from 0 to 70 C and O
2

concentrations in the 0-100 % range, with sensitivities that can go, in the best
cases, down to ppmv values. However, there is a distinct lack of dual sensors
covering high temperatures (above 70 C), and ultra-low oxygen concentrations
(ppbv range).
In this communication we present an optical dual sensor for oxygen and
temperature which is extremely sensitive to oxygen and that at the same time
covers a broad temperature range. The dual sensing is based on luminescence
lifetime measurements. The novel chemical sensor contains two luminescent
compounds incorporated into polymer films for the simultaneous determination
of temperature (ruthenium complex probe) and oxygen partial pressure (fullerene
C
70
probe).[3] The temperature operation range and the detection limits for
oxygen exhibited by the dual sensor material outperform those of all dual oxygen
and temperature sensors reported up to now. The response time was also
evaluated and a bivariate calibration function for the dual sensor was
successfully validated. This optical dual sensor is a key step forward in a number
of important applications including food packaging, monitoring of anaerobic
hyperthermophilic microorganisms and safety and security technology (detection
of oxygen leaks).

[1] C. Baleizo, M.N. Berberan-Santos, Ann. N. Y. Acad. Sci. xxx (2008) xxx.
[2] S. Nagl, C. Baleizo, S.M. Borisov, M. Schferling, M.N. Berberan-Santos, O.S.
Wolfbeis. Angew. Chem. Int. Ed. 46 (2007) 2117.
[3] C. Baleizo, S. Nagl, M. Schferling, M.N. Berberan-Santos, O.S. Wolfbeis.
submitted.
47


Figura 1. Dimetro hidrodinmico das
partculas, a vrias temperaturas, medidos
por disperso de luz dinmica
NANOPARTICULAS POLIMRICAS PARA
RECONHECIMENTO DE DNA

Leila M. Moura, Telmo Prazeres, J. P. S. Farinha*,

J. M. G. Martinho
Centro de Qumica-Fsica Molecular, Instituto Superior Tcnico, 1049-001 Lisboa
*farinha@ist.utl.pt

A poli(N-isopropilacrilamida)
(PNIPAM) um polmero
termossensivel, com uma temperatura
crtica de soluo inferior (LCST) em
gua prxima de 31-33C. Estes
materiais tm sido estudados com
vista sua aplicao na libertao
controlada de frmacos, em testes
imunolgicos, na concentrao e
isolamento de protenas, DNA, RNA
ou vrus de amostras biolgicas, etc.
Neste trabalho apresentamos a
sntese por polimerizao em
emulso de nanopartculas mono-
dispersas com um ncleo vtreo de
poli(metacrilato de metilo) (PMMA)
e uma coroa de PNIPAM contendo
cargas positivas. Estas partculas
ncleo-coroa so usadas como
suporte para DNA com vista aplicao em testes diagnsticos em suspenso.
Em primeiro lugar so adsorvidos oligonucletidos (ODN) marcados com uma
sonda fluorescente doadora de energia electrnica. O colapso da coroa de
PNIPAM acima da LCST usado para orientar as cadeias de ODN de forma a
optimizar o seu reconhecimento pelo ODN complementar, marcado com uma
sonda aceitante de energia. Foi utilizada uma sequncia de DNA associada ao
Factor V Lieden, a causa gentica mais comum de tromboses. O reconhecimento
detectado por transferncia no-radiativa de energia electrnica (FRET).
Figura 2. Micrografia TEM das partculas
48


METABONOMICS IN FOOD SCIENCE: WHERE TO NOW?

Ana M. Gil*
CICECO, Departamento de Qumica, Campus Universitrio de Santiago, Universidade
de Aveiro, 3810-193 Aveiro, Portugal
*agil@ua.pt

Nuclear Magnetic Resonance (NMR) spectroscopy is now an established
method for the rapid profiling (or metabonomics) of complex mixtures such as
foods, natural extracts and biological samples. Many liquid foods (e.g. juices,
wine, beer) have been, in the past, characterised in relation to their metabolite
composition and several attempts have been made to correlate metabolite
composition with quality indicators e.g. geographic origin, process authenticity,
adulteration, natural vs genetically modified products. Results generally point to
the potential of NMR-based methods to establish, in a few minutes and minimal
sample preparation, a composition profile for each type of product but, once this
is achieved, new clear avenues must be opened.
Two areas are proposed as the main promising directions along which the fast
NMR profiling methods may be put to use. One of these relates to the building of
sturdy chemometrics models to validate the correlations between changes in food
composition and the quality of the product. A model such as this, built with a
high enough number of samples of a controlled nature, may truly be put to use in
the daily routine of the food industry. Examples of this are applications to assess
1) orange juice authenticity and 2) the quality of beer and beer processing. Such
an approach should also bring together more sensitive methods such as GC and
MS, in tandem with NMR, in order to attain a fuller chemical picture of the
origins of the food metabolome. A second developing area, just emerging at
present, is the attempt to understand the interaction between organism and food
and achieve knowledge about the effects of certain foods or diets on the
metabolome of the organism. Examples are shown regarding the effects of soya
flavones in pregnant women or of camomile tea in a controlled group of subjects.
This is, clearly, the newer and almost unexplored area of food metabonomics and
its predicted future is discussed.
49


A TCNICA DE ICP-MS EM ANLISE FORENSE

Agostinho A. Almeida
a
*, Agostinho J. C. Santos
b
, Teresa M. S.
Magalhes
b
, Joana M. F. Tuna
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha 164, 4050-047, Porto, Portugal
b
Instituto de Medicina Legal, Faculdade de Medicina da Universidade do Porto,
Portugal. Instituto Nacional de Medicina Legal, I.P. Delegao do Norte. Jardim
Carrilho Videira, 4050-167 Porto, Portugal
*aalmeida@ff.up.pt

A tcnica de ICP-MS (Inductively Coupled Plasma-Mass Spectrometry),
comercialmente disponvel desde o incio dos anos 1980, tornou-se, no decurso
dos anos seguintes, uma tcnica instrumental da maior importncia no contexto
da anlise elementar inorgnica, essencialmente devido a reunir as seguintes
caractersticas: a) ampla cobertura de elementos permite a determinao da
grande maioria dos elementos da tabela peridica; b) elevado desempenho
analtico em poucos minutos (3-4 min.) possvel analisar um grande painel
(algumas dezenas) de elementos; c) elevada sensibilidade, o que conjugado com
o baixo sinal de fundo (background) permite obter limites de deteco muito
baixos (ng/L na maioria dos casos); d) amplo intervalo de trabalho (at 9 ordens
de magnitude) nas mesmas condies, permite determinar nveis de
concentrao muito diferentes; e) capacidade para fornecer informao isotpica
[1]. Este conjunto de caractersticas fez com que, actualmente, a tcnica de ICP-
MS seja usada em virtualmente todos as reas analticas, com destaque para a
anlise ambiental, geolgica, alimentar e petroqumica, na indstria nuclear e de
semicondutores, e na anlise farmacutica e biomdica (anlises clnicas) [1]. A
sua chegada aos laboratrios de anlise forense ocorreu um pouco mais
tardiamente, mas hoje em dia assiste-se a uma utilizao rapidamente crescente.
Nesta comunicao sero apresentados alguns exemplos demonstrativos do
contributo que a tcnica de ICP-MS pode dar no contexto das investigaes
forenses e, em particular, os resultados mais recentes do nosso trabalho na rea:
1) confirmao do diagnstico de afogamento em corpos encontrados em
ambiente aqutico; 2) determinao do tempo decorrido aps a morte atravs da
anlise do humor vtreo (determinao de diversos elementos vestigiais, de modo
a constituir uma alternativa clssica determinao do potssio); 3) avaliao da
distncia de disparo de armas de fogo atravs da anlise (determinao de Pb, Sb
e Ba) dos resduos depositados em volta do orifcio de entrada do projctil [2].

[1] ICP-MS: Inductively Coupled Plasma Mass Spectrometry A Primer. Agilent
Technologies, 2005.
[2] A. Santos, T. Magalhes, D.N. Vieira, A.A. Almeida, A.V. Sousa. Am.
J. Forensic. Med. Pathol. 28 (2007) 24.

50


APRENDIZAGEM AUTOMTICA COM BASES DE DADOS DE
REACES QUMICAS: ESTIMATIVAS DE REACTIVIDADE

Gonalo V. S. M. Carrera
a,b
*, Joo Aires-de-Sousa
a
a
REQUIMTE, CQFB, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b
CQFM, Instituto Superior Tcnico, Universidade Tcnica de Lisboa, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
*goncalo.carrera@dq.fct.unl.pt

A estimativa de reactividades qumicas a partir da estrutura dum composto
hoje muito importante. Por exemplo na indstria qumica, farmacutica ou
cosmtica necessrio prever a viabilidade de uma dada reaco, ou estimar
actividades biolgicas (incluindo toxicidade) [1]. Concretamente, so necessrios
modelos de reactividade em relao a cadeias laterais de aminocidos, que
evitem a experimentao animal, na obteno do potencial de um composto para
causar dermatite de contacto alrgica [2]. Para codificar a estrutura de
determinado composto foram desenvolvidos descritores MOLMAP, utilizados na
aprendizagem automtica de modelos de classificao/previso [1] de
reactividade. Estes descritores baseiam-se no mapeamento em rede de kohonen
das diversas ligaes presentes numa molcula segundo propriedades fsico-
qumicas e topolgicas.
Neste trabalho foram usados descritores MOLMAP e tcnicas de
aprendizagem automtica para estimar a reactividade qumica de um composto
em relao butilamina, que simula a cadeia lateral do aminocido lisina (reage
nucleofilicamente segundo mecanismo inicial de sensibilizao cutnea). Foi
treinada uma Random Forest (1000 rvores, mtry = 75) para classificar
compostos em termos de reaco ou no com a butilamina, usando um conjunto
de treino com 1844 compostos codificados por MOLMAPs de tamanho 29x29.
Foi obtida uma percentagem de acertos de 92% para um conjunto de teste com
49 objectos e de 69% de acertos para um conjunto de 32 reagentes testados in
vitro na presena de lisina [3]. Noutro estudo semelhante, usou-se uma base de
dados de reaces envolvendo cianoborohidreto de sdio. Foi usado um conjunto
de treino de 638 compostos e dois conjuntos de teste, um com 48 objectos e outro
com 25 (baseado na reactividade descrita [4] para determinadas funcionalidades).
Foi treinada uma Random Forest (1000 rvores, mtry = 75) usando MOLMAPs
15x15 sendo obtida uma percentagem de acertos de 94% para o conjunto de teste
de 48 objectos e 100% para o conjunto de teste de 25 objectos.

[1] S. Gupta, S. Matthew, P.M. Abreu, J. Aires-de-Sousa, Bioorganic & Medicinal
Chemistry 14 (2006) 1199.
[2] A.O. Aptula, G. Patlewicz, D.W. Roberts, Chem. Res. Toxicol. 18 (2005) 1420.
[3] G.F. Gerberick, J.D. Vassallo, R.E. Bailey, J.G. Chaney, S.W. Morrall, J. Lepoittevin,
Toxicol. Sci. 81 (2004) 332.
[4] J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Oxford
University Press, Oxford, 2001.
51


SISTEMA SIA-LOV PARA A DETERMINAO
ENZIMTICA DE PERXIDO DE HIDROGNIO

Susana S. M. P. Vidigal, Ildik V. Tth, Antnio O. S. S. Rangel*
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, Rua Dr. Antnio
Bernardino de Almeida, 4200-072 Porto, Portugal
*aorangel@esb.ucp.pt

Os sistemas de anlise em fluxo tm demonstrado ser uma excelente soluo
para a automatizao de metodologias analticas. No que se refere a ensaios
bioqumicos, a diminuio do consumo de reagentes constitui uma vantagem
assinalvel. A utilizao do conceito de anlise por injeco sequencial, no
formato lab-on-valve (SIA-LOV) permite ainda uma maior miniaturizao dos
ensaios uma vez que o sistema de amostragem e de deteco se encontram na
prpria vlvula.
O objectivo do trabalho foi o desenvolvimento de uma metodologia
enzimtica para a determinao espectrofotomtrica de perxido de hidrognio
utilizando um sistema SIA-LOV. O mtodo desenvolvido tem por base a reaco
de oxidao do ABTS com o perxido de hidrognio na presena da enzima
peroxidase (HRP). O ABTS oxidado ento medido espectrofotometricamente a
410 nm. O consumo de amostra e de reagentes reduzido, gastando-se apenas 15
L de amostra, 9,0 g de ABTS e 51,9 g de HRP por ensaio. aplicvel at
4,28 mg/L de perxido de hidrognio apresentando um baixo limite de deteco
e de quantificao: 0,20 e 0,45 mg/L, respectivamente. Apresenta um ritmo de
45 determinaes por hora.
O perxido de hidrognio um eficaz agente antimicrobiano e esporicida,
como tal usado como desinfectante em vrios produtos farmacuticos, como
por exemplo em solues de desinfeco de lentes de contacto. Por outro lado,
apresenta elevada toxicidade para o epitlio ocular e para a crnea de tal forma
que deve ser neutralizado. Assim, a monitorizao da neutralizao do perxido
de hidrognio no processo de desinfeco/neutralizao de extrema
importncia. Uma vez que a soluo de limpeza contm uma elevada
concentrao de perxido de hidrognio, para que a monitorizao in-situ do
processo de neutralizao do perxido de hidrognio aquando da desinfeco das
lentes de contacto possa ser efectuada no sistema SIA-LOV, foi necessrio
introduzir uma diluio em linha. Esta diluio foi efectuada com uma
membrana hidroflica (dilise) numa unidade de transferncia de massa linear. O
consumo de reagentes e amostra manteve-se inalterado com a introduo da
diluio em linha, abrangendo um intervalo de resposta linear at 342 mg/L de
perxido de hidrognio com baixo limite de deteco de 16,1 mg/L.

Agradecimentos: Susana Vidigal e Ildik Tth agradecem Fundao para a Cincia e a
Tecnologia (FCT) e ao FSE (III Quadro Comunitrio) pelas bolsas SFRH/BD/23040/2005
e SFRH/BPD/5631/2001, respectivamente.
52


Figura 1. Imagem SEM
de OMS-2/MnO
x

OXIDAO TOTAL DE ACETATO DE ETILO USANDO
CATALISADORES DE XIDO DE MANGANS

V. P. Santos, M. F. R. Pereira, J. J. M. rfo, J. L. Figueiredo*
Laboratrio de Catlise e Materiais, Departamento de Engenharia Qumica, Faculdade
de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*jlfig@fe.up.pt

Recentemente os xidos de mangans tm vindo
a ocupar um lugar de destaque nos processos
catalticos heterogneos, em particular nos
processos de oxidao, devido ao seu baixo custo e
elevada actividade. Numerosos trabalhos tm sido
publicados sobre a sntese deste tipo de materiais,
em especial os que se apresentam sob a forma de
peneiros moleculares octadricos (OMS) [1]. O
criptomelano (OMS-2) caracterizado por
apresentar tneis na sua estrutura porosa, dentro dos
quais se encontram caties de potssio. A estrutura
porosa e a valncia mista do mangans na rede
deste xido, conferem-lhe excelente actividade em reaces de oxidao. A
oxidao cataltica considerada um mtodo eficaz na remoo de compostos
orgnicos volteis (COV). Sendo a formulao do catalisador um passo essencial
na optimizao deste processo, o presente trabalho tem como objectivo a
avaliao de xidos de mangans na oxidao total do acetato de etilo.
Os xidos de mangans foram sintetizados utilizando a reaco directa entre
o acetato de mangans e o permanganato (Na, K, Cs), em condies de refluxo e
a pH cido. Estudou-se o efeito de parmetros como o pH e a natureza do catio.
Verificou-se que apenas se forma criptomelano na presena de caties potssio e
numa gama restrita de pH. Fora dessas condies obtm-se na maioria dos casos
uma mistura de xidos de mangans (Figura 1). Os ensaios de oxidao foram
realizados num reactor de leito fixo (BTRS Jr. Autoclave Engineers), presso
atmosfrica, usando-se uma corrente de alimentao de COV de 1600 ppmv e
mantendo-se uma velocidade espacial de 16 000 h
-1
. Estes ensaios permitiram
concluir que o criptomelano se distingue dos restantes xidos de mangans, pela
sua elevada actividade e selectividade em CO
2
, diminuindo a temperatura
necessria para oxidar completamente o acetato de etilo em CO
2
. A presena de
vapor de gua e CO
2
na alimentao no afecta significativamente a actividade
deste catalisador.
Agradecimentos: Fundao para a Cincia e Tecnologia (FCT) e FEDER
BD/23731/2005, POCTI/1181 e PTDC/AMB/69065/2006.
[1] R.N. Deguzman, Y.F. Shen, E.J. Neth, S.L. Suib, C.L. Oyoung, S. Levine and J.M.
Newsam, Chem. Mat. 6 (1994) 815.

53


THERMINFO: A CHEMOINFORMATICS DATABASE
SYSTEM FOR ONLINE PROPERTIES PREDICTION

Rui C. Santos
a
*, Hugo F. M. C. Martiniano
a,b
, Joo P. Leal
a,c
, Benedito
J. Costa Cabral
b
, Jos A. Martinho Simes
a,d

a
Centro de Qumica e Bioqumica, Faculdade de Cincias, Universidade de Lisboa, 1749-
016 Lisboa, Portugal
b
Grupo de Fsica-Matemtica da Universidade de Lisboa, Av. Professor Gama Pinto 2,
1649-003 Lisboa, Portugal
c
Departamento de Qumica, Instituto Tecnolgico e Nuclear, 2686-953 Sacavm,
Portugal
d
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av.
Repblica, 2780-157 Oeiras, Portugal
*rjcs@fc.ul.pt

The project ThermInfo aims to develop an online computational application
to compile and present critically evaluated and thermodynamically consistent
experimental thermochemical properties. The application will include the
implementation of prediction methods, such as an extension of the Laidler
scheme [1] for estimation of standard enthalpies of formation at 298.15 K for
organic compounds.
A database with thermochemical and structural information for almost 3000
organic compounds was reviewed. The parameters needed for application of the
extended Laidler scheme to hydrocarbons (alkanes, alkenes, alkynes, polyenes,
poly-ynes, cycloalkanes, cycloalkenes, benzene derivatives, and polyphenyls)
were calculated and tested.
Several disagreements between estimated and experimental values were
investigated by using quantum chemistry calculations.

Acknowledgments: R.C.S. and H.F.M.C.M. gratefully acknowledges Fundao para a
Cincia e a Tecnologia (FCT) for a post-doctoral (SFRH/BPD/26610/2005) and a Ph.D.
grant (SFRH/BD/27577/2006), respectively.

[1] J.P. Leal. J. Phys. Chem. Ref. Data 35 (2006) 55.
54


PH-INDUCED ADSORPTION OF CYTOCHROME C TO
ACIDIC SELF-ASSEMBLED MONOLAYERS ON GOLD
SURFACES AND NANOPARTICLES

Maria J. Feio
a
, Krisztina Istvn
a,b
, Ins Gomes
b
, Pedro Quaresma
a
,
Nuno C. Santos
c
, Peter Eaton
a
, Ricardo Franco
b
*
a
REQUIMTE and Departamento de Qumica, Faculdade de Cincias da Universidade do
Porto, R. Campo Alegre, 687, 4169-007 Porto, Portugal
b
REQUIMTE, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

c
Instituto de Medicina Molecular, Faculdade de Medicina da Universidade de Lisboa, Av.
Prof. Egas Moniz, 1649-028 Lisboa, Portugal
*r.franco@dq.fct.unl.pt

The adsorption characteristics of horse heart cytochrome c (HCc) onto self-
assembled monolayers of mercaptoundecanoic acid (MUA) on gold surfaces and
gold nanoparticles (AuNP) were studied by quartz crystal microbalance (QCM),
atomic force microscopy (AFM), UV-visible spectroscopy and -potential
measurements.
QCM studies provided quantitative information regarding the adsorption of
HCc onto bare gold (Au) and MUA self-assembled monolayers on gold
(Au/MUA). Results of experiments carried out with this pseudo-two dimensional
system at pH 7.4 and 4.5 showed that the presence of MUA favors protein
adsorption at the higher pH but does not significantly influence the process at
lower pH values. These data suggest that the interaction MUA/HCc is mainly of
an electrostatic nature and that pH can be used as an adsorption modulator. AFM
studies of this system in solution provided images showing the distribution of
individual protein molecules adsorbed to the Au/MUA surfaces.
UV-visible data on AuNP/MUA/HCc bionanoprobes and AuNP/MUA
complexes show aggregation as a function of the solution pH, inducing a shift of
the AuNP plasmon band corresponding to a red-to-blue color change in the
solution. This behavior was not observed in the AuNPs and protein alone.
AuNP/MUA/HCc bionanoprobes aggregate at pH 6.5, whereas AuNP/MUA
aggregate at pH 4.5, reminiscent of the pK
a
value of MUA (pK
a
= 5.7 0.2). A
similar aggregation pattern with pH is observed by -potential measurements,
where the AuNP/MUA complexes have a surface potential of ca. 35 mV
between pH 10 and 6 but which approaches zero in the pH range 6 to 2.
Taken together, the data indicates that HCc adsorbs to MUA self-assembled
monolayers on Au surfaces and nanoparticles in an electrostatic and pH-
dependent manner. Further, the amount of HCc on the Au surface can be
modulated by the pH value of the solution, with 7.4 being the switching pH
value.
55


BI-PHOBIC CELLULOSE FIBERS VIA SURFACE
MODIFICATION WITH PERFLUORINATED
COMPOUNDS

Ana G. Cunha*, Carmen S. R. Freire, Armando J. D. Silvestre,
Carlos Pascoal Neto, Alessandro Gandini
CICECO and Department of Chemistry, University of Aveiro, Aveiro, Portugal
*gcunha@ua.pt

The controlled heterogeneous modification of cellulose fibers constitutes,
nowadays, a hot topic in the realm of polymer science

because, as opposed to
homogeneous conditions (extensively explored), reactions can be limited to the
groups present in the accessible regions of the fibers, and thus the ensuing fibers
can be used in a variety of novel applications.
Accordingly, we have studied the controlled heterogeneous modification of
cellulose fibers with two types of fluorinated reagents, those which generate
readily hydrolysable moieties (trifluoroacetic anhydride TFAA) [1, 2] and
those which provide more stable structures in this context (trifluoropropionic
acid TFP and pentafluorobenzoyl chloride PFBz) [3, 4].
The resulting modified fibers show remarkable low surface energies (
s
) and
high contact angles with both polar and non polar liquids (Table 1) which reflect
their high bi-phobic character, even at very low substitution degrees (DS).
Details on the chemical modification procedures and structural characterization
will be presented.

Table 1. DS, contact angles ranges (with water and diiodomethane) and surface energy
values for the perfluoroacetylated fibers studied.
Sample DS
Contact angle

s
(mJ/m
2
)
Water CH
2
I
2

Fiber - 56 37 55.2
TFAA-Fiber 0.04 - 0.3 119 - 126 94 - 104 6.7 - 11.7
PFBz-Fiber 0.0014 - 0.39 120 - 128 71 - 82 ~20
TFP-Fiber <0.006 - 0.30 113 - 122 84 - 91 ~15

[1] A. G Cunha, C. S. R. Freire, A. J. D. Silvestre, C. P. Neto, A. Gandini. J. Col. Interf.
Sci. 301 (2006) 333.
[2] A. G Cunha, C. S. R. Freire, A. J. D. Silvestre, C. Pascoal Neto, A. Gandini, E.
Orblin, P. J. Fardim. Col. Interf. Sci. 316 (2007) 360.
[3] A. G Cunha, C. S. R. Freire, A. J. D. Silvestre, C. Pascoal Neto, A. Gandini, E.
Orblin, P. Fardim. Langmuir 23 (2007) 10801.
[4] A. G Cunha, C. S. R. Freire, A. J. D. Silvestre, C. Pascoal Neto, A. Gandini, E.
Orblin, P. Fardim. Biomacromolecules, 8 (2007) 1347.

56


Figure 1. Experimental aqueous solubility
data (, salicylic acid; , gallic acid; ,
trans-cinnamic acid; crossed circles,
caffeic acid; , ferulic acid) and modelling
results by CPA (solid line) and UNIQUAC
(dotted line).
T / K
280 300 320 340 360
M
o
l
e

F
r
a
c
t
i
o
n

S
o
l
u
b
i
l
i
t
y
10
-5
10
-4
10
-3
10
-2
PHASE EQUILIBRIA OF SOME PHENOLIC
COMPOUNDS: EXPERIMENTAL AND MODELLING

Antnio J. Queimada
a
*, Ftima L. Mota
a
, Simo P. Pinho
b
, Eugnia
A. Macedo
a

a
LSRE, Laboratory of Separation and Reaction Engineering, Departamento de
Engenharia Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr.
Roberto Frias s/n, 4200-465 Porto, Portugal
b
LSRE, Laboratory of Separation and Reaction Engineering, Departamento de
Tecnologia Qumica e Biolgica, Instituto Politcnico de Bragana, Campus de Santa
Apolnia, Apartado 1134, 5301-857 Bragana, Portugal
*ajq@fe.up.pt, fax: +351225081674

Several phenolic compounds are important for the food, chemical and
pharmaceutical industries, some of them presenting complex chemical structures
with different and multiple functional group substitutions.
To describe the phase equilibria of these complex chemicals, models able to
take into account different intermolecular interactions, such as association, are
required. To evaluate, improve or
develop models an extensive database
of experimental data is required.
In this work, solubilities were
measured for some phenolic
compounds in the temperature range
288 - 323 K, by the shake-flask
method coupled with quantitative
spectrophotometric analysis. Besides
solubility, melting data and acid
dissociation constants were also
determined, providing a broader
knowledge about the solubilization
process of these molecules.
These new measurements and
other literature data were combined to
develop a methodology to model the
phase equilibria of phenolic compounds using the Cubic-plus-Association (CPA)
equation of state [1]. The modified UNIQUAC model [2] was also evaluated
using the measured data. Both CPA and the modified UNIQUAC model showed
to be appropriate tools to represent the solubility of these molecules.

Ftima Mota acknowledges her FCT PhD scholarship SFRH/BD/32372/2006.

[1] F.L. Mota, A.J. Queimada, S.P. Pinho E.A. Macedo. Ind.Eng.Chem. Res. (accepted).
[2] M. Peres,E.A. Macedo, Fluid Phase Equilibria 123 (1996) 71.
57


MATERIAL STUDY OF AN ARRAIOLOS TAPESTRY
FROM THE 18
TH
CENTURY

Ana Manhita
a
, Vanessa Pimenta
a
, Helena Vargas
b
, Isabel Ribeiro
b
,
Teresa Pacheco
c
, Jos Miro
a,d
, Teresa Ferreira
a,e
, Antnio
Candeias
a
, Cristina T. da Costa
a
*
a
University of vora, Chemistry Department and CQE, R. Romo Ramalho, 59, 7000
vora, Portugal
b
Museums and Conservation Institute, Materials Studies Department, Portugal
c
National Museum of Ancient Art (MNAA), Lisboa, Portugal
d
University of vora, Geosciences Department & Geophysics Center of vora, Portugal
e
CCMM, Faculty of Sciences, University of Lisbon, Portugal
*cmtc@uevora.pt

The embroidered tapestries of Arraiolos constitute one of the most interesting
popular artistic industries born in Portugal. These embroidery tapestries were
produced in Arraiolos village since the late 1600s but literature concerning their
manufacture is scarce. Dating historical Arraiolos
tapestries is a difficult task and it is done usually
based solely in stylistic details.
This work is part of the project REMATAR
Rediscovering the Materials of Arraiolos tapestries
(PTDC/HAC/64045/2006), which intends to obtain
systematized information on the composition,
structure and degradation processes and to use these
data to improve conservation methodologies.
Fibre samples were taken from an 18
th
century rug
(Fig. 1) from the Arraiolos collection belonging to the National Museum of
Ancient Art (MNAA). Morphological characterization of the wool threads was
done by scanning electronic microscopy (SEM), showing that in some cases the
wool fibers used for the embroidery presented roughened surfaces with damage
of the scale structure due to wear and natural ageing. SEM analysis also
suggested the use of linen fibers to make the canvas. Microanalyses by EDS and
-PIXE were used for mordant identification. EDS and -PIXE results showed
the presence of aluminium as mordant in most of the samples, except for the
brown fibers, clearly mordanted with iron. Unusually, some yellow fibers were
also mordanted with iron. Aluminium was detected in wool fibers dyed in blue,
suggesting pre-mordanting procedures in wool dyeing processes. LC-DAD-MS
enabled the identification of the materials used to dye the wool fibers.

Acknowledgement: Ana Manhita gratefully acknowledges a PhD scholarship
SFRH/BD/22411/2005 granted by FCT.

[1] S. Pessanha, Tapetes de Arrayollos, Typographia do Annuario Comercial, Lisboa, 1917.
Figure 1. Detail from
Arraiolos rug #38 from
MNAA collection
58


A MICROSCOPIA QUMICA ASSOCIADA AO ESTUDO
DA SRIE ELECTROQUMICA DOS METAIS

Hermnio Diogo
a
*, Manuel E. Minas da Piedade
b
, Clementina
Teixeira
a

a
Centro de Qumica Estrutural, Instituto Superior Tcnico, Universidade Tcnica de
Lisboa, Av. Rovisco Pais 1049-001 Lisboa, Portugal
b
Departamento de Qumica e Bioqumica, Faculdade de Cincias, Universidade de
Lisboa,1749-016 Lisboa, Portugal
*hdiogo@ist.utl.pt (electroqumica); clementina@ist.utl.pt (microscopia qumica)

A Microscopia Qumica, explorada ao nvel do ensino, permite uma
abordagem muito apelativa das reaces de oxidao-reduo, pelo menos do
ponto de vista qualitativo. Com ampliaes at 15x possvel, para alm disso,
obter informao sobre reaces paralelas e, ao mesmo tempo, registar em forma
de fotomicrografia e filme, padres susceptveis de serem utilizados para
aplicaes comerciais e industriais (indstria txtil, papel, plsticos, artes
grficas, antiguidades, ourivesaria, etc). A srie electroqumica dos metais foi
estudada por este mtodo, conjugando-a com a interpretao de diagramas de
Latimer e de Frost, E pH, e com a determinao experimental das foras
electromotrizes padro de reduo pela equao de Nernst, constantes de
equilbrio termodinmica e estequiomtrica, tendo em conta os desvios
idealidade (determinao de coeficientes de actividade). Foram estudadas pilhas
galvnicas de concentrao, composio e precipitao, para os metais Cu, Ag,
Zn e Pb. Foram ainda discutidos conceitos de qumica descritiva envolvendo
metais e ligas metlicas, electrlise, sobretenso, corroso, nodos sacrificiais de
Mg, estanhagem e zincagem, etc. (programas de Qumica do ensino secundrio).












Figura 1. Microscopia Qumica: sistema Cu/ AgNO
3
, rvores metlicas (cristais
dendrticos de prata, disco de cobre em soluo de nitrato de prata).
Financiamento FCT e Projecto Cincia Viva, CV/VI/ID976.
[1] C. Teixeira, V. Andr, N. Loureno, M. J. Rodrigues, Cincia e Tecnologia dos
Materiais 19 (2007) 66.
[2] H. Diogo, M.E. Minas da Piedade, Estudo de Clulas Galvnicas, IST (2004).



59


A PLATAFORMA MOODLE NO ENSINO DA QUMICA:
EXPERINCIAS E PISTAS DE INOVAO

Emanuel A. C. F. Reis
a,b
*

a
Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre, 687, 416- 007
Porto, Portugal
b
Escola Bsica Integrada com Jardim de Infncia do Couo Coruche, Rua Padre Joo
2010-908 Couo
*emanreis@gmail.com

A chegada do computador e mais recentemente da Internet escola, tem
provado ser um valioso auxiliar do processo educativo. Diversos estudos
comprovam que a introduo das novas tecnologias de informao e
comunicao na educao tem efeitos positivos [1].
De facto, os alunos portugueses tm uma grande apetncia para o uso de
ferramentas informticas, e gostam muito de trabalhar com computadores [2].
No de surpreender, portanto, que professores e instituies de ensino de
todos os nveis e reas utilizem cada vez mais o computador e a WWW nas suas
aulas [3].
Uma plataforma de aprendizagem uma aplicao informtica suportada na
WEB que permite desenvolver materiais de aprendizagem, disponibilizar cursos
aos estudantes, proceder a testes e avaliaes e gerar bases de dados de
estudantes com possibilidade de monitorizao dos respectivos resultados e
progresso, por via electrnica [4].
Em Portugal, tem-se vindo a generalizar o uso da plataforma Moodle [5].
O presente workshop pretende apresentar alguns mdulos e funcionalidades
especialmente teis para o ensino da Qumica e debruar-se sobre contextos e
oportunidades da sua utilizao em regimes de e-learning ou b-learning.

[1] Grgoire, R., Bracewell, R., Laferrire, T. The contribution of new technologies to
learning and teaching in elementary and secondary schools: Documentary Review.
Laval University and McGill University, 1996.[em linha] [consultado em
07/05/2007], acessvel em: http://www.tact.fse.ulaval.ca/fr/html/apport/impact96.html
[2] PAIVA (2002) Paiva, Jacinta As Tecnologias de Informao e Comunicao:
Utilizao pelos Professores. Lisboa: Programa Nnio Sculo XXI, Ministrio da
Educao,DAPP.2002 [em linha] [consultado em 09/07/2006], Acessvel em:
http://www.giase.minedu.pt/nonio/pdf/utilizacao_tic_profs.pdf
[3] Mason, R. Globalising education: Trends and Applications. London Routledge, 1998.
[4] Keegan, Desmond - E-learning : o papel dos sistemas de gesto da aprendizagem na
Europa coord. Carina Baptista, Ana Dias. - Lisboa: INOFOR, 2002.
[5] MOODLE Sites - Portugal, [em linha] [consultado em 01/02/2008], Acessvel em:
http://moodle.org/sites/index.php?country=PT
60


QUIMICA E BIOLOGIA NA COZINHA: UM CONTRIBUTO
PARA O ENSINO EXPERIMENTAL DAS CINCIAS NO
ENSINO SECUNDRIO

M. Manuela F. Silva
a
*, M. Nair Alua
b
, Pedro F. Galego
b
, M. Celeste
Serra
b
a
Escola Secundria Fonseca Benevides, Rua dos Lusadas 1300-364 Lisboa
b
Centro de Estudos de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa,
Rua Conselheiro Emdio Navarro, 1, 1959-007 Lisboa
*mmfsilva99@hotmail.com

O ensino experimental das cincias constitui uma importante meta que se
encontra patente em todos os programas das disciplinas de Fsica, Qumica e
Biologia do ensino bsico e secundrio. Por outro lado, a experincia de ensino
tem mostrado que o nvel de motivao dos alunos elevado quando se lhes
prope a realizao de actividades experimentais que possam responder a
problemas reais do quotidiano. neste contexto que o Projecto Qumica e Biologia
na cozinha, apoiado pelo Programa Cincia Viva VI, se tem desenvolvido em
trabalho colaborativo entre o Centro de Estudos de Engenharia Qumica do
Instituto Superior de Engenharia de Lisboa e a Escola Secundria de Fonseca
Benevides, instituies com larga tradio no ensino experimental das cincias.
O Projecto, dirigido a alunos do 11 e 12 anos do Curso Profissional de
Tcnico de Anlise Laboratorial, iniciou-se em Janeiro de 2006 e encontra-se em
fase de finalizao. Este Projecto baseou-se em actividades experimentais
realizadas pelos alunos nos laboratrios de Anlise Instrumental do
Departamento de Engenharia Qumica do ISEL no mbito da anlise de produtos
alimentares. Assim, de acordo com os objectivos e contedos programticos da
disciplina de Anlises Qumicas foram seleccionadas e adaptadas actividades
experimentais j desenvolvidas no ISEL [1, 2].
Aps preparao prvia das actividades em sala de aula na Escola Secundria
Fonseca Benevides, os alunos deslocaram-se ao ISEL onde realizaram o trabalho
experimental em pequenos grupos e procederam ao respectivo tratamento de
resultados cuja discusso e anlise crtica foi, posteriormente, efectuada em sala
de aula.
Idnticas actividades experimentais foram, tambm, implementadas nos
laboratrios de Qumica da Escola Secundria Fonseca Benevides com a
colaborao dos alunos.
Encontra-se em elaborao um caderno de protocolos das actividades
experimentais realizadas, o qual constituir um dos produtos finais do Projecto, a
divulgar nos sites das Instituies participantes.

[1] C. J. Fenk, N. Kaufman, D. G. Gerbig, Jr, J. Chem. Educ, 84, 10 (2007) 1676.
[2] M. L. S. S.Gonalves, Mtodos Instrumentais para a Anlise de
Solues Anlise Quantitativa, 4ed., Fundao Calouste Gulbenkian, 2001.
61


COM ABBORAS, CENOURAS, BATATAS, MAS

Maria Goreti Matos
a
*, Ana Mafalda Silva
b
, Bruno Mendes
b
, Tiago
Filipe
b

a
Professora de Fsica e Qumica, Oficinas de S. Jos, Praa S. Joo Bosco, 34, 1399-
007Lisboa
b
Alunos do 10. ano, Oficinas de S. Jos, Praa S. Joo Bosco, 34, 1399-007Lisboa
*maria_goreti@hotmail.com

Conceitos como massa volmica e percentagem em massa, entre outros,
parecem-nos bsicos at ao momento em que descobrimos que os nossos alunos
perceberam tudo ao contrrio daquilo que queramos ensinar! O que que falha
na nossa tentativa de os ensinar e de fazer com que apreendam alguma coisa?
Um ensino livresco e longe da manipulao de variveis em contexto real
associado s vivncias dos alunos? Um formulrio imenso que, actualmente, no
legtimo que ocupe espao de memria cerebral dos nossos alunos? para
pensar
Nesta apresentao no dada
resposta a nenhuma das questes
anteriores, apenas inteno
partilhar experincias de
aprendizagem, que tm sido
algumas tentativas de conseguir
melhores resultados na qualidade
das aprendizagens (no)
conseguidas pelos nossos alunos.
Contemplam-se actividades
experimentais realizadas pelos
alunos, e a forma como os resultados
das mesmas foram tratados. Os
recursos utilizados foram do
quotidiano dos alunos, as ferramentas
de tratamento so as que as TIC lhe
oferecem, o trabalho, esse, dos
alunos, e as dificuldades foram
muitas
Qual foi efeito que estas
actividades tiveram na apreenso dos
conceitos? Talvez o tempo nos
responda, um dia


Figura 1. Estudo da massa volmica
Figura 2. Estudo da percentagem em massa
62




COMUNICAES
EM PAINEL


Figure 1. Diastereoselective ortho-lithiation of I followed by reaction
with an electrophile.

OXAZAPHOSPHOLIDINE-OXIDE, A VERSATILE
ORTHO-DIRECTING GROUP

Nelson C. Martins
a,b
*, Amadeu F. Brigas
b
, Jianliang Xiao
a

a
Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, U.K.
b
CIQA, Faculdade de Cincias e Tecnologia, Universidade do Algarve, 8005-139 Faro,
Portugal
*n.martins@liverpool.ac.uk

Among several types of chiral ligands, ferrocene derivatives have been
highlighted for their desirable features and significant contribution in asymmetric
catalysis.
1
Many methodologies have been applied in the synthesis of 1,2-
disubstituted, planar chiral, ferrocenyl ligands, one of them being the direct ortho
metalation (DoM).
2
The pioneering work of Ugi et al. led to the development of
a series of other ortho-directing groups in addition to Ugis amine, namely,
sulfoxides, acetals, oxazolines, azepines, pyrrolidines, hydrazones, sulfoximines,
O-methyl ephedrine derivatives, imidazolines, phosphine oxides,
oxazaphospholidine oxide and of late methoxy-imino auxiliaries.
1-3











In our group the oxazaphospholidine oxide moiety has revealed to be an
excellent ortho-directing group for the diastereoselective deprotonation of
ferrocene allowing the synthesis of 1,2-disubstituted ferrocene derivatives, with
planar chirality.
2
We herein report the synthesis of a new epimer (2S,4S,5R)-3,4-
dimethyl-2-ferrocenyl-5-phenyl[1,3,2]oxazaphospholidine 2-oxide (I) and its
diastereoselective ortho-lithiation to afford several new, planar chiral,
compounds (II) as well as the brief comparison of some of these ligands in the
allylic alkylation of rac-1,3-diphenyl-3-acetoxyprop-1-ene.
Further studies on this ortho-directing group are discussed, specifically its
use in the synthesis of new, planar chiral, 1,2-disubstituted, ferrocenes
containing a primary phosphine group and in the synthesis of ferrocene ligands
presenting both planar chirality and a scalemic P-chiral phosphine group.

[1] R. Arrays, J. Adrio, J. Carretero, Angew. Chem., Int. Ed. 45 (2006) 7674.
[2] D. Vinci, N. Mateus, S. Wu, F. Hancock, A. Steiner, J. Xiao, Org. Lett. 8 (2006) 215.
[3] B. Ferber, S. Top, P. Herson, G. Jaouen, Organometallics. 26 (2007) 1686.

THF -78C-RT
Overnight
P
O
N
Fe
O
Me
Ph
t
BuLi 1.
EX 2.
P
O
N
Fe
O
Me
Ph
E
46-61%, 99% de
-78C
E: Me, TMS, TES, PPh
2
, PCy
2
...
(I)
(II)
65


Figura 1. Curvas cinticas de adsoro
de NO, a 25C e 80 kPa, nos diferentes
materiais estudados.
0
2
4
6
8
10
12
0 20 40 60
Tempo / h
%

d
e

N
O

n
o

s

l
i
d
o
MOR CaA ETS-4
PILC Argila
MATERIAIS POROSOS PARA ADSORO
DE XIDO NTRICO

Moiss L. Pinto
a,b
*, Joo Pires
a
, Joo Rocha
b

a
Departamento de Qumica e Bioqumica e CQB, Faculdade de Cincias, Universidade
de Lisboa, Campo Grande, 1749-016 Lisboa
b
Departamento de Qumica e CICECO, Universidade de Aveiro, 3810-193 Aveiro
*moises.pinto@fc.ul.pt

Embora seja bastante txico em concentraes elevadas, o xido ntrico (NO)
um agente biolgico crucial na regulao dos sistemas cardiovascular, nervoso
e imunitrio. O fornecimento de NO exgeno pode ser uma terapia atractiva para
uma serie de patologias, mas a diversidade dos seus efeitos no corpo humano
levanta preocupaes, o que tem
dificultado o desenvolvimento de
algumas aplicaes de NO. Uma via para
superar estas dificuldades o
desenvolvimento de materiais que
armazenem NO e possam liberta-lo em
locais especficos do corpo. Os materiais
adsorventes podem ser utilizados com
esta finalidade [1].
No presente trabalho, foram
estudados diferentes materiais
adsorventes, nomeadamente dois zelitos
- mordenite (MOR) e CaA-, um
titanosilicato (ETS-4) e dois materiais
argilosos - uma argila com pilares (PILC)
e uma argila natural. Foi efectuada adsoro de NO e estudadas por
infravermelho amostras com NO adsorvido.
Os resultados de adsoro revelaram comportamentos muito diferentes por
parte dos materiais estudados, no s quanto sua capacidade, mas tambm em
relao as velocidades de adsoro. Como pode ser observado na Figura 1,
alguns materiais atingem praticamente o equilbrio ao fim de 20 horas (MOR),
enquanto que outros ao fim de 60 horas ainda se encontram claramente longe do
equilbrio (ETS-4). As cinticas de desadsoro de NO so tambm muito
diferentes entre os materiais, existindo sempre uma quantidade considervel de
NO que no removido.
Os estudos por FTIR revelaram a presena de NO adsorvido nos materiais,
mesmo depois de submetidos a vcuo. Estes dados evidenciam que a adsoro de
NO acompanhada de fortes interaces com a superfcie, com a eventual
formao de outros xidos de azoto.

[1] P. S. Wheatley, A. R. Butler, M. S. Crane, S. Fox, B. Xiao, A. G. Rossi, I. L. Megson,
R. E. Morris, J. Am. Chem. Soc. 128 (2006) 502.
66


PARTIAL OXIDATION OF METHANE OVER
HETEROBIMETALLIC COPPER-LANTHANIDE OXIDES

A. Ferreira, A. Janeco, N. Pinho, A. P. Gonalves, J. Branco*
Departamento de Qumica do Instituto Tecnolgico e Nuclear, Estrada Nacional 10,
2686-953 Sacavm, Portugal
*jbranco@itn.pt

The objective of this work is to study partial oxidation of methane over
heterobimetallic copper-lanthanide oxides. The main goal is the production of
syngas (CO+H
2
) eq. 1, with high selectivity and an optimized ratio H
2
/CO=2,
which is ideal for the synthesis of methanol through the Fischer-Tropsch process,
a process of great commercial importance.
(1)
Binary intermetallic compounds of the type LnCu
2
(Ln=La, Ce, Pr, Eu and
Dy) were used as catalytic precursors
1
and a comparison with simple oxides was
also undertaken.
In this communication, we will only go to approach the results of cerium
compounds that were compared with those of a commercial catalyst of rodium
(5%Rh/Al
2
O
3
), that it is known to be sufficiently active and stable. This study
was performed within the temperature range 350 800C and for a high GHSV
(8500 ). For both catalysts, it was observed an increase of the
selectivities to H
2
and CO with the temperature and a significant reduction of the
selectivity to CO
2
. At 750 C, the CH
4
conversion is of the order of 90% over the
two catalyst and the ratio H
2
/CO=4 (selectivities to H
2
and CO of 80% and 20%,
respectively).
These results are very interesting because the intermetallic catalyst is cheaper
than noble catalyst, and it become an excellent option for future application.

[1] Danielle Ballivet-Tkatchenko, Joaquim Branco, Antonio Pires de Matos. J. Phys.
Chem. 99 (1995) 5481; J. Alloys Compd. (2007), doi:10.1016/j.jallcom.2007.10.001.
67


HYDROFORMYLATION OF KAURANE DERIVATIVES:
MECHANISTIC STUDIES

Andreia F. Peixoto
a
*, Marisela Reyes
b
, Ricardo R. Contreras
b
,
Eduardo N. dos Santos
c
, J. Carles Bayn
d
, Mariette M. Pereira
a

a
Departamento de Qumica Universidade de Coimbra, 3004-535 Coimbra
b
Departamento de Qumica, Universidade de Los Andes, Mrida, Venezuela
c
Departamento de Qumica-ICEx, UFMG, 31270-901 Belo Horizonte, Brazil
d
Universitat Autnoma de Barcelona, Bellaterra, 08193 Barcelona, Spain
*apeixoto@qui.uc.pt

Kaurenic and grandiflorenic acids and Kaurenol are typical examples of
natural diterpenes [1] known to show a interesting biological activity [2]. Both
acids and Kaurenol contain an exocyclic methylenic double bond that allows
further functionalization on their structure. In order to expand the number of
derivatives of these natural products, we have undertaken a study on the
hydroformylation of the methyl esters of the two acids and the trimethylsilyl
ether of kaurenol. The substrates have been hydroformylated by using
unmodified Rh catalysts, as well as
Rh/PPh
3
and Rh/tris-(o-t-butyl
phenyl) phosphite catalytic systems
at 100C and 20 bar of CO/H
2
(1:1).
For the three substrates, the two Rh
catalysts modified with P-donor
ligands allowed high conversions
and chemo- and regioselectivities in
the diastereoisomeric pair of linear
aldehydes. In all cases, the
stereoselectivity observed is
strongly dependent of the system used, being the most diastereoselective the
least hindered unmodified Rh/CO catalyst. A correlation between the higher
diastereoselectivity and the faster |-elimination of the metal-alkyl intermediate
observed in the unmodified system will be presented [3].

Acknowledgments: The authors thank FCT (PTDC/QUI/66015/2006) for financial
support. A. Peixoto also thanks FCT the PhD grant (SFRH/BD/29681/2006).

[1] A. Usubillaga, M.C. Capra, Fitoterapia LIX 5 (1988) 383.
[2] E.L. Ghisalberti, Fitoterapia LXVIII 4 (1997) 303.
[3] A. F. Peixoto, D. S. de Melo, Tnia F. Fernandes, Y. Fonseca, E. V. Gusevskaya, A.
M.S. Silva, R. R. Contreras, M. Reyes, A. Usubillaga, E. N. dos Santos, M. M.
Pereira, J. C. Bayn, Appl Catal A: Gen (2008), doi:10.1016/j.apcata.2008.02.015.
68


OZONIZAO CATALTICA DE COMPOSTOS
ORGNICOS MODELO EM SOLUO AQUOSA

Patrcia C. C. Faria*, Jos J. M. rfo, Manuel F. R. Pereira
Laboratrio de Catlise e Materiais, Departamento de Engenharia Qumica, Faculdade
de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*pfaria@fe.up.pt

A ozonizao cataltica heterognea tem sido estudada intensivamente no
mbito da aplicao em tratamento de guas e guas residuais, com o objectivo
de aumentar o grau de mineralizao de poluentes orgnicos.
Neste trabalho apresentam-se os resultados da ozonizao de compostos
aromticos (cido benzenosulfnico, cido sulfanlico e anilina) e de cidos
carboxilicos seleccionados (cidos oxlico e oxmico) catalisada por carvo
activado, xido de crio e por um compsito de carvo activado e xido de crio
[1,2]. Faz-se a avaliao da actividade cataltica do carvo activado e dos
catalisadores contendo crio na ozonizao de compostos orgnicos modelo e
mostra-se a existncia de um efeito sinrgico entre o carvo activado e o xido
de crio. Os materiais contendo crio foram caracterizados por XRD, SEM e
XPS com o intuito de se correlacionar a actividade dos catalisadores com a sua
estrutura e composio qumica. Ambos
os materiais contendo crio revelaram ser
altamente eficientes na ozonizao
cataltica dos compostos seleccionados.
Comparativamente com o desempenho do
carvo activado obteve-se uma melhoria
signifivativa no grau de mineralizao
dos referidos compostos, em particular
nos casos do cido oxlico e do cido
benzenosulfnico, tendo-se conseguio
alcanar mineralizaes completas para
tempos de reaco relativamente curtos
(Figura 1). Verificou-se a existncia de
um efeito sinrgico entre o carvo
activado e o xido de crio. O mecanismo de ozonizao catalisada pelo
compsito envolve reaces de superfcie, semelhantes s que ocorrem na
ozonizao na presena carvo activado, e formao de radicais HO

promovida
pela presena do xido de crio.
Agradecimentos: Fundao para a Cincia e a Tecnologia - BD/18169/2004 and
POCTI/FEDER (POCTI/1181).
[1] P.C.C. Faria, J.J.M. rfo, M.F.R. Pereira, Appl. Catal. B-Environ. 79 (2008) 237.
[2] P.C.C. Faria, J.J.M. rfo, M.F.R. Pereira, Appl. Catal. B-Environ.
doi:10.1016/j.apcatb.2008.02.010.
Figura 1. Ozonizao cataltica do
cido benzenosulfnico (C
0
= 1mM,
pHi = 3.0, catalisador = 0.5 g/L).
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0


T
O
C
/
T
O
C
0
t (min)
O
3
O
3
/AC
0
O
3
/Ce-O
O
3
/AC
0
-Ce-O
69


REDUO CATALTICA COM HIDROGNIO DE
NITRATOS E NITRITOS EM GUA

Olvia Salom G. P. Soares, Jos J. M. rfo, Manuel F. R. Pereira*
Laboratrio de Catlise e Materiais, Departamento de Engenharia Qumica, Faculdade
de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*fpereira@fe.up.pt

A reduo cataltica de nitratos uma das tecnologias emergentes mais
promissoras no tratamento de guas poludas. Este processo consiste na
converso de nitratos em azoto na presena de catalisadores bimetlicos por
aco de um agente redutor [1,2]. Neste trabalho, avaliaram-se as actividades e
as selectividades de vrios catalisadores suportados em carvo activado com o
objectivo de seleccionar os sistemas mais promissores na reduo de nitratos e
nitritos em guas. Estudaram-se dez catalisadores monometlicos na reduo de
nitratos e nitritos e treze catalisadores bimetlicos na reduo de nitratos. Os
ensaios catalticos foram realizados num reactor semi-fechado temperatura
ambiente e presso atmosfrica usando hidrognio como agente redutor.
0 30 60 90 120 150 180 210 240 270 300
0
10
20
30
40
50
60
70
80
90
100
1% Pt_ACo
1% Pd_ACo
1% Cu_ACo
1% Sn_ACo
1% Ru_ACo
1% Rh_ACo
1% Ni_ACo
1% Ir_ACo
1% Fe_ACo
1% Zn_ACo
ACo
Branco
C
N
O
2 - (
m
g
/
L
)
t(min)
0 30 60 90 120 150 180 210 240 270 300
0
10
20
30
40
50
60
70
80
90
100
C
N
O
3 - (
m
g
/
L
)
t(min)
1% Pd - 1% Cu_ACo
1% Pt - 1% Cu_ACo
1% Rh - 1% Cu_ACo
1% Ru - 1% Cu_ACo
1% Pd - 1% Ir_ACo
1% Pd - 1% Sn_ACo
1% Pd - 1% Fe_ACo
1% Pd - 1% Ni_ACo
1% Pd - 1% Zn_ACo
1% Ir - 1% Cu_ACo
1% Rh - 1% Sn_ACo
1% Pt - 1% Sn_ACo
1% Pt - 1% Fe_ACo

Figura 1. Concentrao de nitrito em
funo do tempo na presena dos
catalisadores monometlicos.
Figura 2. Concentrao de nitrato em
funo do tempo na presena dos
catalisadores bimetlicos.
(C
i
=100 mg/L; pH=5,5; catalisador=0,5 g/L; Q
H2
=100 Ncm
3
/min; Q
CO2
=100 Ncm
3
/min; T=25C).


Observou-se que os catalisadores monometlicos so praticamente inactivos
para a reduo de nitratos, com excepo do catalisador de Ru. O nitrito
reduzido na presena de catalisadores monometlicos com a seguinte ordem de
actividades: Pd >> Ir > Pt >> Rh >> Cu > Zn Ru; os outros metais testados no
apresentam actividade (Figura 1). Nos catalisadores bimetlicos observou-se a
seguinte ordem de actividades: Rh-Cu >> Pd-Cu >> Ir-Cu Pt-Cu Rh-Sn >>
Pd-Ni > Ru-Cu Pt-Sn. Nas condies testadas os catalisadores bimetlicos Pd-
Ir, Pd-Sn, Pd-Fe, Pd-Zn e Pt-Fe so inactivos (Figura 2). O par Rh-Cu apresenta
a converso mais elevada mas o catalisador de Pd-Cu parece ser o melhor
quando se considera tambm a selectividade em azoto.
Agradecimentos: Fundao para a Cincia e a Tecnologia (FCT) - BD/30328/2006 e
POCTI/FEDER (POCTI/1181).
[1] K.D. Vorlop, T. Tacke, Chem. Ing. Tech. 61 (1989) 836.
[2] A. Pintar, Catal. Today 77 (2003) 451.
70


NEW HETEROGENEOUS CHIRAL VANADIUM(V) SALEN
CATALYSTS FOR THE STRECKER REACTION

M. Alexandra Esteves
a
*, Joo C. Oliveira
a
, A. Margarida Guerreiro
a
,
Clia Santos
a
, Carlos Baleizo
b
a
INETI-DTIQ, Estrada do Pao do Lumiar, 1649-038 Lisboa
b
Centro de Qumica-Fsica Molecular, IST, Av. Rovisco Pais 1049-001 Lisboa
*alexandra.esteves@ineti.pt, fax:217168100

The addition of cyanide to imines (Strecker reaction) using a chiral catalyst
constitutes one of the most direct and viable strategies for the asymmetric
synthesis of chiral o-amino acids derivatives, which are important building
blocks in a variety of biologically-interesting natural products. Homogeneous
metal complexes with chiral ligands are currently the most widely used and
versatile enantioselective catalysts. Metallic salen complexes, such as
aluminium(III) and vanadium(V) salen, proved to be very efficient homogeneous
catalysts for the Strecker reaction.[1,2] In spite of the good results achieved with
these homogeneous catalysts
(excellent enantioselectivities
conjugated with high yields), if
they were transformed into
heterogeneous systems,
environmental and experimental
advantages would be obtained,
since the separation of the catalyst
would be done by simple filtration,
avoiding the production of wastes
and leading to economic benefits, due to their reuse.[3]
As a part of an ongoing project, herein, we present the preparation of five
new heterogeneous catalysts resulting from the immobilization of vanadium(V)
salen complexes to solids supports, namely a polystyrene polymer and an
amorphous silica, using several anchoring strategies. The solid catalysts were
characterized by analytical and spectroscopic techniques and tested in a Strecker
type reaction, the asymmetric addition of hydrogen cyanide (generated in situ
from TMSCN) to N-benzyl benzylimine.[2]

[1] J. F. Larrow, E. N. Jacobsen; Topics Organomet. Chem., 6 (2004) 123.
[2] J. Blacker, L. A. Clutterbuck, M. R. Crampton, C. Grosjean, M. North; Tetrahedron:
Assymetry, 17 (2006) 1449.
[3] C. Baleizo, H. Garcia; Chem. Rev., 106 (2006) 3987.
A
O
N N
O
V
O
OH
2
S OEt
O
O
O
A = NH or SH
71


AMINE-FUNCTIONALISED SILICA NANOPARTICLES AS
SUPPORTS FOR [M(ACAC)
2
] CATALYSTS

Jos F. Silva
a
, Clara Pereira
a
*, Susana L. H. Rebelo
a
, Ana P. Carvalho
b
,
Joo Pires
b
, Cristina Freire
a

a
REQUIMTE, Departamento de Qumica, FCUP, 4169-007 Porto, Portugal
b
Departamento de Qumica e Bioqumica and CQB, FCUL, 1749-016 Lisboa, Portugal
*clara.pereira@fc.up.pt

Copper(II) and vanadyl(IV) acetylacetonate complexes, [Cu(acac)
2
] and
[VO(acac)
2
], are efficient homogeneous catalysts in the aziridination of olefins
and in the epoxidation of allylic alcohols respectively [1]. These catalytic
reactions are of great importance since aziridines and epoxides are valuable
intermediates in organic synthesis. The immobilisation of these complexes onto
solid supports presents several advantages for catalytic reactions, namely
improving the chemical stability of the anchored catalyst and facilitating its
separation and reuse in further cycles. These complexes have already been
microencapsulated in polystyrene and immobilised onto amine-functionalised
inorganic supports such as activated carbons, mesoporous silicas and clays [3].
Silica nanoparticles are promising materials for application in several
research areas such as Medicine, Biology, Chemistry and Materials Science,
mostly due to their biocompatibility and easy surface modification.
In this work, [Cu(acac)
2
] and [VO(acac)
2
] complexes were immobilised onto
silica nanoparticles previously functionalised with 3-aminopropyltriethoxysilane
(Scheme 1).

Scheme 1. Schematic representation of catalysts preparation

The materials were characterised by chemical analysis, FTIR, XPS, N
2

adsorption isotherms at -196 C and solid state NMR (
13
C and
29
Si). Finally, the
[Cu(acac)
2
] and the [VO(acac)
2
] based materials were tested as heterogeneous
catalysts in the styrene aziridination using PhI=NTs as nitrogen source and in the
geraniol epoxidation using t-BuOOH as oxygen source, respectively.

Acknowledgements: This work was partially funded by FCT and FEDER through project
PTDC/CTM/65718/2006. CP thanks FCT for a PhD grant.

[1] (a) P. Mller et al. Chem. Rev. 103 (2003) 2905. (b) C. Bolm, Coord. Chem. Rev. 237
(2003) 245.
[2] (a) C. Pereira et al. J. Colloid Interface Sci. 316 (2007) 570. (b) C. Pereira et al. J.
Mol. Catal. A: Chem. 283 (2008) 5.

dry toluene, 24 h ref lux
CHCl
3
, 24 h ref lux
OH
OH
Si C
2
H
5
O
O
(CH
2
)
3
NH
2
O
Si C
2
H
5
O
C
2
H
5
O
(CH
2
)
3
NH
2
C
2
H
5
O
O
M
O
CH
3
CH
3
O
O
H
3
C
H
3
C
Si C
2
H
5
O
O
(CH
2
)
3
N
O
O
M
CH
3
H
3
C
O O
CH
3
H
3
C
72


NEW Rh/CHIRAL MONOPHOSPHITE CATALYST IN
HYDROFORMYLATION OF STYRENE DERIVATIVES

Rui M. B. Carrilho
a
*, Artur R. Abreu
a
, Paula S. S. Lacerda
a
, Maria
Jos S. M. Moreno
b
, Mariette M. Pereira
a
, Joan C. Bayn
c

a
Departamento de Qumica, F.C.T. - Univ. de Coimbra, Rua Larga, 3004-535 Coimbra
b
CEF, Fac. de Farmcia da Universidade de Coimbra,Rua do Norte, 3000-295 Coimbra
c
Departament de Qumica Inorganica, Universitat Autnoma de Barcelona, Bellaterra,
08193 Barcelona, Spain
*rmcarrilho@gmail.com

Catalytic asymmetric hydroformylation of olefins is a highly attractive and
useful method for the preparation of optically active aldehydes, which can be
important intermediates for the synthesis of biologically active compounds.[1]
Several rhodium catalytic systems bearing diphosphine, diphosphite and
phosphine-phosphite ligands have been widely investigated in hydroformylation
reactions,[2-4] however the enantioselectivity of asymmetric hydroformylation
of styrene with Rh catalytic systems
using monophosphites as ligands
was generally poor.[1]
In this communication, a new
bulky monophosphite ligand (L)
derived from chiral binaphtol is
featured, figure 1.
Its application in rhodium-
catalyzed asymmetric hydroformy-
lation of styrene and its derivative
1,2-dimethoxy-4-propenil-benzene
has been evaluated. For both
substrates, the effect of pressure and
temperature on the activity, chemo,
regio and enatioselectivity of the Rh/L catalytic system will be discussed. The
same catalytic system was also evaluated in the hydroformylation of steroids.
Acknowledgements: The authors thank FCT for supporting the project
PTDC/QUI/66015/2006. Rui M. B. Carrilho also thanks FCT for the research grant from
the mentioned project.
[1] L.L Wang, R.W. Guo, Y.M. Li, A.S.C. Chan, Tetrahedron: Asymmetry 16 (2005)
3204.
[2] M. Diguez, M.M. Pereira, A.M. Masdeu-Bult, C. Claver, J.C. Bayn, J. Mol. Catal.
A: Chemical 143 (1999) 111.
[3] S. Deerenberg, P.C.J. Kamer, P.W.N.M. van Leuwen, Organometallics 19 (2000)
2065.
[4] T.P. Clark, C.R. Landis, S.L. Freed, J. Klosin, K.A. Abboud, J. Am. Chem. Soc. 127
(2005) 5040.
O
O
P
O
O
O
O
Ph
Ph
Ph
R'
R'
R'
R'
C
CO / H
2
1.a,b
R R
O H
Rh-L
L =
2.a,b
a) R = H , R' = H
b) R = CH
3
, R' = OCH
3
(> 94%)
Figure 1. Hydroformylation of styrene
derivatives with a Rh/monophosphite catalyst
73


Ni-Cu RANEY-TYPE CATALYSTS FOR CO
X
-FREE
HYDROGEN PRODUCTION VIA METHANE CRACKING

A. F. Cunha, J. J. M. rfo, J. L. Figueiredo*
Laboratrio de Catlise e Materiais, Departamento de Engenharia Qumica, Faculdade
de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*
jlfig@fe.up.pt

Increasing concerns about the emission of greenhouse gases, together with
the depletion of fossil fuel reserves, have stimulated the search for alternative
energy solutions [1], such as low temperature Proton Exchange Membrane Fuel
Cells (PEMFC), which use hydrogen as fuel. However, PEMFC tolerate very
low levels of CO. In principle, the production of CO
x
-free hydrogen is possible,
via methane decomposition, when appropriate catalysts are available (CH
4

C + 2 H
2
). This process can even be of economic interest when the formed
carbon solids consist of high-value carbon nanofibers (CNF) and carbon
nanotubes (CNT) as in the case of the present work. Skeletal Raney-type
catalysts used in this work were prepared from AmperkatSK Me-Al alloys
(Me=Ni,Cu), supplied by H.C.Starck Gmbh, Bayer Material Science Company.
The alloys were activated by leaching the Al, at room temperature, with a
concentrated NaOH solution [2]. Three catalysts were prepared from these
alloys: monometallic Ni, monometallic Cu and bimetallic Ni-Cu (1:1 by weight).
They were placed in a tubular reactor and dried overnight under a N
2
stream. The
original alloys, the resulting catalysts and the carbon deposits where
characterized by appropriate techniques; Table 1 summarises the main results:
atomic ratios (R=M/(M+Al)), average particle diameters and specific BET
surface areas. Isothermal runs were carried out at 600C, with a total volumetric
flow-rate of 110 Ncm
3
/min (CH
4
/N
2
= 0.1). The conversions obtained at 2 and 5
hours are included in Table 1. They show that although Cu has no appreciable
activity, its incorporation into the Ni catalyst significantly enhances its stability.

Table 1: Characterization of the alloys and catalysts and CH
4
conversions after 2 and 5 h
Sample Alloy Catalyst CH
4
conversion


d
[m]
R

d
[m]
R
S
BET

[m
2
/g]

h
CH
X
2
4

[%]
h
CH
X
5
4

[%]
Ni30 285 0.17 156 0.85 64 72.0 33.2
Cu50 50 0.65 46 0.95 17 2.5 1.9
Ni30-Cu50 / / 83 0.90 36 66.3 59.9

Acknowledgements: Fundao para a Cincia e a Tecnologia (FCT) and FEDER
(BD/16035/2004 and POCTI/1181).

[1] N. Muradov, T.N. Veziroglu, Int. J. Hydrogen Energy 30 (2005) 225.
[2] U. Birkenstock, U.S. Patent 5,090,997 H.C.Starck GmbH, Bayer AG (1992).
74


DESENVOLVIMENTO DE CARVES ACTIVADOS A
PARTIR DE PRECURSORES NATURAIS

Joo M. Valente Nabais*, Peter J. M. Carrott, Manuela L. Ribeiro
Carrott, Jos A. F. L. Gomes
Centro de Qumica de vora & Departamento de Qumica, Universidade de vora, Rua
Romo Ramalho, 59, 7000-671 vora
*jvn@uevora.pt

Os materiais de carbono, e em particular os carves activados, so
actualmente um dos materiais adsorventes mais relevantes e fundamentais na
nossa sociedade e nas mltiplas reas da actividade humana. Os carves
activados so usados numa vasta gama de aplicaes industriais e na vida do dia-
a-dia, quer em fase gasosa quer em fase lquida, que vo desde aplicaes em
medicina at armazenamento de gases passando por remoo de poluentes,
separao de gases, remoo de odores e catlise, entre muitas outras. Uma das
reas que mais tem motivado, e que continua intensamente a motivar, os
investigadores de todo o mundo a procura de novos precursores e metodologias
para a produo de carves activados a custos mais moderados e que permitam
obter materiais com caractersticas qumicas e texturais controladas tendo em
mente algumas aplicaes especficas. neste mbito que o presente trabalho foi
desenvolvido.
Como precursores foram utilizados dois resduos biomssicos com
caractersticas diferentes, a colza e o kenaf. O teor em lignina e halocelulose em
percentagem mssica respectivamente de 26 e 56% e de 18 e 70% para a colza
e para o kenaf. Os carves activados foram produzidos por carbonio a 400C e
activao com dixido de carbono a 700C durante tempos variados por forma a
obter diferentes graus de queima. Os carves activados so produzidos na forma
granular e possuem caractersticas bsicas com ponto de carga zero entre 9.27 e
9.98, determinado pelo mtodo das titulaes mssicas. As caractersticas
porosas determinadas a partir de isotrmicas de adsoro de azoto a 77K e
anlise das isotrmicas por mtodos convenientes mostraram que os materiais
so essencialmente microporosos com rea superfical aparente BET de
aproximadamente 1000m
2
/g, volume poroso 0.5cm
3
/g e rea externa abaixo de
100m
2
/g.
De notar que o presente trabalho encontra-se neste momento em fase de
desenvolvimento e portanto os resultados agora relatados so apenas parcelares.
No decorrer do Encontro sero apresentados os resultados da total caracterizao
dos materiais e tambm ensaios de adsoro em fase lquida de compostos
fenlicos.

Os autores agradecem Fundao para a Cincia e Tecnologia (FCT) e FEDER o
financiamento concedido no mbito do projecto PTDC/CTM/66552/2006.
75


CARACTERIZAO E ESTABILIDADE ESTRUTURAL DE
TITANOSSILICATOS MESOPOROSOS

J. Valrio, C. Galacho, M. M. L. Ribeiro Carrott*, P. J. M. Carrott
Centro de Qumica de vora and Departamento de Qumica, Universidade de vora, Rua
Romo Ramalho n59 7000-671 vora Portugal
*manrc@uevora.pt

A introduo de titnio em materiais mesoporosos com estrutura ordenada,
do tipo MCM-41 e SBA-15, perfila-se como sendo de grande interesse no mbito
da catlise heterognea oxidativa dado que permite ampliar a gama de
aplicabilidade a substratos de maiores dimenses, de reconhecida importncia
em Qumica Fina. No entanto, esta potencial aplicao industrial e tecnolgica
implica que os referidos materiais exibam estabilidade estrutural,
designadamente, estabilidade mecnica, hidrotrmica e trmica.
No presente trabalho apresenta-se um estudo referente sntese,
caracterizao e resistncia aplicao do aumento progressivo de presso
externa unidireccional de amostras de Ti-MCM-41 e de Ti-SBA-15, contendo
diferentes teores de metal (5Si/Ti100), preparadas por substituio isomrfica
durante a sntese.
Os estudos de estabilidade mecnica
foram efectuados por compresso da amostra
numa prensa hidrulica (Specac) e a
caracterizao estrutural das amostras foi
efectuada por adsoro de N
2
a 77K
(Sorptomatic 1990) e difraco de raios X
(Bruker AXS, D8 advance). A ttulo
exemplificativo apresenta-se na Fig. 1 os
difractogramas de raios X obtidos para a
amostra Ti-SBA15-100 sujeita ao aumento
progressivo de presso externa entre 0 e
814MPa. Verifica-se que a estrutura
mesoporosa ordenada caracterstica dos
materiais SBA-15 observada, pelo menos,
at valores de 518MPa e que o colapso da
mesma ocorre aproximadamente a 814MPa.

Figura 1. DRX da amostra
Ti-SBA15-100.
Analogamente ao que se verificou para os materiais Ti-MCM-41, preparados
temperatura e presso ambiente [1,2], os resultados obtidos indiciam que os
materiais em estudo apresentam uma considervel estabilidade mecnica e que a
mesma praticamente independente da razo molar de sntese Si/Ti.

[1] C. Galacho, M.M.L. Carrott, P.J.M. Carrott. Micropor. Mesopor. Mater. 108 (2008)
283.
[2] C. Galacho, M.M.L. Carrott, P.J.M. Carrott. Micropor. Mesopor. Mater. 100 (2007)
312.
0 2 4 6 8 10
2u /
I
n
t
e
n
s
i
d
a
d
e

/

u
.
a
.0MPa
74MPa
148MPa
222MPa
370MPa
518MPa
666MPa
814MPa
76


ADSORO DE O-DICLOROBENZENO EM
CARBONIZADOS DE P DE CORTIA

Ana S. Mestre*, Marta Andrade, Joo Pires, Ana P. Carvalho
Departamento de Qumica e Bioqumica, Centro de Qumica e Bioqumica, Faculdade de
Cincias, Universidade de Lisboa, Campo Grande Ed. C8, 1749-016, Portugal
*asmestre@fc.ul.pt

Dioxina a designao geral usada para dibenzo-p-dioxinas policloradas e
dibenzofuranos policlorados, que apresentam mais de 200 ismeros. Estes
compostos so produzidos por diversas fontes, sendo a mais importante os
processos de incinerao de desperdcios industriais e urbanos. De entre as
metodologias que permitem uma reduo efectiva das emisses de dioxinas, as
que usam carves activados como adsorventes esto entre as mais comuns. A
tecnologia de injeco de carvo activado permite a remoo eficiente destes
poluentes, tendo como grande vantagem uma fcil implementao [1].
Uma das formas de diminuir os custos deste processo de controlo de
emisses gasosas reduzir a quantidade de adsorvente injectado ou recorrer a
materiais menos onerosos. Nesta linha, iniciou-se o estudo de preparao de
carbonizados de p de cortia, um desperdcio industrial muito importante no
nosso pas (produo anual ~ 35 000 ton). Os custos de produo destes
carbonizados so inferiores aos dos carves activados, uma vez que so
preparados num nico passo e recorrendo a temperaturas mais baixas, o que
diminui o consumo energtico. Os carbonizados apresentam uma estrutura
porosa menos desenvolvida do que os carves activados. Contudo, tendo em
vista uma aplicao em tecnologias de injeco no essencial uma elevada
capacidade de adsoro, uma vez que estes os adsorventes esto em contacto
com as dioxinas durante um intervalo de tempo muito curto no chegando, muito
provavelmente, a atingir a saturao.
Nesta comunicao apresentam-se os
resultados da caracterizao textural de
carbonizados de p de cortia em diferentes
condies experimentais (Fig. 1). As suas
potencialidades como adsorventes de dioxinas
foram avaliadas pela adsoro de uma molcula
modelo deste tipo de poluentes,
o-diclorobenzeno. Os resultados obtidos mostram
que, nos instantes iniciais, os carbonizados retm
um maior volume de adsorvato, apesar de
apresentarem menor capacidade de adsoro
global que o carvo comercial usado para
comparao.

[1] G. McKay. Chem. Eng. J. 86 (2002) 343.
Figura 1. Isotrmicas de
adsoro de CO
2
a 0 C nos
carbonizados temperatura
indicada.
77


Figura 1. Isotrmicas de
adsoro de N
2
a -196 C.
ACTIVAO DE CAROOS DE PSSEGO COM K
2
CO
3


Ana S. Bexiga
a
*, Ana S. Mestre
b
, Isabel M. Fonseca
a
, Ana P. Carvalho
b

a
Departamento de Qumica, REQUIMTE, CQFB, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, Quinta da Torre, 2829-516 Caparica, Portugal
b
Departamento de Qumica e Bioqumica, Centro de Qumica e Bioqumica, Faculdade
de Cincias, Universidade de Lisboa, Campo Grande Ed. C8, 1749-016, Portugal
*anabexiga@gmail.com

Na sequncia dos estudos que tm vindo a ser desenvolvidos sobre a
valorizao de resduos industriais nacionais (p de cortia), apresentam-se nesta
comunicao os resultados relativos a carves activados com K
2
CO
3
, preparados
a partir de desperdcios da indstria de sumos: caroos de pssego.
Os caroos de pssego foram modos e peneirados recolhendo-se a fraco
com granulometria inferior a 0.297 mm, no tendo sido realizado qualquer pr-
tratamento a este material. Foram preparados dois carves activados a partir da
referida fraco, seguindo o procedimento utilizado para preparar os carves de
p de cortia [1]. A amostra PAC foi obtida por activao qumica com K
2
CO
3

(K
2
CO
3
:caroo de pssego razo mssica 1:1) a 700 C durante 1h com fluxo de
azoto de 5 cm
3
s
-1
. Depois de arrefecida sob fluxo de azoto, a amostra foi lavada
com gua destilada at pH 7 e seca a 100 C. A amostra PPAC foi preparada por
activao fsica da amostra PAC com vapor de gua a 750 C durante 1h. O
vapor de gua foi gerado pela presso de vapor da gua temperatura ambiente,
tendo sido transportado por um fluxo de azoto de 5 cm
3
s
-1
. As activaes foram
realizadas num forno horizontal (Thermolyne, modelo 21100).
Os carves activados foram caracterizados
por adsoro de N
2
a -196 C num
equipamento volumtrico convencional
equipado com medidor de presso MKS-
Baratron (310BHS-1000, 0-133kPa). As
isotrmicas mostram que a metodologia
utilizada permitiu obter amostras
essencialmente microporosas, com reas
especficas aparentes da ordem de 1000 m
2
g
-1
.
O teor em cinzas foi determinado pela massa
residual obtida aps a combusto das amostras
em ar de acordo com o procedimento descrito
na Ref. 1. As propriedades qumicas superficiais foram caracterizadas
determinando o ponto de carga zero (PZC) por titulao mssica e determinando
a quantidade de CO
2
e CO libertados por dessoro a temperatura programada
(TPD) associada com espectrometria de massa (TPD/TPR Micromeritics 2900 e
GC/MS Fisons DM 800).

[1] A.S. Mestre, J. Pires, J.M.F. Nogueira, A.P. Carvalho. Carbon 45 (2007) 1979.
78


SNTESE DE 2,2-BI S-BINOL QUIRAIS: AVALIAO
CATALTICA NA ALQUILAO DE ALDEDOS

Artur R. Abreu
a,b
*, Mariette M. Pereira
a
, Ermelinda Eusbio
a
, Mrio
T. S. Rosado
a
, J. Carles Bayon
b

a
Departamento de Qumica da Universidade de Coimbra, R. Larga, Coimbra, Portugal
b
Departament de Qumica Inorgnica, Universitat Autnoma de Barcelona, Bellaterra,
Spain
*aabreu@qui.uc.pt


O 1,1-bi-2-naftol (BINOL) um ligando quiral que tem demonstrado uma
excelente eficcia na induo de assimetria em diversos sistemas catalticos
[1,2]. Para modelar a selectividade foram recentemente sintetizados derivados do
BINOL contendo diferentes grupos
volumosos/funcionais no anel aromtico. No
entanto de referir que na literatura existem
poucos exemplos de ligandos constitudos por duas
unidades de BINOL (Bis-BINOL) separadas por
uma ponte. Nesta comunicao apresentamos uma
estratgia sinttica para a sntese de uma famlia de
ligandos do tipo L= 2,2-di-hidroxi-1,1-binaphtol
separados por cadeias carbonadas de diferentes
tamanhos. Ser tambm discutido o efeito do
tamanho e tipo da cadeia na enantiosselectividade
da reaco de alquilao de aldedos aromticos com dietilzinco na presena de
isopropxido de titnio. Os melhores excessos enantiomricos foram obtidos
com o ligando L=(1'R,1''R)-2',2''-[propano-1,3-diilbis(oxi)]di-1,1'-bi-2-naftol. Os
valores de ee oscilaram entre 45 e 74% dependendo do substrato e solvente
utilizado na reaco cataltica. Foi tambm sintetizado e testado o ligando
resultante da hidogenao de um dos anis de BINOL, tendo-se obtido o
correspondente ligando L=2',2''-[(propano-1,3-diil-bis(oxi)-bis(5,5',6,6',7,7',8,8-
octa-hidro]-1,1'-bi-2-naftol. Sero apresentados resultados comparativos do
efeito da estrutura na estereosselectividade da reaco, uma vez que com o
ligando parcialmente hidrogenado obtiveram-se excessos enantiomricos
superiores a 80%. Para interpretao dos resultados o estudo foi acompanhado
por modelao molecular dos ligandos e dos respectivos complexos de titnio,
utilizando o hamiltoniano semiemprico PM6 recentemente desenvolvido [3].

Agradecimentos: Os autores agradecem FCT-Feder PTDC/Qui/66015/2006, pelo
financiamento. A Abreu agradece a bolsa SFRH/BD/21314/2005.

[1] J. M. Brunel, Chem Rev. 107 (2007) 1.
[2] J. Balsells, T.J. Davis, P. Carrol, P.J. Walsh, J. Am. Chem. Soc. 124 (2002) 10336.
[3] J.J.P Stewart, J. Mol. Modeling 13 (2007) 1173.

O
Ti(O
i
Pr)
3
Et
2
Zn
Ligando
OH

OH
O O
HO
n
OH
O O
HO
n
L=
79


IMOBILIZAO DE COMPLEXOS DE MOLIBDNIO(II)
EM MCM-41 E SUA APLICAO EM CATLISE

Marta S. Saraiva*, Maria Jos Calhorda, Carla D. Nunes
Departamento de Qumica e Bioqumica, FCUL, Campo Grande, 1749-016 Lisboa,
Portugal
*mssaraiva@fc.ul.pt

Complexos [Mo(
3
-C
3
H
5
)Br(CO)
2
(N-N)] (1, 2) foram preparados a partir do
complexo [Mo(q
3
-allyl)Br(CO)
2
(CH
3
CN)
2
] por reaco com os ligandos 2-(2-
piridil)-imidazole (L1) e 2-(2-piridil)-benzimidazole (L2) e caracterizados por
FTIR e RMN de
1
H e
13
C.[1]


Figura 1. 2-(2-piridil)-imidazole (L1) e 2-(2-piridil)-
benzimidazole (L2)

Aps preparao de MCM-41, este foi funcionalizado com Cl(CH
2
)
3
Si(OEt)
3
,
ficando esta espcie ligada covalentemente s paredes do material. Este MCM
funcionalizado (MCM-Cl) reage com molculas contendo grupos N-H (ligandos L1,
L2), obtendo-se um material poroso com ligando (MCM-Ln) que reagiu com o
complexo, [Mo(q
3
-C
3
H
5
)Br(CO)
2
(CH
3
CN)
2
], formando materiais com os complexos
organometlicos imobilizados (MCM-n), como se representa na Figura 2.

Figura 2. Processo de funcionalizao do MCM-41

Todos os materiais foram caracterizados por FTIR, difraco de raios-X de
ps, RMN de slidos de
13
C e
29
Si MAS e CP MAS, anlise elementar e
isotrmicas de adsoro de N
2
.
Tanto os complexos como os materiais foram testados como catalisadores em
reaces de oxidao cataltica de olefinas (cicloocteno, estireno), tendo-se
verificado atravs dos resultados preliminares que possuem actividade cataltica,
convertendo as olefinas em epxidos, e que os catalisadores heterogneos
(materiais) apresentam maior actividade que os homogneos (complexos).

[1] J:R. Ascenso, C.G. Azevedo, M.J. Calhorda, M.A.A.F. C.T. Carrondo, P. Costa, A.R.
Dias, M.G.B. Drew, V. Flix, A.M. Galvo, C.C. Romo, J. Organomet.Chem. 632
(2001) 197.

Cl
(EtO)
3
Si
MCM-41
OH
OH
OH
OH
OH
OH
OH
OH
O
O
OH
Cl
Si
OEt
MCM-Cl
L1
OH
OH
OH
OH
OH
OH
OH
OH
O
O
OH
Si
OEt
MCM-L1
N
N
H
N
N
N
N
OH
OH
OH
OH
OH
OH
OH
OH
O
O
OH
Si
OEt
Mo
OC
CO
Br
N
N
N
MeCN
MeCN
Mo
CO
CO
Br

N
N
H
N
N
H
N
N
L1
L2
80


ESTERIFICAO DE CIDO PALMTICO A
BIODIESEL NA PRESENA DE POLMEROS
COM GRUPOS CIDO SULFNICO

Catarina S. Caetano
a
, Ana M. Ramos
b
, Isabel M. Fonseca
b
, Joaquim
Vital
b
, Jos E. Castanheiro
a
*
a
Centro de Qumica de vora, Departamento de Qumica, Universidade de vora, 7000-
671 vora, Portugal
b
REQUIMTE, CQFB, Departamento de Qumica, FCT, Universidade Nova de Lisboa,
2829-516 Caparica, Portugal
*jefc@uevora.pt

O biodiesel um combustvel renovvel que pode ser produzido a partir de
leos vegetais e gordura animal. Tem um baixo impacto ambiental, devido
emisso mnima de poluentes ( isento de enxofre) e apresenta caractersticas
fsico-qumicas semelhantes s caractersticas do gasleo [1].
Tradicionalmente, o biodiesel pode ser sintetizado, quer por
transesterificao de triglicerdeos existentes em leos vegetais com metanol ou
etanol na presena de um catalisador cido ou bsico, quer por esterificao de
cidos gordos, existentes na gordura animal e/ou vegetal, com metanol ou etanol,
na presena de catalisadores cidos [1, 2].
Estas reaces so normalmente realizadas na
presena de catalisadores homogneos. No
entanto, os catalisadores heterogneos so
preferveis, oferecendo fcil separao da
mistura reaccional e possibilidade de
reutilizao [3-5].
Polmeros com grupos cido sulfnico tm
sido utilizados como catalisadores em
reaces de hidratao, desidratao,
eterificao e hidrlise [6].
Neste trabalho estuda-se a esterificao de cido palmtico com metanol e
etanol na presena de poliestireno e poli(lcool vinlico) com grupos cido
sulfnico. A figura 1 mostra a converso de cido palmtico com metanol e
etanol a 60C e 80C, na presena de PVA_SO
3
H.

[1] J. Gerpen, Fuel Processing Technology 86 (2005) 1097.
[2] F. Ma, M. Hanna, Bioresource Technology 70 (1999) 1.
[3] L. Guerreiro, J. Castanheiro, I. Fonseca, R. Martin-Aranda, A. Ramos, J. Vital,
Catalysis Today, 118 (2006) 166.
[4] U. Schuchardt, R.M. Vargas, G. Gelbard, J. Mol. Cat. A: Chem. 99 (1995) 65.
[5] K. Rao, S. Tavener, N. Young, K. Wilson, Green Chemistry 8 (2006) 790.
[6] M.A. Harmer, Q. Sun, Appl. Cat. A: Gen. 221 (2001) 41.
0
20
40
60
80
100
0 10 20 30
Tempo (h)
C
o
n
v
e
r
s

o

(
%
)
Metanol (60C)
Etanol (60C)
Etanol (80C)
Figura 1. Esterificao de cido palmtico
na presena de PVA_SO
3
H.
81


ADSORO DE CORANTES EM MATERIAIS DE
CARBONO MESOPOROSOS MODIFICADOS

J. P. S. Sousa
a
, C. A. Orge
a
, F. Gonalves
a
, C. Freire
b
, J. L. Figueiredo
a
,
M. F. R. Pereira
a
, J. J. M. rfo
a
*
a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, 4200-465 Porto, Portugal.
b
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre, 4169-007 Porto, Portugal.
*jjmo@fe.up.pt

possvel controlar as condies de preparao de materiais de carbono, tais
como os xerogis e as rplicas via slidos inorgnicos nanoestruturados, para
que eles apresentem um elevado grau de mesoporosidade e uma rea superficial
idntica dos carves activados. Alm disso, a sua utilizao em adsoro e
catlise pode ser vantajosa relativamente aos carves activados, em consequncia
nomeadamente da maior abertura dos poros, facilitando assim o acesso de
molculas de grandes dimenses. Neste trabalho, avaliou-se o comportamento
deste tipo de materiais na adsoro de corantes txteis de diferentes classes,
dando especial ateno influncia das caractersticas qumicas superficiais [1].
O xerogel de carbono foi sintetizado a
pH 6.0 por policondensao do resorcinol e
do formaldedo, seguida de carbonizao em
azoto a 800C [2]. As rplicas via slica
SBA-15 foram produzidas de acordo com
[3]. A qumica superficial dos materiais de
carbono preparados foi posteriormente
modificada atravs de tratamentos qumicos
ou trmicos adequados. A natureza e a
quantidade dos grupos oxigenados
superficiais presentes nas vrias amostras
foram determinadas por dessoro a
temperatura programada (TPD) (Figura 1).
A caracterizao qumica das amostras foi
completada com determinaes de pH
pzc
e
de acidez e basicidade. A caracterizao textural baseou-se na determinao das
isotrmicas de adsoro de N
2
a 77 K.
Agradecimentos: Universidade do Porto e Caixa Geral de Depsitos - Projecto IPG58;
Fundao para a Cincia e a Tecnologia (FCT) e FEDER - POCTI/1181.
[1] P.C.C. Faria, J.J.M. rfo, M.F.R. Pereira, Water Res. 38 (2004) 2043.
[2] N. Job, R. Pirard, J. Marien, J.P. Pirard, Carbon 42 (2004) 619.
[3] S. Jun, S.H. Joo, R. Ryoo, M. Kruk, M. Jaronice, Z. Liu, T. Ohsuna, O. Terasaki, J.
Am. Chem. Soc. 122 (2000) 10712.
0 250 500 750 1000
0.0
0.3
0.6
0.9
0 250 500 750 1000
0.00
0.05
0.10
0.15
b)
a)
C
O

(

m
o
l
.
s
- 1
.
g
- 1
)
Temperatura (C)
CX
CX-HNO
3
CX-O
2
C
O
2

(

m
o
l
.
s
- 1
.
g
- 1
)
Temperatura (C)
Figura 1. Espectros de TPD de
CO
2
e de CO para alguns dos
xerogis de carbono preparados.
82


INFLUNCIA DE CLCIO E SDIO NA ACTIVAO
QUMICA DE LENHINA COM CIDO FOSFRICO

Paulo A. M. Mouro*, Peter J. M. Carrott, Manuela Ribeiro Carrott,
Rita I. L. S. Lopes
Centro de Qumica de vora e Departamento de Qumica, Universidade de vora,
Colgio Lus Antnio Verney, 7000-671 vora, Portugal
*pamm@uevora.pt

Na actualidade a produo de carves activados a partir de matrias-primas
naturais de baixo valor e disponveis em grandes quantidades representa uma das
vias com maior interesse [1]. Nesta linha, justifica-se o elevado potencial da
lenhina como percursor, uma vez que a segunda matria-prima mais abundante
na natureza. A ttulo de exemplo, durante o processo de cozimento da madeira
produzem-se cerca de 50 milhes de toneladas por ano deste polmero. A maior
parte desta quantidade utilizada como combustvel na prpria industria
papeleira, mas cada vez mais surge um interesse crescente na sua utilizao
como precursor na produo de carves activados, em resultado da sua
composio ser maioritariamente carbono e possuir uma estrutura semelhante
do carvo betuminoso [2, 3]. Em 1993 e 1994 surgem os primeiros trabalhos em
que se testa a produo de carves activados a partir de lenhina [3].
Nesta linha, o nosso interesse prende-se com o estudo do efeito cataltico
resultante da incorporao de metais alcalinos e metais alcalino-terrosos durante
o processo de activao qumica da lenhina hidroltica. Assim, apresentam-se os
resultados da produo de carves activados quimicamente por impregnao
com H
3
PO
4
e simultaneamente o efeito da incorporao de sdio e clcio via
adio de NaCl e CaCl
2
. Correlacionam-se ainda essas variveis com o efeito nos
parmetros estruturais (volume poroso, rea superficial e largura de poro) e no
rendimento do processo de activao. Estudos envolvendo anlises
complementares (entre outras FTIR, anlise elementar, contedo em cinzas) e
uma gama superior de clcio e sdio, esto a ser realizados no nosso laboratrio,
para uma melhor avaliao do seu efeito cataltico durante a activao.
Analisando o comportamento da lenhina neste processo, ser possvel definir
as condies experimentais (em termos trmicos, relao precursor/H
3
PO
4
e
quantidade de metal incorporado) mais favorveis obteno de carves
activados com caractersticas especficas reduzindo simultaneamente os custos
energticos.

[1] J.S. Mattson, H.B. Mark, Activated Carbon Surface Chemistry and Adsorption from
Solution, Marcel Dekker, New York (1971).
[2] Informao acessvel em www.ili-lignin.com.
[3] Suhas, P.J.M. Carrott, M.M.L. Ribeiro Carrott, Bioresour. Technol., 98 (2006) 2301.
83


SNTESE E APLICAO EM OZONIZAO CATALTICA
DE MATERIAIS DE CARBONO MESOPOROSOS

C. A. Orge
a
, J. P. S. Sousa
a
, F. Gonalves
a
, P. C. C. Faria
a
, C. Freire
b
,
J. J. M. rfo
a
, M. F. R. Pereira
a
*

a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, 4200-465 Porto, Portugal.
b
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre, 4169-007 Porto, Portugal.
*fpereira@fe.up.pt

Os materiais de carbono, em particular os carves activados, catalisam a
ozonizao de poluentes orgnicos em solues aquosas, sendo possvel em
alguns casos atingirem-se nveis de mineralizao muito prximos dos 100% [1].
Este efeito promotor reside na capacidade de decompor o ozono em espcies
oxigenadas altamente reactivas (e.g. radicais hidroxilo), por sua vez capazes de
atacar com elevada eficincia as molculas dos compostos orgnicos, quer na
fase lquida quer superfcie do catalisador. Neste ltimo mecanismo, a adsoro
do poluente desempenha obviamente um papel importante. Para facilitar a
adsoro vantajoso no s adequar a qumica superficial do material de
carbono como tambm facilitar o acesso das molculas ao interior dos poros,
factor particularmente crtico quando elas tm grandes dimenses, como por
exemplo as molculas dos corantes txteis. Neste trabalho so apresentados
resultados cinticos de descolorao e mineralizao de solues de corantes de
diferentes classes por ozonizao na presena de materiais de carbono
mesoporosos (xerogis e rplicas via SBA-15). Para avaliar as sinergias entre o
ozono e os materiais preparados, realizaram-se tambm no mesmo reactor
laboratorial ensaios de adsoro e de ozonizao no cataltica. Os xerogis de
carbono foram preparados a pH 6.0 segundo o mtodo referido em [2]. A slica
SBA-15 foi sintetizada atravs da adio de uma fonte de silcio (TEOS) a uma
soluo aquosa de HCl e de um surfactante apropriado. Em seguida, a
polimerizao do lcool furfurlico no interior dos poros foi promovida usando
cido paratoluenossulfnico. O compsito SBA-15/polmero foi carbonizado em
N
2
a 800 C e, posteriormente, a slica foi removida com uma soluo de HF,
obtendo-se um material com uma estrutura mesoporosa altamente ordenada [3].
Foi tambm avaliada a influncia da qumica superficial, para o que se fizeram
tratamentos qumicos e trmicos adequados sobre as amostras preparadas.
Agradecimentos: Universidade do Porto e Caixa Geral de Depsitos - Projecto IPG58;
Fundao para a Cincia e a Tecnologia (FCT) e FEDER - POCTI/1181.
[1] P.C.C Faria, J.J.M rfo, M.F.R Pereira, Appl. Catal. B: Environ. 79 (2008) 237.
[2] N. Job, R. Pirard, J. Marien, J.P. Pirard, Carbon 42 (2004) 619.
[3] S. Jun, S.H. Joo, R. Ryoo, M. Kruk, M. Jaroniec, Z. Liu, T. Ohsuna, O. Terasaki, J.
Am. Chem. Soc. 122 (2000) 10712.
84


COVALENT SIDEWALL FUNCTIONALIZATION OF
CARBON NANOTUBES BY METALLOPORPHYRINS
THROUGH 1,3-DIPOLAR CYCLOADDITION

D. Teixeira
a
*, S. L. H. Rebelo
a
, F. Gonalves
b
, A. M. G. Silva
a
, M. F.
R. Pereira
b
, J. J. M. rfo
b
, C. Feire
a

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre, 4169-007 Porto
b
Laboratrio de Catlise e Materiais, Departamento de Engenharia Qumica, Faculdade
de Engenharia, Universidade do Porto, 4200-465 Porto
*Dalila_Teixeira396@hotmail.com

Carbon nanotubes (CNT) have been extensively studied for applications in
nanotechnology, electronics, optics and other fields of materials science; for
those proposes their chemical modification is often required. Functionalization
of CNT can be achieved by covalent reactions on end and defect sites and more
recently, methodologies for sidewall functionalization have been developed [1].
The immobilisation of transition metal complexes with catalytic properties
onto solid supports is a theme of intense research, due to its importance towards
the goals of Green Chemistry. As a result, improved catalyst performance,
stability and reusability can be obtained [2].
In this work, the anchoring of metalloporphyrins onto multiwall carbon
nanotubes (MWCNT) is described, based on the 1,3- dipolar cycloaddition of
azomethine ylides to the CNT sidewall (Figure 1). The new materials were
characterized by elemental analysis, XPS, FTIR, N
2
adsorption and TPD and will
be tested in selective oxidation of organic compounds and ozonation of
pollutants.

Figure 1: Anchoring of metalloporphyrins onto carbon nanotubes

Acknowledgments: This work was partially funded by Projecto de Investigao Cientfica
na Pr-Graduao 2007, Universidade do Porto e Caixa Geral de Depsitos, Proj. IPG58.
S. L.H. R. thanks FCT for a Post-Doc grant.
[1] V. Georgakilas, K. Kordatos, M. Prato, D. M. Guldi, M. Holzinger, A. Hirsch. J. Am.
Chem. Soc.124 (2002) 760.
[2] A. R. Silva, V. Budarin, J. H. Clark, B. de Castro, C. Freire. Carbon 43 (2005) 2096.

R
2
CHO
R
1
-NH-CH
2
- COOH
I R
1
= Spacer -Metalloporphyrin; R
2
= H
II R
1
= CH
3
; R
2
= Spacer -Metalloporphyrin
N
R
2
R
1
85


FUNCIONALIZAO DE SLICA GEL COM 2-AMINO-
1,3,4-TIADIAZOL E Mo(II)

Maria Vasconcellos Dias
a
*, Newton L. Dias Filho
b
, Paula Ferreira
c
,
Carla D. Nunes
a
, Maria Jos Calhorda
a
, Ftima C. M. Portugal
a
, Jos
M. F. Nogueira
a

a
Centro de Qumica e Bioqumica, Departamento de Qumica e Bioqumica, FCUL, Ed.
C8, Campo Grande, 1749-016 Lisboa
b
Departamento de Fsica e Qumica, UNESP-Faculdade de Engenharia de Ilha Solteira,
Av.Brasil, 56, Caixa Postal 31, 15385-000 Ilha Solteira-SP, Brasil
c
Departamento de Engenharia Cermica e do Vidro, CICECO, Universidade de Aveiro,
Campus Universitrio de Santiago, 3810-193 Aveiro, Portugal
*mmdias@fc.ul.pt

A slica gel um material usado
frequentemente para suporte de
catalisadores. A reaco dos grupos
SiOH superficiais com
Cl(CH
2
)
3
Si(OEt)
3
o primeiro passo na
obteno de um novo catalisador
heterogneo contendo Mo(II).
Molculas contendo grupos NH como o
2-amino-1,3,4-tiadiazol (L) podem
imobilizar-se no segundo passo. Este
ligando pode por sua vez substituir dois
grupos CH
3
CN no complexo
[Mo(q
3
-C
3
H
5
)Br(CO)
2
(CH
3
CN)
2
],
obtendo-se um novo material, como se
representa na Figura 1. Os vrios
materiais foram caracterizados por
FTIR, RMN de
13
C e
29
Si e anlise
elementar. Preparou-se o complexo
[Mo(q
3
-C
3
H
5
)Br(CO)
2
(L)] que foi
igualmente caracterizado. Tanto o
complexo como o material contendo
molibdnio foram testados como
precursores na catlise de oxidao de
olefinas, em fase homognea e
heterognea, respectivamente, na
presena de hidroperxido de t-butilo,
tendo a reaco sido seguida por
cromatografia gasosa acoplada
espectrometria de massa.

O O O
OH
Cl
Si
OEt
O O
H H H
Cl
(EtO)
3
Si
H
2
N
S
N
N
MeCN
MeCN
Mo
CO
CO
Br
O O O OH
Si
OEt
O O
H H H
O O O
H H H
O O O
H H H
N
H
S
N
N
O
O O OH
Si
OEt
O O
H H H
HN
S
N N
Mo
OC
OC
Br
86


PREPARAO DE XIDOS METLICOS POR
EXOTEMPLATING EM MATERIAIS DE CARBONO

S. S. T. Bastos, F. Gonalves, V. P. Santos, J. J. M. rfo, M. F. R.
Pereira, J. L. Figueiredo*
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*jlfig@fe.up.pt

A sntese de materiais inorgnicos com elevada porosidade e rea superficial
tem vindo a ser investigada devido sua interessante aplicao em vrias reas,
nomeadamente em catlise heterognea. O procedimento por exotemplating pode
ser usado para sintetizar este tipo de materiais [1]. Os templates podem ser
materiais com uma estrutura porosa
adequada, a qual preenchida com o
precursor do slido a preparar. Aps remoo
do template, obtm-se um material com uma
elevada rea superficial. Os materiais de
carbono renem condies excelentes para
servirem como templates, pois para alm de
possurem uma elevada porosidade, so
relativamente baratos e podem ser removidos
facilmente por combusto. Os xidos de
mangans, crio e titnio so muito
interessantes para aplicaes catalticas, mas
quando sintetizados pelo processo tradicional tm como principal limitao as
baixas reas superficiais obtidas. O objectivo principal deste trabalho estudar a
preparao dos mencionados xidos por exotemplating em materiais de carbono
e avaliar o aumento da rea superficial. Os xidos preparados foram testados
como catalisadores na oxidao cataltica de compostos orgnicos volteis.
Os xidos foram preparados pelo mtodo de impregnao em vcuo no
carvo activado NORIT ROX 0.8, usando solues saturadas do metal precursor
do xido. Assume-se que os poros do carvo so preenchidos pelo precursor, o
qual se transforma no xido durante a calcinao. Aps remoo do carvo
obtm-se o xido com os poros correspondentes parte slida do carvo
activado. Para determinar a temperatura de gasificao em ar do carvo activado,
analisaram-se por termogravimetria (TG) o xido preparado com e sem
templating e as respectivas matrizes (Figura 1). Os materiais foram tambm
caracterizados por SEM, XRD e adsoro de N
2
a 77K.

Agradecimentos: FCT e FEDER - PTDC/AMB/69065/2006 e POCTI/1181.

[1] Ferdi Schth, Angew. Chem. Int. Ed. 42 (2003) 3604.
Figura 1. TG em ar do xido de
titnio puro e impregnado.
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800
C
o
n
v
e
r
s

o
(
%
)
T (C)
xido de Titnio
por Exotemplating
Precursor
Precursor
Impregnado
xido de Titnio
Carvo Activado
87


ACETOXILAO DE GLICEROL COM
HETEROPOLICIDOS IMOBILIZADOS EM ZELITO Y

Patrcia Ferreira
a
, Ana M. Ramos
b
, Isabel M. Fonseca
b
, Joaquim M.
Vital
b
, Jos E. Castanheiro
a
*
a
Centro de Qumica de vora, Departamento de Qumica, Universidade de vora, 7000-
671 vora, Portugal
b
REQUIMTE, CQFB, Departamento de Qumica, FCT, Universidade Nova de Lisboa,
2829-516 Caparica, Portugal
*jefc@uevora.pt

A crescente produo de biodiesel por transesterificao de leos vegetais
com metanol ou etanol, na presena de catalisadores cidos ou bsicos,
responsvel pelo aumento da produo de
glicerol. Por cada 90 m
3
de biodiesel
produzido so gerados 10 m
3
de glicerol
[1]. Torna-se assim imperativo o
desenvolvimento de processos que
permitam uma valorizao do glicerol.
Uma possvel estratgia de valorizao de glicerol a esterificao com cido
actico. Os steres obtidos so utilizados quer na indstria de qumica fina quer
como bioaditivos nos combustveis [2].
Tradicionalmente, as reaces de esterificao so realizadas na presena de
cido sulfrico. Contudo, a necessidade de desenvolver tecnologia mais Amiga
do Ambiente tem levado substituio dos actuais processos homogneos por
processos heterogneos.
Os catalisadores slidos cidos tm a vantagem de serem fceis de separar da
mistura reaccional, a possibilidade de reutilizao e so mais seguros no seu
manuseamento do que os catalisadores homogneos.
Os heteropolicidos (HPAs) apresentam acidez de Brnsted e so mais fortes
do que os slidos cidos convencionais. Os HPAs, por apresentarem uma rea
especfica baixa, tm sido heterogeneizados em slica, alumina, zelitos, carves
activados e polmeros [3].
Neste trabalho estuda-se a esterificao de glicerol com cido actico na
presena de cido dodecamolibdofosfrico encapsulado nas grandes cavidades
do zelito Y. Estes catalisadores foram preparados de acordo com o
procedimento de Mukai et al. [4]. Os produtos obtidos foram mono-ster, di-
ster e o tri-ster.

[1] J. Gerpen, Fuel Processing Technology 86 (2005) 1097.
[2] H. Nabeshima, K. Ito, JP patent 276787 (1995).
[3] I. Kozhevnikov, Chem. Rev. 98 (1998) 171.
[4] S. Mukai, T. Masuda, I. Ogino, K. Hanhimoto, Appl. Catal. A: Gen. 165 (1997) 219.


HO OH
OH
AcOH
Ac OH
Ac
Ac Ac
Ac
Ac OH
OH
H
2
O + +
88


TITANIUM DIOXIDE SUPPORTED Pt CATALYSTS FOR
CINNAMALDEHYDE HYDROGENATION

Bruno F. Machado
a
*, Helder T. Gomes
a,b
, Joaquim L. Faria
a

a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM, Departamento
de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, Portugal
b
Departamento de Tecnologia Qumica e Biolgica, Escola Superior de Tecnologia e de
Gesto, Instituto Politcnico de Bragana, Portugal
*bmachado@fe.up.pt

The use of reducible metal oxides as supports in the selective hydrogenation of
unsaturated aldehydes has been studied for many years. It is well known that
reduction of group VIII metals supported on these materials, when performed at
high temperatures, produces a strong electronic effect, named strong metal support
interaction (SMSI), that can enhance selectivity towards the desired C=O bond.
In this work, two different types of TiO
2
were used to support Pt: (a) prepared
by an acid-catalyzed sol-gel process starting from the alkoxide precursors [1] (SG,
100% anatase); (b) commercial Degussa P-25 (DEG, 80% anatase and 20% rutile).
The photochemical deposition procedure, aiming at 5 wt. % Pt load, was carried
out at atmospheric pressure and ambient temperature, as described elsewhere [2].
The resulting materials were calcined and reduced at 773K. The obtained catalysts
were tested in the liquid-phase hydrogenation of cinnamaldehyde, performed in a
100 mL stainless steel reactor at 363 K and 10 bar, total pressure.
After calcination at 773K there was no noticeable difference in the X-ray
diffraction pattern of Pt/DEG whereas in Pt/SG, ca. 35% of anatase had
transformed to rutile phase. This increase in rutile content was accompanied by a
specific surface area decrease. Regarding the catalytic results, Pt/SG exhibited the
highest selectivity towards cinnamyl alcohol (COL). The Pt/DEG catalyst had an
overall worst performance, in spite of producing lower amounts of hydro-
cinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL) (Table 1).

Table 1. Selectivity results obtained at 50% conversion of cinnamaldehyde.
Catalyst S
COL
(%) S
HCAL
(%) S
HCOL
(%) S
OTHERS
(%)
Pt/DEG 56 3 8 33
Pt/SG 82 6 12 0

Catalysts prepared by a simple photodeposition method revealed an
outstanding activity and selectivity for hydrogenation of cinnamaldehyde into
cinnamyl alcohol. SMSI effect was found to be responsible for the elevated
catalytic performance.
BFM acknowledges FCT the PhD grant SFRH/BD/16565/2004. Work supported by FCT
and POCI/FEDER (POCI/EQU/58252/2004).
[1] W. Wang, Ph. Serp, Ph. Kalck, J.L. Faria, Appl. Catal. B: Env. 56 (2005) 305.
[2] Z.B. Zhang, C.C. Wang, R. Zakaria, J.Y. Ying, J. Phys. Chem. B 102 (1998) 10871.
89


Fig. 1 HRTEM micrograph
of Pt/Ce-Ti-O.
PHOTODEPOSITION OF PT NANOPARTICLES ON Ce-Ti-O

Adrin M. T. Silva
a
*, Bruno F. Machado
a
, Helder T. Gomes
a,b
, Jos
L. Figueiredo
a
, Goran Drazic
c
, Joaquim L. Faria
a

a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
b
Departamento de Tecnologia Qumica e Biolgica, Escola Superior de Tecnologia e de
Gesto do Instituto Politcnico de Bragana, Campus de Santa Apolnia, 5300-857
Bragana, Portugal
c
Jozef Stefan Institute, Department of Nanostructured Materials, Jamova 39, SI-1000
Ljubljana, Slovenia
*adrian@fe.up.pt

Hydrogenation reactions are the most common examples where transition
and noble metal nanoparticles are applied in colloidal solution as quasi-
homogeneous catalysts [1]. The main drawback in the use of colloidal
nanoparticles for catalysis concerns the recovery and reuse of these particles.
This is especially important if environmental issues are considered. Therefore,
attention has been drawn to the use of supported nanoparticles.
In this work, Ce-Ti-O supports were synthesized by the solvothermal method
using methanol and a cationic surfactant (CTAB). Pt
nanoparticles were then supported by photochemical
deposition using a low-pressure mercury lamp with
an emission line at 254 nm (ca.3 W of radiant flux)
during 4 h. The catalysts were calcined in N
2
(4 h,
100 mL min
-1
), reduced in H
2
(2 h, 20 mL min
-1
) and
flushed again with N
2
during 30 min at 773 K.
Ultrafine platelet shaped CeO
2
particles with
sizes ~ 3-8 nm were also produced by the
solvothermal method. When Ti was combined with
Ce, a nanostructured network was obtained. It was
proved that Pt spherical nanoparticles (diameter ~ 2-4 nm) can be efficiently
photodeposited on these supports. Fig.1 shows a HRTEM micrograph of the
Pt/Ce-Ti-O catalyst, where a Pt nanoparticle (marked by an arrow) can be
identified. These catalysts were tested in the selective hydrogenation of
cinnamaldehyde to cinnamyl alcohol. Enhancement in the catalytic activity for
cinnamaldehyde hydrogenation and higher selectivity for cinnamyl alcohol
production was observed with the Pt nanoparticles supported on Ce-Ti-O when
compared with the single-oxide supports (CeO
2
and TiO
2
).
Acknowledgments: FCT (Portugal-Slovenia Cooperation in S&T 2008-2009;
POCI/N010/2006; SFRH/BD/16565/2004).
[1] C. Burda, X. Chen, R. Narayanan, M.A. El-Sayed. Chem. Rev 105 (2005) 1039.
90


SYNTHESIS, CHARACTERIZATION
AND CATALYTIC APPLICATION OF A CHIRAL
MENTHYLDIMETHYLTIN MOLYBDATE

Marta Abrantes
a,c
, Anabela A. Valente
b
, Martyn Pillinger
b
, Carlos C.
Romo
a
, Isabel S. Gonalves
b
*
a
Instituto de Tecnologia Qumica e Biolgica da Universidade Nova de Lisboa, Av. da
Republica, Estao Agronmica Nacional, 2780-157 Oeiras, Portugal
b
Department of Chemistry, CICECO, University of Aveiro, Campus de Santiago, 3810-
193 Aveiro, Portugal
c
Laboratrio de Processos de Separao e Reaco, Faculdade de Engenharia da
Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

*igoncalves@dq.ua.pt


Research on organic-inorganic hybrid materials with infinite (polymeric)
structures has grown exponentially over the last ten years. Although a large
number of potential applications can be envisaged for these hybrid materials,
particularly in the fields of optics, electronics, gas adsorption and catalysis, most
of the published work has been restricted to synthesis and characterization.
We have been studying polymeric organotin molybdates as catalysts for the
liquid-phase oxidation of organic compounds [1]. The catalytic results depend on
the nature of the tin-bound R groups and this has led us to synthesize chiral
catalytic systems by using chiral organotin compounds.
In the present work, the introduction of chirality into the system
[(Me
3
Sn)
2
MoO
4
] has been achieved by the substitution of one of the methyl
groups by the ()-menthyl group. The resultant compound
[((Me)
2
(menthyl)Sn)
2
MoO
4
(H2O)
3.5
] (1) has
been characterized in the solid state and
examined as a catalyst for the epoxidation of
cyclooctene and several unfunctionalized
prochiral olefins. EXAFS-derived structural
information for (1) (distances in ) is
summarized in the figure. The compound
can be used as a recyclable solid catalyst for the selective epoxidation of
cyclooctene and several unfunctionalized prochiral olefins by t-BuOOH. The
corresponding epoxide isomers are obtained with fairly good to excellent
selectivity, albeit with low enantiomeric or diastereomeric excesses [2].

[1] (a) M. Abrantes, A.A. Valente, M. Pillinger, I.S. Gonalves, J. Rocha and C.C.
Romo, Chem. Eur. J. 9 (2003) 2685; (b) M. Abrantes, A.A. Valente, I.S. Gonalves,
M. Pillinger, C.C. Romo, J. Mol. Catal. A: Chem. 238 (2005) 51.
[2] M. Abrantes, A.A. Valente, M. Pillinger, C.C. Romo, I.S. Gonalves, Catal. Letters
2007, 114, 103.
O Sn
Me
Mo
O 8
H
iPr
Me
Me
2.23
2.14
1.76
3.80

91


GOLD NANOPARTICLES ON CERIA SUPPORTS FOR
THE OXIDATION OF CARBON MONOXIDE

S. A. C. Carabineiro
a
*, A. M. T. Silva
a
, G. Drazic
b
, J. L. Figueiredo
a

a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
b
Jozef Stefan Institute, Department of Nanostructured Materials, Jamova 39, SI-1000
Ljubljana, Slovenia
*sonia.carabineiro@fe.up.pt

The oxidation of carbon monoxide is a reaction of outstanding importance in
pollution control (CO removal), fuel cells, and gas sensing [1]. Although simple
and intensively studied, this reaction is still poorly understood and their
mechanistic pathways are still uncertain.
Gold on ceria (CeO
2
) has proved as a very effective catalyst for reactions
such as water-gas shift (WGS) [1, 2] and preferential oxidation of CO in the
presence of hydrogen (PROX) [1, 3]. These results are of particular interest since
ceria is extensively employed as a component in automotive, three-way
emission-control catalysts, due to its capacity to undergo a rapid change in
oxidation state upon changes in the redox potential of the exhaust gases [1].
Some studies showed Au/ceria can also be highly active for CO oxidation [1, 4].
In the present work, ultrafine platelet shaped CeO
2
particles were prepared by
the solvothermal method (150C, autogeneous pressure, 150 min) using
methanol and CTAB. Different conditions of synthesis were investigated. Au
was loaded on the obtained ceria supports by incipient wetness impregnation,
double impregnation [5] and liquid phase reductive deposition [6]. The main
advantage of the latter two methods is that chloride is removed from the catalyst
sample, which is well known to cause sintering of Au nanoparticles, thus turning
them inactive [1]. A commercial CeO
2
(Fluka) was also used for comparison.
Samples were mainly characterised by HRTEM/SAED/EDXS and XRD.
Activities for CO oxidation are compared and results are discussed.
Acknowledgments: FCT (Programa CIENCIA 2007); Portugal-Slovenia Cooperation in
S&T 2008-2009; POCI/N010/2006).
[1] S.A.C. Carabineiro, D.T. Thompson, Catalytic Applications for Gold
Nanotechnology, In: Nanocatalysis, Eds. U. Heiz and U. Landman, Springer-Verlag,
Berlin, Heidelberg, New York (2007) pp. 377-489 (ISBN-13 978-3-540-32645-8).
[2] C.H. Kim, L.T. Thompson, J. Catal. 244 (2006) 248.
[3] A. Luengnaruemitchai, S. Osuwan, E. Gulari, Int. J. Hydrogen Ener. 29 (2004) 429.
[4] S. Carrettin, P. Concepcin, A. Corma, J.M.L. Nieto, V.F. Puntes, Angew. Chem. Int. Ed.
43 (2004) 2538; A.M. Venezia, G. Pantaleo, A. Longo, G. Di Carlo, M. Casaletto, F.L.
Liotta, G. Deganello, J. Phys. Chem. B 109 (2005) 2821; U.R. Pillai, S Deevi, Appl Catal
A 299 (2006) 266; V. Aguilar-Guerrero, B.C. Gates, Chem, Commun. (2007) 3210.
[5] M. Bowker, A. Nuhu, J. Soares, Catal. Today, 122 (2007) 245.
[6] Y. Sunagawa, K. Yamamoto, H. Takahashi, A. Muramatsu, Catal. Today 132 (2008) 81.
92


Table 1. Textural properties, surface chemistry and catalytic results obtained.
Sample
S
BET

(m
2
/g)
S
meso

(m
2
/g)
CO
(molg
-1
)
CO
2

(molg
-1
)
X
ANL, 60 min
(%)
S
NOC, 60 min

(%)
CX 724 524 709 217 94 84
CCX 475 117 1565 516 96 58


PREPARATION OF HIGHLY MESOPOROUS CARBON
CATALYSTS FOR WET OXIDATION OF ANILINE

Purnakala V. Samant
a
, Helder T. Gomes
a,b
*, Jos L. Figueiredo
a
,
Joaquim L. Faria
a

a
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
b
Departamento de Tecnologia Qumica e Biolgica, Escola Superior de Tecnologia e de
Gesto do Instituto Politcnico de Bragana, Campus de Santa Apolnia, 5300-857
Bragana, Portugal
*htgomes@ipb.pt

Carbon xerogels were synthesized from different organic precursors in order
to obtain materials with high surface area and well developed mesoporosity. In
addition, oxygen surface groups were introduced on these materials by proper
chemical or thermal treatments. In a previous work [1] we have shown that
mesoporous carbon xerogels with proper surface chemistry could be efficiently
applied in wet oxidation reactions.
In this work, the xerogels synthesized by poly-condensation from the organic
precursors resorcinol/formaldehyde (CX) and resorcinol/cresol/formaldehyde
(CCX) were used as catalysts in the wet oxidation of aniline. The reaction was
carried out at 200C and 20 bar of oxygen partial pressure. The textural
properties and surface chemistry of the synthesized carbon materials, as well as
the catalytic results obtained with them are given in Table 1.
Analysis of the textural properties of both materials shows that CX is highly
mesoporous in contrast with the modest mesoporosity of CCX. On the contrary,
the surface chemistry of CCX is more pronounced than that of CX. Comparing
their catalytic performance, it was found that CX is an efficient catalyst for the
degradation of aniline, high activity and high selectivity to the formation of non-
organic compounds being obtained. The influence of texture and surface
chemistry on the catalysts efficiency will be discussed. The activity of CX was
assigned to the amount and nature of oxygen functional groups present at their
surface, while the selectivity reflects the textural properties of the material.

Acknowledgments: FCT (POCI/58252/EQU/2004, POCTI/1181/2003)

[1] H.T. Gomes, B.F. Machado, A. Ribeiro, I. Moreira, M. Rosrio, A.M.T. Silva, J.L.
Figueiredo, J.L. Faria. J. Hazard. Mater. (2008) doi:10.1016/j.jhazmat.2008.02.070.
93


UNUSUAL POLARITY AND SURFACE POTENTIAL
PROPERTIES IN BINARY MIXED LIPID BILAYERS
ACCESSED WITH PYRENE BASED FLUOROPHORES

Jorge Martins
a,b
*, Dalila Arrais
a
, Miguel Manuel
a

a
IBB - Institute for Biotechnology and Bioengineering, CBME - Center for Molecular and
Structural Biomedicine
b
DQBF, Faculdade de Cincias e Tecnologia, Universidade do Algarve, Campus de
Gambelas, P-8005-139 Faro
*jmartin@ualg.pt

We present here further developments in probing surface potential and
polarity properties of lipid bilayers, using pyrene and some of its derivatives, to
study: the equivalent polarity properties of binary mixtures of DMPC/cholesterol
and DPPC/cholesterol, in liquid-ordered (l
o
) and liquid-disordered (l
d
) phases,
probed by means of the pyrene Ham Effect [1], and the partition of the anionic
probe 1-pyrenesulfonate (PSA) into liposomes composed by POPC
(zwitterionic) and by mixtures of zwitterionic and anionic phospholipids
(bilayers with negative surface potential), using UV double-derivative
spectrophotometry [2].
We demonstrate an additional effect of cholesterol in the l
o
phase of lipid
bilayers. In this phase, the polarity of the bilayer and its temperature dependency
varies largely with the chemical composition in respect to the cholesterol
proportion. Distinctively, for higher proportions of cholesterol, the thermal
dependence of polarity shows a profile more akin with apolar solvents, yet
displaying higher polarities. We additionally refine the structural dependence of
the mixed lipid bilayers polarity, by monitoring the spectral shifts of pyrene-3-
carboxyaldehyde dependent on the solvent polarity.
Contrasting with recent studies indicating a decrease in the partition of
anionic probes into phospholipid bilayers having negative surface potential, we
find that the Nernstian partition constant of PSA into multilamellar (MLV) and
unilamellar (LUV) vesicles at 25C, increases from K
p
=6,710
3
for pure POPC
bilayers (zwitterionic), to K
p
=3,410
4
for bilayers composed by 5% mol of
POPS (anionic) and 95% mol of POPC, and it is even higher for 10% mol of
POPS, K
p
=7,310
4
. We propose a self-consistent interpretation, based on the
interfacial properties of mixed zwitterionic/anionic bilayers.

Acknowledgments: Work partially funded through the projects POCTI/QUI/45090/2002
and POCTI/BCI/46174/2002, from Fundao para a Cincia e a Tecnologia, Portugal.

[1] D. Arrais, J. Martins Biochim. Biophys. Acta Biomembranes 1768 (2007) 2914.
[2] M. Manuel, J. Martins. Chem.Phys. Lipids (2008) submitted.
94


Comparison between the adsorption and covalent
binding of Gum Arabic on MNPs
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.0000 0.0050 0.0100 0.0150 0.0200
%wt [GA] in eq.
g

a
d
s

o
r

b
o
u
n
d
/
g

M
N
P
s
Covalent binding of
GAon glutaraldehyde
functionalized MNPs
Covalent binding of
GAon aminated
MNPs
GAadsorbed on
MNPs
SURFACE MODIFICATION OF MAGNETIC
NANOPARTICLES

Ana S. Cardoso, Ana C. A. Roque*

REQUIMTE/CQFB, Centro de Qumica Fina e Biotecnologia, Faculdade de Cincias e
Tecnologia, Departamento de Qumica, Universidade Nova de Lisboa, 2829-516
Caparica, Portugal
*cecilia.roque@dq.fct.unl.pt

Magnetic nanoparticles (MNPs) have been widely used in industry and in
biomedicine for In vitro and In vivo applications [1, 2]. Several studies have been
performed using surfactants to modify the surface of magnetic nanoparticles so
as to control their size, inhibit agglomerate formations during synthesis and
improve biocompatibility [3]. The aim of this work was the functionalization of
magnetic nanoparticles with Gum Arabic, a natural polymer used as an
emulsifying agent [3, 4]. In order to
obtain these functionalized MNPs several
studies were performed: optimization of
Gum Arabic (GA) quantification in
aqueous solutions using the BCA Assay,
study and optimization of adsorption and
covalent coupling of GA to magnetic
nanoparticles and displacement studies of
GA in the presence of phosphate ions.
The main results are represented in Figure
1, showing that it was possible to obtain
0.58 g of GA adsorbed /g MNP for 0.013
% wt [GA] in equilibrium (1h adsorption reaction), 0.32 g GA bound/g MNP for
0.0064 % wt [GA] in equilibrium in the covalent binding reaction of GA to the
functionalized MNPs with glutaraldehyde, and 0.48 g GA bound/g MNP for
0.011% wt [GA] in equilibrium for the covalent binding reaction between
functionalized GA with EDC and aminated MNPs. Displacement of Gum Arabic
by phosphate ions was observed only for nanoparticles containing adsorbed GA
subjected to 100mM and 1000mM phosphate buffers and the results were 1.3%
and 2.14 % displacement respectively.

[1] T. Kobayashi, A.I., M. Shinkai, H. Honda, Journal of Bioscience and Bioengineering
100 (2005) 1.
[2] S.J. Webb, K.P.L., R.J. Mart, J. Am. Chem. Soc. 129 (2007) 12080.
[3] D.N. Williams, K.A.G., T.R.P. Holoman, S.H. Ehrman, O.C. Wilson Jr. J
Nanoparticle Research 8 (2006) 749.
[4] R. Bandyopadhaya, E.N.-R., O. Regev, R. Yerushalmi-Rozen, Nano Letters 2 (2002)
25.
Figure 1. - Comparison between the
adsorption and covalent binding of
Gum Arabic on MNPs.

95


ADSORPTION OF PROTEINS ON MAGNETIC
NANOPARTICLES

Vera Castro, Ana S. Pina, Ana S. Cardoso, Abid Hussain, Ana C. A.
Roque*
REQUIMTE/CQFB, Chemistry Department, Faculdade de Cincias e Tecnologia, Costa
da Caparica
*cecilia.roque@dq.fct.unl.pt

The modification of magnetic nanoparticles (MNPs) in order to confer new
functionalities, nontoxicity and biocompatibility has been widely studied. These
modifications make MNPs valuable tools in medical applications (e.g. drug
targeting and delivery, cancer treatment and diagnostics), as well as in
biomolecular separations [1, 2]. In this work, we studied the surface modification
of MNPs with functional moieties and its potential use as a support for protein
adsorption. The characterization of modified MNPs was performed by
colorimetric methods, FTIR, BET and SEM. A model protein labelled with a
fluorophore was adsorbed on the functionalised MNPs in the presence of
different affinity metal ions (Cu2+, Ni2+ and Zn2+), and the amount of protein
bound/unbound was followed by fluorescence methods. The ratios between the
mean grey values of negative and positive controls were considered in the
evaluation of the several steps of a typical protein adsorption-desorption
protocol. The metal ions that had more success in the immobilization of the
protein were Ni2+ Cu2+ Zn 2+ in decreasing order.



[1] C. Hung, et al. Biochemical Engineering Journal 38 (2008) 164.
[2] A. Ito, et al. Journal of Bioscience and Bioengineering 100 (2005) 1.
96


MAPEAMENTO DE INTERACES ENTRE CADEIAS
LATERAIS DE PARES DE AMINOCIDOS

Miguel M. de Sousa*, Cristian Munteanu, Alexandre L. Magalhes
REQUIMTE, Universidade do Porto, R. Campo Alegre, 687, 4169-007 Porto, Portugal
*migueldesousa@adsl.tvtel.pt

Uma aproximao ao problema de determinao de estruturas secundrias e
tercirias de protenas a partir de sequncias de aminocidos a procura de
padres estruturais em protenas com estruturas tridimensionais determinadas
experimentalmente. A ocorrncia de padres de aminocidos e a sua localizao
dentro de hlices alfa no aleatria [1]. A compreenso da formao e
estabilidade de estruturas secundrias em protenas passa pela avaliao
completa e detalhada dos factores que para elas contribuem [2]. Pequenas
sequncias de resduos podem ter relevo na formao e estabilidade de protenas,
em particular pares de aminocidos (i, i+4) que so estabilizadores de hlices [3].
A primeira abordagem ao mapeamento de interaces entre cadeias laterais
realizada, resultou na publicao de um atlas de interaces [4] que, datado de
1992, carece de actualizao e refinamento. Iniciou-se uma actualizao deste
atlas, aproveitando a existncia e acesso a uma quantidade de dados
experimentais significativamente superior disponvel anteriormente, e
recorrendo a novas metodologias e que permitem a seleco, utilizao e
tratamento dessa informao de um modo sistemtico. Utilizando mdulos de
BioPython [5], foi criado um programa/interface que permite a obteno de
sequncias e estruturas de protenas relevantes, disponveis em bases de dados
[6]. A partir destes dados, e recorrendo simplificao da representao de
cadeias laterais de aminocidos foram determinados parmetros geomtricos
mdios (dimenses de cadeias, distncias e ngulos diedros) de pares de
aminocidos (i, i+4).

[1] H.M. Fooks, A.C.R. Martin, D.N. Woolfson, R.B. Sessions, E.G. Hutchinson, Journal
of Molecular Biology 356 (2006) 32; B. Goliaei, Z. Minuchehr, Febs Letters 537
(2003) 121; S. Kumar, M. Bansal, Proteins-Structure Function and Bioinformatics 31
(1998) 460; S. Penel, E. Hughes, A.J. Doig, Journal of Molecular Biology 287 (1999)
127.
[2] C. Branden, J. Tooze, Introduction to Protein Structure, Garland Publishing, Inc.,
New York, 1991; N.A. Fonseca, R. Camacho, A.L. Magalhes, Proteins: Structure,
Function, and Bioinformatics 70 (2008) 188.
[3] C.D. Andrew, S. Bhattacharjee, N. Kokkoni, J.D. Hirst, G.R. Jones, A.J. Doig,
Journal of the American Chemical Society 124 (2002) 12706.
[4] J. Singh, J.M. Thornton, Atlas of Protein Side-Chain Interactions, IRL Press, Oxford,
1992.
[5] S. Bassi, PLoS Computational Biology 3 (2007) e199.
[6] H. Berman, K. Henrick, H. Nakamura, Nature Structural Biology 10 (2003) 980; W.
Kabsch, C. Sander, Biopolymers 22 (1983) 2577.
97


MONITORIZAO DE EFLUXO DE POTSSIO E
FOSFATO DE CLULAS BACTERIANAS (LI STERI A
I NNOCUA)

M. Teresa S. O. B. Ferreira, Helena I. S. Teixeira, Ildik V. Tth*,
Francisco M. Campos, Jos A. Couto, Timothy A. Hogg, Antnio O.
S. S. Rangel
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, Rua Dr. Antnio
Bernardino de Almeida, 4200-072 Porto, Portugal
*ivtoth@mail.esb.ucp.pt

Os microrganismos podem ser uma fonte de preocupao na indstria
alimentar, causando doenas de origem alimentar ou deteriorando a qualidade
dos alimentos. Assim, prtica comum submeter os produtos alimentares a
tratamentos fsicos ou qumicos de modo a reduzir ou eliminar microrganismos.
Consequentemente, os laboratrios de controlo de qualidade devem dispor de
mtodos rpidos, exactos e fiveis para avaliar a viabilidade celular aps os
tratamentos. Os mtodos clssicos de ensaio incluem procedimentos laboriosos e
demorados como contagens em placa e tcnicas de microscopia.
Os sistemas de anlise em fluxo e os sensores potenciomtricos so
frequentemente referidos como mtodos eficazes para automatizar anlises
qumicas mas no tm sido usados extensivamente na rea de microbiologia
aplicada. Este trabalho tem como objectivo monitorizar o efluxo de ies de
clulas bacterianas (Listeria innocua), sujeitos a stress provocado pela adio de
agentes qumicos como o etanol e o cido p-cumrico.
Para o estudo de efluxo de anio fosfato implementou-se um sistema de fluxo
(FIA) [1], e para monitorizao de efluxo de catio potssio aplicou-se um
elctrodo sensvel a este io. Condies experimentais (volume de amostra, pH,
concentrao dos reagentes) foram ajustadas de modo a adaptar os mtodos ao
meio de clulas microbianas. As condies de stress aplicadas foram: etanol, de
0 at 25,0% (v/v) e cido p-cumrico entre 1 e 12,0 mM.
Os mtodos aplicados demonstraram ser ferramentas teis na monitorizao
de processos dinmicos como as respostas de populaes microbianas s
condies de stress provocadas.

Agradecimentos: I. Tth agradece o apoio financeiro da FCT e FSE (III Quadro
Comunitrio) atravs da bolsa SFRH/BPD/5631/2001.

[1] A. F. Torres, P. A. R. Mesquita, F. M. Campos, J. A. Couto, I. V. Tth, A. O. S. S.
Rangel, T. A. Hogg,. Microchim. Acta 159 (2007) 87.
98


WHEY PROTEIN ISOLATE - CHITOSAN INTERACTIONS:
A CALORIMETRIC AND SPECTROSCOPIC STUDY

Hilia K. S. de Souza
a
*, Guangyue Bai
b
, Margarida Bastos
b
, Maria
do Pilar Gonalves
a

a
REQUIMTE, Chemical Engineering Department, Faculty of Engineering, University of
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

b
Centro de Investigao em Qumica (UP) CIQ(UP), Department of Chemistry, Faculty
of Sciences, University of Porto, Rua do Campo Alegre, 687, P-4169-007, Porto, Portugal
*hsouza@fe.up.pt


Chitosan [(1-4)-2-amino-2-deoxy-|-D-glucan] is a linear homopolymer
obtained by partial deacetylation of chitin by treatment with strong alkali at high
temperature, and has a global charge that depends on pH. It has widespread
applications, such as food processing, agriculture, biomedicine and micro-
encapsulation. Many chitosan properties depend on its ability to interact with
anionic molecules. For oppositely charged systems (such as
protein/polysaccharide), the interaction can lead to the formation of aggregation
complexes. Theses complexes, or coacervates, have many practical
applications, such as fat substitution, protein separation, microencapsulation of
drugs and additives, etc.
The purpose of the present study is to characterize the interaction between
chitosan (Mw 250-300 kDa, deacetilation degree = 90%) and Whey Protein
Isolate (WPI) in acetate buffer solutions of different pH ( pH 3-6), by isothermal
titration micro-calorimetry (ITC) and UV-vis spectrophometry, at 35C.
At pH around 6, the WPI and chitosan have opposite charges, but at pH<5
both are positively charged. They have similarly charged systems. Therefore the
protein/polymer interaction depends on pH. A strong interaction at pH 6 and a
week interaction at pH 3 were observed by ITC measurements. In order to try to
interpret the obtained results in terms of a possible interaction mechanism we did
perform parallel turbidity measurements (OD) as a function of protein/polymer
ratio.
The obtained results will be presented in detail. The effects of pH change on
the interaction of these complex systems will be discussed. The interaction
enthalpies will be derived, and a possible interaction mechanism will be
suggested.

Acknowledgments: Thanks are due to FCT for financial support to REQUIMTE and
CIQ(UP), and for Post-Doc grant to H.K.S.S (SFRH/BPD/37514/2007) and to G.B
(SFRH/BPD/41407/2007).
99


Figura 1. Termograma
antes da termoxidao
DEGRADAO TERMOXIDATIVA DE COPOLMEROS E
MISTURAS BASE DE EVA

Isabel G. Moura
a
*, Gabriela Botelho
b
, Ana V. Machado
a
a
Departamento de Engenharia de Polmeros, Universidade do Minho, Campus de
Azurm, 4800-058 Guimares, Portugal
b
Departamento de Qumica, Universidade do Minho, Campus de Gualtar, 4710-057
Braga, Portugal
*isabelm@dep.uminho.pt

O desenvolvimento de polmeros biodegradveis tem sido objecto de vasta
investigao |1| nos ltimos anos. O interesse nestes materiais tem aumentado
consideravelmente no s por questes
ambientais, diminuio de resduos ps-consumo
e minimizar a utilizao de recursos energticos,
como tambm pela sua potencial aplicao nas
mais variadas reas, tais como, medicina,
embalagem, indstria automvel, etc. Uma vez
que muitos dos polmeros biodegradveis no
podem ser utilizados tal como existem, h vrios
mtodos para desenvolver e optimizar este tipo
de materiais de modo a obter produtos que
satisfaam os requisitos necessrios. Um dos
mtodos de obter polmeros de elevada performance atravs da mistura de um
polmero biodegradvel e um sinttico, ou pela modificao do um polmero
sinttico no qual so enxertados monmeros de polmeros biodegradveis.
Foram preparados por extruso reactiva copolmeros de etileno acetato de vinilo
(EVA) com cido lctico (LA) e caprolactona (-CL) e misturas de EVA com
PLA e EVA com PCL.
A caracterizao destes materiais foi feita por espectroscopia de
infravermelho, microscopia electrnica de varrimento e cromatografia de
permeao gel. Neste trabalho foi estudada a estabilidade trmica dos
copolmeros e misturas preparados, para isso recorrendo anlise
termogravimtrica (TGA). Na figura 1 apresentam-se alguns dos resultados
obtidos em que possvel observar que o mais estvel termicamente o EVA-28
e que a adio de PLA favoreceu a degradao.

|1| A.V. Machado, I. Moura, F. M. Duarte, G. Botelho, R. Nogueira, A. Brito,
International Polymer Processing XXII (2007) 5.
[2] S. Lee, J. W. Lee, Korea-Australia Rheology Journal 17 (2005) 71.
0
20
40
60
80
100
120
0 100 200 300 400 500 600
Temperature (C)
W
e
i
g
h
t

(
%
)
EVA-28 0h
PLA0h
EVA+PLA0h
EVA-LA0h
100


SELF-AGGREGATION OF MODIFIED DEXTRINS AND
THEIR INTERACTIONS WITH SURFACTANTS

G. Bai
a
*, C. Gonalves
b
, F. M. Gama
b
, M. Bastos
a

a
CIQ (UP), Department of Chemistry, Faculty of Sciences, University of Porto, R. Campo
Alegre, 687, Porto, Portugal
b
IBB-Institute for Biotechnology and Bioengineering, Centre for Biological Engineering,
Universidade do Minho, Campus de Gualtar 4710-057, Braga, Portugal
*gwbai@fc.up.pt

Hydrophobically modified polymers (HMP) are being considered as a new
class of amphiphilic material.

The family of dexC
16
that we study here is a class
of amphiphilic polymers that can be looked upon as a poly-surfactant
connected by hydrophilic spacers at the level of the head groups [1]. Therefore
the hydrophobic side chains can self-assemble to form micelle-like clusters or
hydrophobic microdomains of nanosize dimensions at very low concentration.
We have synthesized a series of new hydrophobically modified polymers
(dexC
16
). Briefly, a hydrophilic dextrin backbone has been grafted with acrylate
groups (VA), which were subsequently substituted with hydrophobic 1-
hexadecanethiol (C
16
), with different degrees of substitution (DS
C16
) [2].
In this work the self-assembling of these polymers in aqueous solution was
studied by steady-state fluorescence and the polymer/surfactant association by
Isothermal Titration Calorimetry (ITC) and fluorescence. The critical
concentrations were estimated for pure dexC
16
and for its mixture with
surfactants from the fluorescence results, and the different critical concentrations
as well as the enthalpy change for the formation of the aggregates of dexC
16

/surfactant were obtained from the ITC results. The association mechanism of
polymer/surfactant can be tentatively inferred from the detailed shape of the
calorimetric titration curves. Further, the effect of changing the number of
hydrophobic chains grafted on the polymer backbone (DS
C16
) on the interaction
will be discussed in detail.

Acknowledgments: Thanks are due to FCT for financial support to CIQ(UP), Unidade de
Investigao 81, and for Post-Doc grant to G.B (SFRH/BPD/41407/2007) and a PhD
grant to C.G. (SFRH/22242/2005).

[1] G. Bai, M. Nichifor, A. Lopes, M. Bastos. J. Phys. Chem. B 109 (2005) 21681.
[2] C. Gonalves, J.A. Martins, F.M. Gama. Biomacromolecules 8 (2007) 392.
101


CARACTERIZAO TRMICA DE MEMBRANAS DE
ACETATO DE CELULOSE/PANI

Daniel A. Cerqueira
a,b
, Artur J. M. Valente
a
*, Guimes R. Filho
b
,
Alfonso Jimnez
c
a
Departamento de Qumica da Universidade de Coimbra, 3004-535 Coimbra, Portugal
b
IQ-UFU, Av. Joo Naves de vila, 2121, 38.400-902,Cx.P. 593 Uberlndia-MG, Brasil
c
Deptartment of Analytical Chemistry, Nutrition and Bromatology, University of Alicante,
PO Box 99, 03080 Alicante, Spain

*avalente@ci.uc.pt

Neste trabalho foram produzidas misturas de polianilina (PANi) com
diacetato (dp) e triacetato (tp) de celulose obtidos a partir da celulose extrada do
bagao de cana-de-acar [1], bem como uma mistura de ambos (dtp) e
comparadas com membranas sem PANi (d, dt e t). As membranas foram
caracterizadas por TGA/DTG e DSC, figura 1.

100 200 300 400 500 600 700
0
25
50
75
100

Temperatura (C)
P
e
r
d
a

d
e

m
a
s
s
a

(
%
)
TGA
7
0
0
6
0
0
5
0
0
4
0
0
3
0
0
2
0
0
1
0
0
-2
-1
0
d
t
d
m
/
d
t
Temperatura (C)
DTG
50 100 150 200 250 300
tp
t
dtp
dt
d
F
l
u
x
o

d
e

c
a
l
o
r

(
m
W
)










e
n
d
o
Temperatura (C)
dp
DSC
Figura 1. TGA, DTG e DSC das membranas.

Observa-se que os perfis de degradao das amostras so muito semelhantes,
iniciando em aproximadamente 320C apresentando um pico de degradao em
aproximadamente 360C. Nesta comunicao o efeito da incorporao de PANi
em derivados de celulose ser discutido com base nos valores das entalpias de
cristalizao (AH
c
), fuso(AH
f
), bem como os valores de cristalinidade (%C)
calculados a partir da diferena entre AH
f
e AH
c
. A anlise por DSC mostra que a
polianilina, mesmo em baixa concentrao aumenta a cristalinidade das
amostras.

Agradecimentos: Os autores agradecem ao Prof. A. Monkman (Univ. Durham) a cedncia
da polianilina. Este trabalho foi parcialmente financiado pelo projecto MAT/2004/03827;
Cerqueira agradece CAPES pela bolsa PEDEB (BEX 0368/07-5).

[1] D.A. Cerqueira, G.R. Filho, C.S. Meireles. Carbohydrate Polymers 69 (2007) 579.
102


PREPARATION AND CHARACTERISATION OF LAYER-BY-
LAYER ASSEMBLED COMPOSITES FROM [Ni(SALEN)]-
TYPE COMPLEX WITH CARBON NANOTUBES

Snia Patrcio
a
, Ana S. Silva
a
, Cosme Moura
b
*, Cristina Freire
a
, A.
Robert Hillman
c

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre 4169-007 Porto, Portugal
b
CIQ, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto, Rua do
Campo Alegre 4169-007 Porto, Portugal
c
Department of Chemistry, University of Leicester, Leicester LE1 7 RH, UK
*cnmoura@fc.up.pt

Since their discovery in the early 90s, [1] carbon nanotubes (CNTs) have
been the subject of great interest due to their unique mechanical, electrical and
optical properties. In recent years, these unique properties have been exploited in
several research areas, more specifically in the electrochemistry field. [2, 3]
However, a crucial step in the applicability of CNTs is their dispersion in
solvents.
In this work, multi-walled carbon nanotubes (MWNTs) were dispersed in
0.5% poly(styrene 4-sulfonate) (PSS) solution, without any previous chemical
modification. The resulting polyelectrolyte-
functionalised MWNTs were characterised
by IR, Raman and UV-Vis spectroscopies,
and then used in the fabrication of layer-by-
layer films with cationic phosphonium
substituted salen-type complex. The
building-up of the multilayers was
monitored by UV-Vis spectroscopy and the
surface analysis was performed by scanning
electron microscopy (SEM-EDS) and X-ray
photoelectron spectroscopy (XPS).



Acknowledgements: This work was partially funded by FCT through project
POCTI/CTM/46 186/2002. SP thanks FCT for the PhD grant.

[1] S. Ijiima. Nature 3 (1991) 5456.
[2] N. Jia, L. Liu, Q. Zhou, L. Wang, M. Yan, Z. Jiang. Electrochim. Acta 51 (2005) 611.
[3] A. Profumo, M. Fagnoni, D. Merli, E. Quartarone, S. Protti, D. Dondi, A. Albini.
Anal. Chem. 78 (2006) 4194.
Figure 1. SEM image of PSS
functionalised MWNTs with
[Ni(salen)] deposited on mica.
103


THE BULK OXYPROPYLATION OF CHITIN
AND CHITOSAN AND THE CHARACTERIZATION
OF THE POLYOLS

S. Fernandes*, C. S. R. Freire, C. Pascoal Neto, A. Gandini
CICECO and Chemistry Dept. University of Aveiro, Portugal
*susanafernandes@dq.ua.pt

Our recent interest in the direct transformation of various agricultural and
forestry by-products (such as cork powder, sugar beet pulp and lignins) into
viscous polyols through a simple oxypropylation reaction, prompted us to extend
these studies to chitin and chitosan with the aim of valorising the less noble
fractions of these otherwise valuable renewable resources.
These systems are particularly straightforward in terms of their
implementation, since they only require the mixing of the activated solid
substrate with propylene oxide (PO) in an autoclave and the subsequent heating
of the ensuing suspension.
In the present context the chitin or chitosan samples were preactivated by an
ethanol KOH solution in order to generate anionic species derived from both OH
and NH
2
groups. Each dried substrate was then reacted with variable amounts of
PO at different temperatures. In some instances, the onset of the oxypropylation
reaction was rather sudden, as shown by a rapid temperature and pressure
increase, followed by a progressive pressure decrease associated with the PO
consumption. In other reactions, the oxypropylation proceeded more smoothly
over periods of time as long as hours.
In all cases the reaction product was a viscous liquid made up of
oxypropylated chitin or chitosan and some PO homopolymer. In some
experiments a solid residue was also formed. The optimization of these systems
consisted, among other aspects, in minimizing this solid residue.
Various separation procedures were applied to isolate each component, which
was thoroughly characterized by FTIR and NMR spectroscopy, DSC, TGA, OH
index and viscosity.
Depending on the actual reaction parameters adopted, the properties of these
polyol mixtures could be made to vary considerably, so they could comply with
different applications, e.g. the preparation of polyurethane foams or alkyd resins.
It is particularly important to emphasize that in a practical context, no
separation of the components is in fact necessary, because the multifunctional
oxypropylated chitin or chitosan on the one hand, and the difunctional PO
oligomers on the other hand, can be used jointly as macromonomers for any
polymer synthesis based on the reactivity of their OH groups. Thus, the systems
bear a promising green connotation given that no solvent is required and no
specific operation (separation, purification, etc.) is necessary to recover the
reaction product.
104


[Ni(SALEN)]-BASED POLYMERS BEARING CROWN
ETHER SUBSTITUENTS

J. Tedim
a
*, S. J. Gurman
b
, C. Freire
c
, A. R. Hillman
a

a
Department of Chemistry, University of Leicester, Leicester LE1 7RH, England
b
Department of Physics, University of Leicester, Leicester LE1 7RH, England
c
REQUIMTE/Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
4169-007 Porto, Portugal
*jat32@le.ac.uk

Conducting polymers based on -conjugated systems are among the most
promising materials for applications such as electrochromic devices [1], lithium
batteries [2] and photovoltaic cells [3].
In addition, conjugated polymers can
be used as transducers/amplifiers in
chemical sensors: conversion of the
chemical interaction between the
indicator and the analyte at molecular
level affects the collective properties
of the supramolecular system [4].
In this work, [M(salen)]
complexes bearing benzo crown ethers
were used as precursors to prepare
conjugated polymers. The resulting
systems were characterised using
electrochemical, spectroscopic,
compositional and structural techniques (Figure 1). The aim is two-fold: (i)
rationalisation of the electrochemical properties of poly[M(salen)] films in terms
of structural aspects, with particular relevance given to ion recognition [5] and
(ii) optimisation of the polymer performance by preparation of composites with
carbon nanotubes.

Acknowledgements: This work was partially funded by Fundao para a Cincia e a
Tecnologia (FCT), Portugal, through project POCTI/CTM/46186/2002. J. Tedim thank
FCT for PhD grant. We thank Daresbury Laboratory for the provision of X-ray beam
time.

[1] M. Mastragostino: Applications of Electroactive Polymers, Chapman & Hall 1
st
ed.,
London, 1993.
[2] N. Furukawa, K. Nishio: Applications of Electroactive Polymers, Chapman & Hall 1
st

ed., London, 1993.
[3] P. R. Somani, S. Radhakrishnan, Materials Chemistry and Physics, 77 (2002) 117.
[4] T. M. Swagger, Acc. Chem. Res., 31 (1998) 201.
[5] J. Tedim, A. Carneiro, R. Bessada, S. Patrcio, A. L. Magalhes, C. Freire, S. J.
Gurman, A. R. Hillman, J. Electroanal. Chem. 610 (2007) 46.

-200 0 200 400 600 800




Ni metal
Ni(NO
3
)
2
50 mmol dm
-3
/H
2
O
[Ni(3-MeOsaltMe)] powder
Energy/eV

/
N
o
r
m
a
l
i
z
e
d

u
n
i
t
s

N N
O O
R
2 R
2
M
R
1
Figure 1: XAS spectra in the region
of Ni K-edge
105


STUDIES ON THE DEPOSITION OF CHROMIUM FROM
CHROMIUM (III) DES USING MICROELECTRODE

Elisabete S. Ferreira*, C. M. Pereira, Fernando Silva
Departamento de Qumica, Faculdade de Cincias da Universidade do Porto, R. Campo
Alegre 687, 4169-007 Porto, Portugal
*elisabete.ferreira@fc.up.pt

Electroplating has, over recent decades, evolved from an art to an exact
science. This development was, and still is, essential for a variety of industries
including electronics, optics, sensors, aerospace, automobile (that uses for
example chrome plating to enhance the corrosion resistance of metal parts) to
mention a few. The electroplating industry is based on aqueous solutions due to
the high solubility of electrolytes and metal salts resulting in highly conducting
solutions [1].
Attempts to deposit chromium from aqueous trivalent chromium solutions
are made since 1900s, these trials are motivated by environmental deficiencies of
the presently used hexavalent process. However, it has been reported that the
electroreduction behaviour of chromium(III) is atypical due to the complex
nature of the chemistry and electrochemistry of chromium(III) species in the
aqueous solutions [2, 3].
A deep eutectic solvent (DES) is a type of ionic solvent with special
properties composed of a mixture which forms a eutectic with a melting point
much lower than either of the individual components. Compared to ionic liquids
which share many charactistics but are ionic compounds and not ionic mixtures,
deep eutectic solvents are cheaper to make by simply mixing the two solids with
gentle heating, until they melt, and then letting them cool, remaining the mixture
liquid [4, 5].
In the present work we studied the electrodeposition of metallic chromium
from chromium (III) deep eutectic solvent bath composed by choline chloride
(ChCl) and chromium(III) chloride hexahydrated (CrCl
3
.6H
2
O), using
electrochemical techniques such as cyclic voltammetry and chronoamperometry
in a glassy carbon microelectrode.

Acknowledments: The authors would also like to thank IONMET for financial support.

[1] Andrew P. Abbott, Katy J. McKenzie, Phys. Chem. Chem. Phys. 8 (2006) 4265.
[2] A. Baral, R. Engelken. J. Electroanal. Soc. 152 (2005) 504.
[3] T. Akiyama, S. Kobayashi, J. Ki, T. Ohgai, H. Fukushima. J. Appl. Electrochem. 30
(2000) 817.
[4] A. P. Abbott, D. Boothby, G. Capper, D. L. Davies, R. K. Rasheed, J. Am. Chem. Soc.
126 (2004) 9142.
[5] Andrew P. Abbott, Glen Capper, Stephen Gray, ChemPhysChem 7 (2006) 803.
106


AFM CHARACTERIZATION OF THE ORGANIZED
MOLECULAR FILMS

E. J. Pereira*, C. Carreira, C. M. Pereira, F. Silva
CIQ- L4, Department of Chemistry, Faculty of Science, University of Porto,

Rua do
Campo Alegre, 687, 4169-007 Porto, Portugal
*elisa.pereira@fc.up.pt

Ultra-thin films of organic molecules prepared by self-assembled monolayers
(SAMs) and LangmuirBlodgett (LB) techniques have received increasing
attention due to their potential applications in molecular electronics, nonlinear
optics, and the development of biological sensors [1].
LangmuirBlodgett (LB) films and self-assembled monolayers (SAMs) are
well organized molecular assemblies that are formed by layer-by-layer
deposition via either Van der Waals force or chemical bonding. The size of the
molecule determines the layer thickness and can be carefully controlled to
produce layers of uniform coverage

[2].
Atomic force microscopy (AFM) is an important method in the analysis of
thin organic films deposited on horizontal surfaces and can giving information
about regularity of the film in nanometer scale.

- The LB films were prepared by spreading a chloroform solution of Au NPs
on a subphase and kept at 20 C. The monolayer was compressed at the speed of
10 mm/min. After compression of monolayer to 15 mN/m, the monolayer was
transferred onto mica substrate by dipping mica on monolayer at a deposition
rate of 5mm/min.
The gold oleyl amine (OLA) functionalized nanoparticles were prepared
accordingly to the literature [3].
- Application of SAM technique consists in the immobilization of the gold
nanoparticles modified with OLA and subsequent deposition of the DNA
molecules on a flat substrate, as mica.
The step of the deposition were analysed by AFM, resulting in a transition
from three-dimensional to a two-dimensional conformation, limited by the
thickness of the layer.

Further results will be presented and discussed.

Acknowledgments: E. Pereira acknowledges to FCT and FEDER for financial support and
research grant project SFRH/BD/39279/2007.

[1] D-Q. Yang, Y. Sun, D-A. Da, Applied Surface Science 144-145(1999) 451.
[2] H. Lee, E. Bae, W. Lee, Thin Solid Films 393(2001) 237.
[3] M. Aslam, L. Fu, M. Su, K. Vijayamohanan, V.P. Dravid, J. Mater. Chem. 14 (2004)
1795.
107


PREPARATION OF NANOCOMPOSITES VIA RAFT
POLYMERIZATION IN MINIEMULSION

Susana Peixoto*, Penka I. Girginova, Manuel A. Martins, Tito
Trindade, Ana Barros-Timmons
CICECO, Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro, Portugal
*susanamrpeixoto@gmail.com

Nanocomposites based on SiO
2
/polymers have been widely investigated due
to their practical interest and because techniques for their preparation and
characterization are well-established. These materials have potential applications
in diverse fields [1] including in Nanomedicine; such is the case of composites
containing magnetic nanoparticles for use in cell separation and targeting drug
delivery [2].
In this work, core-shell nanostructures were prepared by coating inorganic
particles with polymer shells using miniemulsion polymerization. Having in
mind the type of materials envisaged, this polymerization technique shows some
advantages which include the speed of reaction, excellent dispersion of the
nanoparticles in droplets of monomer, low viscosity, and use of water as a
solvent.
While conventional radical polymerization was first used to prepare
SiO
2
@polystyrene and SiO
2
@poly(tert-butyl acrylate), in view of the synthetic
potential of living radical polymerization mechanisms [3], the use of RAFT
(reversible addition-fragmentation transfer polymerization) was then studied in
more detail. Indeed, RAFT proved to be efficient to prepare silica particles
coated with polymer and well defined block copolymers. Upon optimization of
the reaction conditions a nanocomposite formulated as Fe
3
O
4
@SiO
2
@PS was
prepared and fully characterized by a plethora of techniques which included
transmission electron microscopy (TEM), scanning electron microscopy (SEM)
and laser dynamic light scattering (DLS).

Acknowledgments: Grants Penka I. Girginova acknowledges FCT for a PhD Grant
(SFRH/BD/17968/2004) and Manuel A. Martins acknowledges FCT for a PhD Grant
(SFRH/BD/29475/2006). This work was funded by FCT and FEDER (project
PTDC/QUI/67712/2006).

[1] A. C. Esteves, A. Barros-Timmons, T. Trindade, Qumica Nova 27 (2004) 798.
[2] Y.-D. Luo,C.-A. Dai, W.-Y. Chiu, Journal of Polymer Science: Part A: Polymer
Chemistry (2007) 1014.
[3] A. C. C. Esteves, L. Bombalski, T. Trindade, K. Matyjaszewski, A. Barros-Timmons,
Small 3 (2007) 1230.
108


Figure 1. UV kinetic study of a typical
DA linear polymerization involving a
difuran and a bismaleimide monomer.
0
1.0
0.2
0.4
0.6
0.8
200 450 300 400
A
b
s
Wavelength /nm
250 350
0
1.0
0.2
0.4
0.6
0.8
200 450 300 400
A
b
s
Wavelength /nm
250 350
THERMOREVERSIBLE MATERIALS BASED ON THE
DIELS-ALDER REACTION OF FURAN MONOMERS

Dora Coelho*, Alessandro Gandini, Armando Silvestre
CICECO and Chemistry Departament, University of Aveiro, 3810-193Aveiro, Portugal
*dcoelho@ua.pt

The classical [4+2] Diels-Alder (DA) cycloaddition reaction between a diene
and a dienophile is one of the most fundamental and useful reactions in organic
chemistry.

Thanks to its reversible character, the DA reaction, applied to the formation
of thermally labile adducts between furan (diene) and maleimide (dienophile)
moieties, is ideally suited for the synthesis of thermally reversible linear and
crosslinked polymers through different strategies involving the polycondensation
of complementary bis-and poly-functional monomers [1].
In this study, the original application
of UV spectroscopy, coupled with that
of the more conventional
1
H NMR
counterpart, to follow the kinetics of the
formation and decoupling of the DA
adducts, proved particularly valuable.
Figure 1 shows the progressive
formation of adducts followed by the
decrease in the intensity of the
maleimide peak at~300nm. Conversely,
the retro-DA reaction was also be
followed by this technique through the
corresponding growth of the same peak.
The interest of this investigation stems from the thermal reversibility of the
systems involved, because it opens the way to temperature-sensitive materials
with promising applications, like mendability and recyclability, and to the use of
furan monomers and furan chemistry to prepare a new class of functional
macromolecular materials based on renewable resources.

Acknowledgements: Dora Coelho thanks FCT for her PhD Grant (SFRH/BD/28271/2006).

[1] A. Gandini; N.M. Belgacem, ACS Symp. Ser. 954 (2007) 280.
O
R
N
O
O
R' +
N
O
O
R'
O
R
O
R
N
O
O
R'
+
Endo Exo Furan Maleimide
109


Figura 2. TEM a. ncleo de slica; b. ncleo
de slica com perileno
Figura 1. Espectros de emisso/ excitao
das partculas de slica com perileno.
SNTESE E CARACTERIZAO DE NANOPARTCULAS
HBRIDAS COM NCLEO DE SLICA E COROA
POLIMRICA

Tnia R. Ribeiro, J. P. Farinha*
Centro de Qumica Fsica Molecular, Instituto Superior Tcnico, 1049-001 Lisboa
*farinha@ist.utl.pt

Neste trabalho sintetizaram e estudaram-se partculas ncleo-coroa com um
ncleo de slica e uma coroa de poli(butil metacrilato) com vista sua aplicao
em materiais fotnicos.
Foram sintetizadas partculas de
slica (pelo mtodo de Stber)
1
e de
slica com perileno (mtodo de
Stber modificado, utilizando um
derivado do perileno contendo dois
grupos etoxisilano), com dimetros
de 50 a 350 nm.
A superfcie das partculas foi
modificada com 3-mercaptopropil
trimetoxisilano (MPS) e estas foram
utilizadas na polimerizao em
emulso de uma coroa de poli(butil metacrilato).
A partir de disperses
aquosas limpas das partculas
ncleo-coroa com e sem perileno
prepararam-se filmes flexveis
em que a dimenso e
espaamento dos domnios de
slica no filme so controlados
pelas dimenses do ncleo e da
coroa.
Os materiais obtidos foram caracterizados em termos de dimenso,
polidispersividade, morfologia e propriedades pticas, utilizando as tcnicas de
microscopia electrnica de transmisso (TEM), microscopia confocal e
fluorescncia estacionria e resolvida no tempo.

Agradecimentos: Agradecemos ao Dr. Carlos Baleizo (CQFM) e ao Dr. Marek Kluciar
(CQFM) o perileno modificado.

[1] W. Stber, A. Fink, E. Bohn, J. Colloi. Inter. Sci. 26 (1968) 62.
a
b
110


CHARACTERIZATION OF MICELLAR AGGREGATES
OF POLY(DCA-B-DEA) AMPHIPHILIC
COPOLYMERS IN WATER

Gema Marcelo, Telmo J. V. Prazeres, J. P. S. Farinha,

J. M. G.
Martinho*
Centro de Qumica-Fsica Molecular, Instituto Superior Tcnico, 1049-001 Lisboa
*jgmartinho@ist.utl.pt

Amphiphilic block copolymers of poly(N-decylacrylamide-b-N,N-
diethylacrylamide) (p(DcA-b-DEA)), with the same pDcA hydrophobic block
and pDEA hydrophilic blocks of several lengths were synthesized by RAFT.
These copolymers with structure I bear a phenantrene group at the end of the
hydrophobic block.
These copolymers self-assemble in
water forming micelles with dimensions
that vary with temperature owing to the
thermosensitivity of the pDEA block.
The micellar aggregates were
characterized by light scattering. The static light scattering allows the calculation
of the molecular weight, M
w
; and the second Virial coefficient, A
2
, of the
micellar aggregates in water. Owing to the small value of the radius of gyration
the results does not allow their determination. The aggregation number of the
micelles is independent of the length of the hydrophilic block, N
agg
= 30. The
second Virial coefficient is also independent of the length of the hydrophobic
block. Figure 1 shows the variation with temperature of the hydrodynamic radius
of the micelles at several temperatures.
The hydrodynamic radius vary with
temperature according to the scaling law: R
H
=
R
C
+ bm

Derived from then star micelles
model
1,2
. From the global fit of the
experimental curves it was possible to recover
the radius of the core, Rc= 4.3 nm and the
scaling coefficient, a, at several temperatures.
The radius of the core from the model
compares with that obtained from the FRET
measurements between the phenanthrene labeled polymers and anthracene
homogeneous dispersed in the core of the micelles. The scaling coefficient
decreases with temperature from v=0.64 at 7 C to v=0.59 at 25 C according to
the decrease of the quality of water to pDEA with temperature increase.

[1] M. Daoud, J. P. Cotton, J. Phys. 43 (1982) 531.
[2] J. P. S. Farinha, J. M. R. dOliveira, J. M. G. Martinho, R. L. Xu, M. A. Winnik,
Langmuir 14 (1998) 2291.
n
8
m
CH2
CH3
CH
C
N
O
H2C
H3C
CH2
CH3
H2C
NH
H2C CH
C
NH
CH2
O
O S
S
111


CHIRAL SEPARATION OF PROFEN ENANTIOMERS BY
PREPARATIVE LIQUID CHROMATOGRAPHY

Antnio E. Ribeiro
a
, Nuno S. Graa
a
, Lus S. Pais
a
*, Alrio E.
Rodrigues
b

a
Laboratory of Separation and Reaction Engineering, School of Technology and
Management, Bragana Polytechnic Institute, Campus de Santa Apolnia, Apartado
1134, 5301-857 Bragana, Portugal
b
Laboratory of Separation and Reaction Engineering, Faculty of Engineering, University
of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*pais@ipb.pt

Profens are known as a major group of nonsteroidal anti-inflammatory drugs,
marketed as racemic mixtures and used in the treatment of arthritis and related
diseases. Recently, several pharmacological studies shown that profen
enantiomers (such as, ketoprofen and flurbiprofen) can display quite different
behaviours and, even more important, new therapeutic actions in the pure
enantiomeric form. Preparative chiral liquid chromatography is now a widely
accepted alternative separation process to the traditional and too time consuming
crystallization or asymmetrical synthesis techniques for the purification of
pharmaceuticals intermediates and other added-value products.
At an analytical scale, selectivity is commonly the main parameter to be
optimized. However, if the final goal is a preparative separation process
development, other parameters must also be considered. In a preparative
separation process, such as, in a Simulated Moving Bed (SMB) operation, high
productivities are obtained using operating conditions that maximize not only
selectivity but also the loading capacity, high feed concentrations and short cycle
times. Therefore, a correct selection of the mobile phase composition is advised,
since it will affect racemate solubility, selectivity and retention times [1].
In this work, experimental results obtained for the ketoprofen and
flurbiprofen enantiomers systems will be shown, including solubility and
adsorption measurements, and pulse and breakthrough experiments.
Additionally, simulation results, based on the experimental adsorption isotherms
measurements, will be presented to compare the performance of fixed-bed and
SMB processes. The experimental and simulation results show two different
situations. For the separation of ketoprofen enantiomers, pure ethanol is clearly a
better mobile phase than the usual high alkane content mobile phases. On the
other hand, for the separation of flurbiprofen enantiomers, a 10%ethanol/90%n-
hexane is proposed. The results obtained show that an individual study must be
carried out for each enantioseparation system, since different profen drugs can
show different behaviours.

[1] A.E. Ribeiro, N.S. Graa, L.S. Pais, A.E. Rodrigues. Sep. Purif. Technol. 61 (2008)
375.
112


EXTRACO ADSORTIVA EM BARRA (BAE) NOVAS
APLICAES PARA ANLISE DE OPICEOS

Alexandra F. P. Gonalves
a
, Nuno R. Neng
a,b
, Ana S. Mestre
a,b
, Ana
P. Carvalho
a,b
, Jos M. F. Nogueira
a,b
*
Universidade de Lisboa, Faculdade de Cincias,
a
Departamento de Qumica e
Bioqumica e
b
Centro de Qumica e Bioqumica, Campo Grande Ed. C8, 1749-016
Lisboa, Portugal
*nogueira@fc.ul.pt

O consumo de opiceos, como a herona (3,6-diacetilmorfina), cada vez
mais recorrente, sendo considerada uma das epidemias do sculo XX. Para alm
das graves consequncias toxicolgicas, os indivduos dependentes de opiceos
sofrem de depresso, sendo o suicdio cerca de catorze vezes mais frequente
neste grupo do que na populao em geral. O crescente aumento da
disponibilidade de opiceos resultou na indagao de metdos de deteco, em
amostras biolgicas, rpidos e universais, aliados acessibilidade da
interpretao dos dados.
Numerosos mtodos tm sido desenvolvidos para anlises desta classe de
compostos. As metodologias propostas para determinao de opiceos so
geralmente baseadas em processos de derivatizao e enriquecimento, seguidos
de anlise por cromatografia gasosa acoplada espectrometria de massa (GC-
MS). No entanto, as tcnicas de enriquecimento usualmente empregadas, como a
extraco em fase slida (SPE), dispendem tempo analtico e envolvem
considerveis quantidades de solventes orgnicos txicos, o que no se
compadece com o actual conceito de Qumica Verde, tendo em vista o impacto
ambiental que esse comportamento suscita.
Na presente contribuio, proposta uma nova tcnica de enriquecimento, a
extraco adsorptiva em barra, envolvendo materiais adsorventes, como os
carves activados, seguidos de retroextraco lquida e cromatografia lquida de
alta eficincia com deteco por rede de dodos (BAE-LD-HPLC-DAD) para a
determinao dos principais metabolitos da herona, morfina e codena, em
amostras biolgicas.
Constata-se que a tcnica desenvolvida uma excelente alternativa para a
determinao destes compostos polares, sem o tradicional recurso derivatizao
bem como a reduo drstica da utilizao de solventes orgnicos txicos. A
referida tcnica tem sido aplicada com sucesso anlise vestigial de amostras de
gua e urina.

[1] I.I. Galynker, D. Eisenberg, J.A. Matochik, E. Gertmenian-King, L. Cohen, A.S.
Kimes, C. Contoreggi, V. Kurian, M. Ernst, R.N. Rosenthal, J. Prosser, E.D. London,
Drug and Alcohol Dependence 90 (2007) 166.
[2] B. Tienpont, F. David, A. Stopforth, P. Sandra, LC-GC Europe 12 (2003) 2.
[3] A. S. Mestre, J. Pires, J. M . F. Nogueira, A. P. Carvalho. Carbon 45 (2007) 1979.
113


FLUORESCENCE QUENCHING OF A FLUORENE-
PHENYLENE COPOLYMER BY NITROAROMATICS

ngela C. P. Almeida
a
*, H. D. Burrows
a
, S. M. Fonseca
a
, L.
Marques
b
, A. T. de Almeida
b
, Ricardo Mallavia
c

a
Departamento de Qumica, Universidade de Coimbra, 3004-535 Coimbra, Portugal
b
Departamento de Engenharia Electrotcnica e de Computadores, Universidade de
Coimbra, 3030-290 Coimbra, Portugal
c
Instituto de Biologa Molecular y Celular, Universidad Miguel Hernndez, Elche 03202,
Alicante, Espanha
*angeladcpires@hotmail.com

Because of international concern about security and terrorist attacks, there is
an increasing need for new and more sensitive detection techniques for
explosives. Fluorescence techniques have high sensitivity and through the use of
luminescent conjugated polymers it is possible to
increase this further to the sub-g level by amplified
fluorescence quenching [1]. Nitroaromatics, such as
trinitrotoluene, are a particularly important group of
compounds, and their high electron affinities also
make them strong fluorescence quenchers. We have
studied the quenching of the fluorescence of the
fluorene-phenylene alternating copolymer poly-(9,9-
bis (6-N,N,N-trimethylammonium) hexyl) - fluorene
phenylene) bromide (HTMA-PFP [2]) by
nitroaromatics in both solution and polymer films. Results will be presented on
the effect of the nitroaromatic structure on quenching behaviour and suggestions
made on possible design of an optical sensor for these compounds. Initial results
will also be presented on theoretical simulations of the quenching interactions.

[1] S.W. Thomas, G.D. Joly, T.M. Swager, Chem.Rev. 107 (2007) 1339.
[2] M. Montesern, H.D. Burrows, A.J.M. Valente, V.M.M. Lobo, R. Mallavia, M.J.
Tapia, I.X. Garca-Zubiri, R.E. Di Paolo, A.L. Maanita, J.Phys.Chem.B 111 (2007)
13560.
Figure 1. HTMA-PFP
structure

114


TRANSFERNCIA DE ENERGIA ENTRE UM POLMERO
CONJUGADO CATINICO E PORFIRINAS ANINICAS

Sara M. A. Pinto
a
*, Hugh D. Burrows
a
, Mariette M. Pereira
a
,

Sofia
M. Fonseca
a
, Ricardo Mallavia
b

a
Departamento de Qumica, Universidade de Coimbra, 3004-535 Coimbra, Portugal
b
Instituto de Biologa Molecular y Celular, Universidad Miguel Hernndez, Elche 03202,
Alicante, Espanha
*smpinto@qui.uc.pt

Os polmeros conjugados constituem um importante grupo de materiais com
diversas aplicaes nomeadamente, em dodos emissores de luz, clulas
fotovoltaicas, sensores biolgicos e qumicos [1]. Recentemente, existe um
interesse crescente no domnio da investigao relacionada com os
polielectrlitos conjugados. A solubilidade destes em gua facilita o seu
processamento recorrendo a tcnicas do tipo ink-jet printing. Alm disso, este
tipo de compostos forma estruturas agregadas com caractersticas bastante
interessantes.
Actualmente existe um interesse considervel no desenvolvimento de
sistemas com uma boa gama de deteco e onde exista transferncia de energia
electrnica a partir de um polmero conjugado para um aceitador, que
posteriormente emita a luz. De facto, com a
utilizao de aceitadores contendo metais
pesados, foi possvel obter dispositivos
electrofosforescentes com alguma eficincia.
Contudo, este tipo de sistemas apresenta como
principal desvantagem o facto de ocorrer
separao de fase, o que provoca um
decrscimo na respectiva eficincia do
dipositivo [2]. Uma forma de evitar esta perda
utilizando self-assembly e neste contexto
apresentamos alguns resultados de transferncia de energia entre um sistema
deste tipo contendo o polielectrlito conjugado catinico poli{9,9-bis[6-N,N,N-
trimetilamnio)alquil]fluoreno-co-1,4-fenileno] iodo e porfirinas carregadas
negativamente. O efeito de alguns factores na eficincia da transferncia de
energia, como por exemplo a presena de substituintes halogenados e a
sobreposio espectral sero apresentados e discutidos.

Agradecimentos: Sara M. A. Pinto agradece ao Instituto de Investigao Interdisciplinar
da Universidade de Coimbra, Cmara Municipal de Coimbra e Bluepharma pelo apoio
financeiro. Este trabalho foi financiado por POCI/FCT/FEDER projecto
POCI/QUI/58291/2004.

[1] S. M. Borisov, V. V. Vasilev, Journal of Analytical Chemistry 59 (2004) 155.
[2] M. A. Baldo, M. E. Thompson, S. R. Forrest, Nature 403 (2000) 750.
Energy
transfer N
N N
N
X' X
R
X'
X R
X'
R
X
X'
X R
M
R SO
3
H
X H, Cl, F
X H, Cl, F
* *
N N H3C
CH3
CH3
H3C
CH3
CH3
n
Emission of
light
115


SYNTHESIS AND CHARACTERIZATION OF PORPHYRIN
MODIFIED INORGANIC MATERIALS AS SENSITIZERS
IN PHOTODEGRADATIVE PROCESSES

M. Silva
a,b
*, M. E. Azenha
b
, M. M. Pereira
a
, H. D. Burrows
b
, M.
Sarakha
c

a
Catalysis and Fine Chemistry Group, Department of Chemistry, Faculty of Sciences and
Technology, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal
b
Photochemistry Group, Department of Chemistry, Faculty of Sciences and Technology,
University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal
c
Laboratoire de Photochimie Molculaire et Macromolculaire, Universit Blaise Pascal,
24, Avenue des Landais, 63177 Aubire, France
*mas@fe.up.pt

Porphyrins and various metalloporphyrins are being synthesised and
immobilized on robust inorganic solids such as purely siliceous MCM-41
(channel diameter varied between 26.1 and 36.5 ), and zeolites NaY/HY
(channels with 7.4 ). Two different strategies for the preparation of these
immobilized sensitizers are being explored, the first based on the cage size effect
(route A) and the second involving template synthesis (route B). The
immobilization of the macrocycles into solid supports can have a marked
influence on the chemistry and photochemistry of these free systems, including
their thermal and mechanical stability, and the local environment of reactions.
The route A is based on the diffusion of sensitizers into a previously metal
exchanged inorganic support. The sensitizers need to be sufficiently stable
during the adsorption process. The route B involves the synthesis of the
porphyrins inside the support. In this case, aromatic aldehydes and pyrrole are
adsorbed into the exchanged support, are cyclized and then the metal is
incorporated.
The synthesized materials were characterized by physical techniques,
normally used, such as XRD, UV-Vis spectroscopy, and NMR.
These materials are expected to be good photosensitizers [1] and will be
tested in photodegradation reactions of pesticides, namely mecoprop, under
controlled pH, using light excitation at 366 nm.

[1] H.D. Burrows, M.Canle, J.A. Santaballa, S. Steenken, J. Photochem. and Photobiol.
B: Biology 67 (2002) 71.
116


FLUORESCENCE PROPERTIES OF FULLERENE C
70
IN
IMIDAZOLIUM IONIC LIQUIDS

Sofia Martins*, Paulo Forte, Pedro Gis, Carlos A. M. Afonso,
Carlos Baleizo, Mrio N. Berberan-Santos
Centro de Qumica-Fsica Molecular, Instituto Superior Tcnico, Universidade Tcnica
de Lisboa, 1049-001 Lisboa, Portugal
*sofia.a.martins@ist.utl.pt

Room temperature ionic liquids (ILs) are usually salts of bulky and
asymmetric organic cations. They have unique chemical and physical properties
such as negligible vapor pressure, good thermal stability, high ionic conductivity
and the ability to dissolve a wide range of substances. One of the driving forces
behind research on ionic liquids is their application as green solvents in
alternative to the conventional volatile and toxic organic solvents, nevertheless
they have also been applied in synthesis, catalysis, batteries, and fuel cells [1].
Some work has also focused on the photochemistry and photophysics both of
ILs and in ILs [2]. A very important aspect here is the optical purity of the ILs
that are frequently colored even after purification. This color results from
impurities that are difficult to remove [3]. Only recently have a few
spectroscopic studies been published using ultra-pure ILs [4].
Fullerenes and their potential applications opened a new field of research.
The most common fullerenes, C
60
and C
70
, present unique photophysical
properties. One of the most interesting, first observed in our group [5], is
thermally activated delayed fluorescence (TADF). Outstanding temperature and
oxygen sensors based on the TADF of fullerene C
70
were recently developed [6].
Encouraged by the particular spectroscopic properties of fullerenes and the
advantages of the use of ionic liquids as solvents, we decided to study the
fluorescence properties of fullerene C
70
in several ultra-pure imidazolium ionic
liquids. The fluorescence behavior of C
70
in these ILs will be presented and
discussed.

[1] R.A. Sheldon. Chem. Commun. (2001) 2399.
[2] A. Samanta. J. Phys. Chem. B 110 (2006) 13704.
[3] M.J. Earle, C.M. Gordon, N.V. Plechkova, K.R. Seddon, T. Welton. Anal. Chem. 79
(2007) 758.
[4] R. Katoh, Y. Yoshida, Y. Katsumura, K. Takahashi. J. Phys. Chem. B 111 (2007)
4770.
[5] M.N. Berberan-Santos, J.M.M. Garcia. J. Am. Chem. Soc. 118 (1996) 9391.
[6] C. Baleizo, M.N. Berberan-Santos. Ann. N. Y. Acad. Sci. xxx (2008) xxx.
117


Figure 1. Photochemical and
photocatalytic degradation of
clofibric acid.
PHOTOCATALYTIC OXIDATION OF CLOFIBRIC ACID
WITH NANOCRYSTALLINE TiO
2

Cludia G. Silva*, Joaquim L. Faria
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias s/n 4200-465 Porto - Portugal
*cssilva@fe.up.pt

Water and air treatment systems based in semiconductor heterogeneous
photocatalysis represent an area of major technical importance in our days.
Titanium dioxide (TiO
2
) is the most popular semiconductor material in
photocatalytic applications [1, 2]. It has been recognized that TiO
2
photocatalytic
efficiency is related to surface and structural properties of the semiconductor. In
the present work we produce TiO
2
nanocrystalline powders from Ti(IV)
isopropoxide by an acid catalyzed sol-gel method. We investigate the effect of
calcination temperature on several properties including crystal structure, phase
composition, surface area and particle
size. Materials were tested in the
photocatalytic oxidation of clofibric acid,
the active metabolite of several fibrate
drugs prescribed to reduce blood
cholesterol levels.
The most efficient photo-catalysts are
obtained upon calcinations at 673 K (Fig.
1). As calcination temperature increases, a
decline in the efficiency of the catalysts
was observed, attributed to the phase
transformation from anatase to rutile and
simultaneously, an increase in the
crystallite dimensions.
The photochemical and photocatalytic
oxidation of clofibric acid follows a pseudo-first order kinetic rate law. 4-
Chlorophenol, isobutyric acid, hydroquinone, benzoquinone and 4-
chlorocatechol were detected as main intermediates.

Acknowledgments: The authors gratefully acknowledge FCT and FEDER for financial
assistance (fellowship SFRH/BD/16966/2004 and projects POCI/EQU/58252/2004 and
POCTI/1181/2003).

[1] J.M. Herrmann. Top. Catal. 34 (2005) 49.
[2] C.G. Silva, W. Wang, J.L. Faria. J. Photochem. Photobiol. A 181 (2006) 314.
118


CYCLIC VOLTAMMETRIC ANALYSIS OF 2-
STYRYLCHROMONES

Ana Gomes
a
*, Eduarda Fernandes
a
, M. Beatriz Q. Garcia
a
, Artur M.
S. Silva
b
, Diana C. G. A. Pinto
b
, Clementina M. M. Santos
b
, Jos A. S.
Cavaleiro
b
, Jos L. F. C. Lima
a

a
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia, Universidade
do Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
b
Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro, Portugal
*ana.gomes@ff.up.pt

2-Styrylchromones (2-SC) are a chemical family of heterocyclic compounds,
vinylogues of flavones (2-phenylchromones), whose occurrence in nature has
been reported. Recently, several 2-SC derivatives were demonstrated to entail
antioxidant properties, namely, xanthine oxidase inhibition, hepatoprotection
against pro-oxidant agents in cellular and non cellular systems, and scavenging
activity against reactive oxygen and reactive nitrogen species (ROS and RNS).
Cyclic voltammetry is a widely used electroanalytic technique that allows
determining the redox properties of molecules in a solution. This technique has
previously been used to study the electrochemical oxidation mechanisms of
flavonolic compounds. In the present work, the electrochemical behaviour of
several 2-SC was studied by cyclic voltammetry, together with a number of
flavonoids with well known antioxidant activities, and the results correlated to
their ability to scavenge ROS and RNS.
The results obtained showed that 2-SC with a catecholic B-ring have a low
oxidation peak corresponding to the oxidation of the 3,4-OH (catechol) moiety.
A detailed analysis of this peak indicated a reversible redox process with a
coupled chemical reaction. The compounds with a phenolic B-ring have a
common peak, with oxidation potential values of about +0.4/+0.5 V vs.
Ag/AgCl, corresponding to the oxidation of the 4-OH. The oxidation of the
hydroxyl substituents in the A-ring generated peaks of higher potentials
(+0.7/+0.8 V vs. Ag/AgCl).
The results from the cyclic voltammetry assays were in agreement with those
from scavenging activity assays, i.e., lower values of oxidation potentials
corresponded to higher scavenging effects. The oxidation potentials obtained by
cyclic voltammetry seem to be applicable as a general indicator of radical
scavenging activity.
119


Figura 1. Formas III e IV
da GBP.
POLIMORFISMO E REACTIVIDADE DA GABAPENTINA

Vnia Andr
a
*, M. Teresa Duarte
a
, M. Ftima Minas da Piedade
a,b

a
Centro de Qumica Estrutural, Instituto Superior Tcnico, Av. Rovisco Pais, 1049-001
Lisboa
b
Departamento de Qumica e Bioqumica da FCUL, Campo Grande, 1749-016 Lisboa
*vaniandre@ist.utl.pt

A gabapentina (GBP, cido 1-(aminometil)ciclo-hexanoactico) um dos
princpios farmacologicamente activos (API) usados na teraputica contra a
epilepsia e na dor neuroptica [1].
Nos ltimos anos, o polimorfismo da gabapentina, assim como a sntese de
produtos anlogos, tem suscitado o interesse de vrios grupos de investigao.
No entanto, e ainda que vrios polimorfos deste
API estejam patenteados, at recentemente apenas
a estrutura cristalina da Forma II, a mais estvel,
se encontrava publicada. Duas novas formas
polimrficas Formas III e IV (as quais j se
encontravam patenteadas, mas sem estrutura
publicada) foram determinadas por difraco de
raios X de cristal nico [2,3]. Todos estes polimorfos so zwitteries e em todos
eles o ciclo-hexano apresenta uma conformao em cadeira, em que os grupos
substituintes alternam nas posies equatoriais e axiais. Como esperado,
apresentam conformaes e empacotamentos supramoleculares diferentes,
observando-se inclusiv a presena de ligaes por pontes de hidrognio
intramoleculares num destes novos polimorfos (Forma IV).
Neste estudo incluem-se tambm dois derivados da gabapentina: gabapentina
etil ester (GBP-E) e gabapentina-lactama (GBP-L), sendo que este ltimo foi
obtido na forma de co-cristal com cido benzico [4]. A gabapentina lactama
tem mostrado ter uma actividade farmacolgica relevante mas completamente
distinta da gabapentina, dado ser um neuroprotector [5].

[1] A. Gupta, A. B. Ciavarella, V. A. Sayeed, M. A. Khan, P. J. Faustino. J. Pharm. and
Biom. Analysis 46 (2008) 181.
[2] H. A. Reece, D. C. Levendis. Acta Crystallographica, C64 (2008) o105.
[3] D. Braga, F. Grepioni, L. Maini, K. Rubini, R. Brescello, L. Cotarca, M. T. Duarte, V.
Andr, M. F. M. Piedade. New Journal of chemistry, em submisso.
[4] V. Andr, M. T. Duarte, M. F. M. Piedade, M. M. Marques, P. P. Santos.
CrystEngComm, em submisso.
[5] A. Pielen, M. Kirsch, H-D. Hofmann, T. J. Feuerstein, W. A. Lagrze. Graefes Arch
Clin Exp Ophthalmol, 242 (2004) 240.
120


APLICAO DO MODELO DE ARRHENIUS NA
PREVISO DO TEMPO DE VIDA TIL DE GEOTXTEIS

Jos R. Carneiro
a
*, Paulo J. Almeida
b
, Maria L. Lopes
a

a
Departamento de Engenharia Civil, Faculdade de Engenharia de Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto
b
Departamento de Qumica, Faculdade de Cincias da Universidade do Porto, Rua do
Campo Alegre, 687, 4169-007 Porto
*rcarneir@fe.up.pt

Os geotxteis so materiais polimricos bastante aplicados em Engenharia
Civil (aterros sanitrios de resduos, estradas, tneis, barragens, canais, caminhos
de ferro, reservatrios, entre outras aplicaes) com as funes de separao,
filtrao, drenagem, proteco e/ou reforo. A oxidao uma das principais
causas de degradao qumica dos geotxteis, provocando a ruptura de cadeias
polimricas e, consequente, reduo na resistncia mecnica dos materiais. O
processo de oxidao ocorre segundo um mecanismo em cadeia relativamente
complexo que iniciado pela formao de radicais livres, quer pela aco do
calor (termo-oxidao), quer pela aco da radiao ultravioleta (foto-oxidao).
Na ausncia da radiao ultravioleta e temperatura ambiente, a degradao do
polipropileno (o polmero mais utilizado no fabrico dos geotxteis)
relativamente lenta. No entanto, esta degradao no pode ser desprezada em
materiais polimricos aplicados em obras de Engenharia Civil (normalmente
projectadas para vrias dezenas de anos).
A resistncia dos geotxteis termo-oxidao normalmente determinada
atravs de previses baseadas em dados experimentais obtidos sob condies de
degradao aceleradas (quer atravs do aumento da temperatura, quer atravs do
aumento da concentrao de oxignio). A lentido do processo de oxidao
temperatura ambiente dificulta a obteno de dados experimentais a partir de
casos de obra reais. Alm disso, a aplicao generalizada destes materiais em
construo ainda relativamente recente.
Neste trabalho, estudou-se a resistncia termo-oxidao de dois geotxteis
de polipropileno (um sem qualquer aditivo qumico e o outro estabilizado com
Chimassorb 944). Os geotxteis foram expostos a temperaturas elevadas (80 C,
90 C, 100 C e 110 C) numa estufa com uma atmosfera normal de oxignio
(21% de O
2
) durante diferentes perodos de tempo. O tempo de vida dos
materiais temperatura ambiental foi estimado utilizando o modelo de
Arrhenius; os resultados experimentais da degradao dos geotxteis a
temperaturas elevadas foram utilizados para estimar a velocidade de degradao
dos materiais a temperaturas consideravelmente mais baixas.

Agradecimentos: Os autores agradecem o apoio financeiro do projecto
PTDC/ECM/67547/2006.
121


IDENTIFICATION AND DISCRIMINATION OF
PHARMACEUTICAL RELEVANT BACTERIA BY
INTRINSIC FLUORESCENCE

Ana G. Almeida
a
, Carla S. Coutinho
a,b
*, Lus Meirinhos-Soares
c
,
Joo A. Lopes
b

a
Departamento de Engenharia Qumica e Biolgica, Instituto Superior Tcnico, Av.
Rovisco Pais, 1049-001 Lisboa, Portugal
b
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha 164, 4099-033 Porto, Portugal
c
Direco de Comprovao da Qualidade do INFARMED I.P., Parque de Sade de
Lisboa, Avenida do Brasil, n 53, 1749-004 Lisboa, Portugal
*carla.coutinho@ff.up.pt

Live bacteria contain a variety of intracellular biomolecules that have specific
excitation and emission wavelength spectra characterizing their intrinsic
fluorescence [1]. A new identification and discrimination method for bacterial
Genus, described as common contaminants of Medicines and Medical Devices,
was developed based on the measurement and consequently multivariate analysis
of the spectra of intrinsic fluorescence of aromatic amino acids/nucleic acids
(AAA+NA) and tryptophan (Trp), following their excitation at 250 and 270 nm,
respectively.
Intrinsic fluorescence spectroscopy presents potential advantages over the
time-consuming established phenotypic procedures: it is a very sensitive,
reliable, fast and reagentless technique with high potential to be established for
routine analysis [2].
This study was performed with 32 reference strains belonging to 12 different
bacterial genus: Bacillus, Staphylococcus, Burkholderia, Enterococcus, Kocuria,
Micrococcus, Pseudomonas, Salmonella, Stenotrophomonas, Acinetobacter,
Bordetella and Ralstonia. The fluorescence spectra obtained at 250 and 270 nm
were used to identify chemometrics models for genus classification. Spectra
obtained following excitation at 250 nm (AAA+NA) and 270 nm (Trp) were
modeled by PCA. Results demonstrated that the spectra obtained for the Trp
allow better discrimination. It was possible to cluster isolates belonging to the
different analyzed genus. A PLS regression model was developed based on the
12 reference isolates (using data at 270 nm). The model was validated using 6
strains isolated from contaminated medicines and medical device. The model
was able to correctly identify the genus corresponding to the 6 new isolates.

[1] L. Leblanc, E. Dufour, FEMS Microbiology Letters, 211 (2002) 147.
[2] H. Bhatta, E.M. Goldys, R.P. Learmonth, Appl Microbiol Biotechnol, 71 (2006), 121.
122


ELECTROCHEMICAL CARACTERIZATION OF
CHOLINE CHLORIDE BASED DEEP EUTETIC
SOLVENTS

Marta Figueiredo*, Ana Martins, Fernando Silva
Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007
Porto, Portugal
*martacfigueiredo@gmail.com

Room temperature ionic liquids are being considered an alternative candidate
for a variety of chemical processes [1]. Deep Eutetic Solvents (DES) comprising
substituted quaternary ammonium halide cations such as hydroxyethyltrimethyl-
ammonium (choline) chloride, ChCl, complexed with metal chlorides and / or H-
bond donors such as carboxylic acids, alcohols and amides [2, 3], have also
negligible vapor pressure, tunable viscosities, large electrochemical windows
and good ionic conductivities. DES are being evaluated in several processes such
as electrodeposition, electropolishing and electrowining of several metals [4, 5].
An important topic that needs deeper understanding is the structure of the
solid electrodes/DES interface. This work reports a study of the double layer
properties and the influence of temperature at the glassy carbon electrode / DES
interface for tree ionic liquids: Glyceline (ChCl+Glycerol), Ethaline
(ChCl+Ethylene Glycol) and Reline (ChCl+Urea) using electrochemical
techniques such as cyclic voltammetry and electrochemical impedance
spectroscopy.
The results obtained reveal that the polarization window is larger for Reline
(2V) than for Ethaline and Glyceline (1V).The shape and values (4 - 10 F/cm
2
at 75C) for the capacitance curves however are similar, suggesting that the role
of the ChCl cation is dominant in the structuring of the double layer. Capacitance
variation is expected as a result of reorientation of the ionic liquid ion pairs in the
electrode interface. There is only a slight influence of the applied potential and
temperature suggesting a nearly constant orientation of the ionic liquid ion pairs
at the interface.

Acknowledgments: This work has been carried out under the project IONMET (NMP2-
CT-2005-515743) at CIQ-L4.

[1] K.Seddon, J. Chem. Tech. Biotechnol. 68 (1997) 351.
[2] A. Abbott, G. Capper, S. Gray, ChemPhysChem 7 (2006) 803.
[3] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, Chem. Commun.
(2003) 70.
[4] A.P. Abbott, G. Capper, D. Davies, H. Munro, R.K. Rasheed, V. Tambyrajah, Chem.
Eur. J. 10 (2004) 3769.
123


THERMORESPONSIVE DEXTRAN AND CHITOSAN
HYDROGELS AS DRUG DELIVERY SYSTEMS

Antonio Lopes
a
*, Jos F. Almeida
a,b
, Paula Ferreira
c
, Armando
Alcobia
d
, Maria H. Gil
a

a
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Apartado
127, 2781-901 Oeiras, Portugal
b
Departamento de Engenharia Qumica, Universidade de Coimbra, Rua Slvio Lima,
3030-790 Coimbra, Portugal
c
Universidade Catlica Portuguesa, Centro Regional das Beiras, Campus de Viseu,
Estrada da Circunvalao, 3504-505 Viseu, Portugal
d
Hospital Garcia de Orta, Avenida Torrado da Silva, Pragal, 2801-951 Almada, Portugal
*alopes@itqb.unl.pt

Controlled Release from biocompatible materials has received recently much
attention for its biomedical applications. Due to their different properties, namely
the hydrophilicity, biocompatibility, hydrogels have been a subject of interest in
the biomaterials area.
In this work we prepared graft polymer hydrogels from chitosan and dextran
using N-Isopropylacrylamide as co-polymer to allow a thermo sensitive
behaviour in the final hydrogels. The reaction was initiated either chemically
(using ammonium cerium (IV)-nitrate radical initiator), photochemically (using
isocyanate and a biocompatible photoinitiator, Irgacure 2959) and using
radiation. The systems were fully characterized, namely swelling capacity,
elemental analysis, structure analysis, FTIR and
1
H-NMR. Moreover, the release
pattern of Ondansetron, a potent antiemetic substance used in the prevention of
chemotherapy-induced nausea and vomiting was determined and kinetically
characterized.
FT-IR data for the grafted Dex-NIPAAm systems revealed the presence of
two peaks around ~1650 and ~1550 cm
-1
ascertained with the typical amide I and
II bands of NIPAAm, revealing the success of the grafting reaction; this was also
confirmed by
1
H-NMR. Elementary analysis also showed an increase in the
Nitrogen proportion in all systems with the increase of the amount of co-polymer
used or the reaction time. Results showed that, irrespective of the polymers, there
is a positive correlation between co-polymer concentration and swelling, as well
as with drug incorporation. Release essays showed no significant pH dependence
(in the range of interest) and a moderate dependence with temperature. The
systems with less concentration in co-polymer were the ones showing the fastest
release pattern. As for the dependence with the temperature we verified that all
systems at higher temperature (40C) shown a short release time when compared
with the same systems at room temperature (25C). Nevertheless, the kinetic
patterns of the release for all the drugs used shows no significant changes.
Globally we can say that the most promising gels for topical application were
the gels made using photopolymerization.
124


THE ACETYLCHOLINESTERASE INHIBITION AND
ANTIOXIDANT PROPERTIES OF FENNEL

Maria Eduarda M. Arajo*, Carla Proena, Mrio Neto, Teresa
Duarte, Maria Luisa M. Serralheiro
Departamento de Qumica e Bioqumica/Centro de Qumica e Bioqumica, Faculdade de
Cincias da Universidade de Lisboa, Campo Grande, Ed. C8, 1749-016 Lisboa, Portugal
eduaraujo@fc.ul.pt

Fennel, Foeniculum vulgare Miller, is a plant native in the Mediterranean
region and also in the temperate Asia. Its characteristic anise like taste is much
appreciated and its cultivation was extended to other places. Its most typical for
the cuisines of Southern Europe. Despite its use in cooking fennel is used since
Antiquity for its diverse medicinal properties. Fennel leaves are traditionally
used to treat diarrhea and bronchitis, the leaves and seeds to treat impotency and
the root to stimulate lactation in women. The diuretic properties of the root are
used to treat hypertension. Fennel is described in several Pharmacopoeias [1].
On our on going work on acetylcholinesterase inhibitors we have found that
some aromatic plants were moderate inhibitors [3]. Increasing the levels of
acetylcholine by inhibition of acetylcholinesterase (AChE) is a strategy for the
treatment of Alzheimers disease (AD) and senile dementia, counteracting the
cognitive impairment and memory loss whicht are the more visible symptoms.
The AChE inhibitory activity of fennel extracts, ethanol and aqueous extracts
from stems and also flowers and fruits, was evaluated by the Ellman test. The
antioxidant activity using the DPPH test and the total phenolic content were also
determined [2].

Table 1. AChE, antioxidant activity and total phenolic compounds of fennel

IC
50
AChE
(mg/mL)
Antioxidant Activity
EC
50
(g/mL)
Total phenolics
(mg/g extract)
Extract
Flowers
and fruits
Stems
Flowers
and fruits
Stems
Flowers
and fruits
Stems
Infusion 1.080.27 1.010.20 24.81.6 48.02.5 33.10.9 108.56.6
Decoction 1.010.23 1.020.20 32.91.5 34.61.6 58.01.5 135.21.4
Ethanol 0.470.06 0.890.06 10.71.1 26.10.9 48.94.4 33.73.8

In conclusion, fennel, showing simultaneously antioxidant activity and AChE
inhibitory, capacity can be considered a food having some functional function
besides its traditional value.

[1] A., Proena da Cunha, A. Pereira da Silva, O. R. Roque. Plantas e produtos vegetais
em fitoterapia. Fundao Calouste Gulbenkian. Lisboa, 2003.
[2] A. T. Mata, C. Proena, A. R. Ferreira, M. L. M. Serralheiro, J. M. F. Nogueira, M. E.
M. Arajo. Food Chemistry, 103 (2007) 778.
125


STUDIES ON SONLO PROPERTIES OF HALF-SANDWICH
COMPLEXES USING TD-DFT CALCULATIONS

Tiago Silva*, A. J. P. Carvalho, Paulo J. Mendes
Centro de Qumica de vora, Universidade de vora, Rua Romo Ramalho, 59, 7000-671
vora, Portugal

*tjlsilva@gmail.com

During the last decades theres been a growing interest in the use of
organometallic complexes as potential building blocks for second-order
nonlinear optical (SONLO) materials, namely for photonics and integrated optics
applications [1]. q
5
-Monocyclopentadienylmetal complexes are known to be
good candidates for SONLO purposes. Systematic studies in these systems give
the basis to predict that the combination of substituted acetylide thiophene
chromophores with ruthenium and iron metal centers can enhance the first
hyperpolarizabilitiy [2,3]. Also, it is well known that the first hyperpolarizability
of purely organic push-pull molecules increases strongly with the length of the
conjugated chain. Nevertheless, the exploitation of this effect in several q
5
-
monocyclopentadienylmetal complexes showed contradictory results. The time-
dependent density functional theory (TD-DFT) method within the DFT frame
provides the satisfactory molecular orbital explanation for the electronic
excitation, which is usually recommended for calculating the excited-state
behaviours. In the case of organometallic complexes, the TDDFT method is one
of the most suitable choices to calculate accurately the excited energy and first
hyperpolarizabilities.
In this work we used the TD-DFT method to study the first
hyperpolarizabilities of [MCp(P_P)(CC{SC
4
H
2
}
n
Y)] complexes (M=Ru, Fe;
P_P= H
2
PCH
2
CH
2
PH
2
, DPPE; Y= CHO, NO
2
;

n= 1,2) (Figure 1). The effect of
the bidentate phosphine, different electron-withdrawing groups and the
conjugated length of the chromophore will be evaluated. Our interest is not only
to predict the values but also to investigate the microscopic SONLO
mechanism in these complexes.

[1] M.H. Garcia, et al. Handbook of Advanced Electronic and Photonic Materials and
Devices, Vol 9 (2001) 127.
[2] M.H. Garcia, M.P. Robalo, A.R. Dias, M.T. Duarte, W. Wenseleers, G. Aerts, E.
Goovaerts, M.P. Cifuentes, S. Hurst, M.G. Humphrey, M. Samoc,; B.L. Davies.
Organometallics 21 (2002) 2107.
[3] M.H. Garcia, P.J. Mendes, M.P. Robalo, A.R. Dias, J. Campo, W. Wenseleers, E.
Goovaerts. J. Organomet. Chem. 692 (2007) 3027.
126


Figure 1. Experimental solubilities (,
paracetamol; , budesonide; ,
furosemide; , allopurinol) in water and
modeling results ().
T/K
300 305 310 315 320
M
o
l
e

f
r
a
c
t
i
o
n
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
SOLID-LIQUID EQUILIBRIA OF SOME
PHARMACEUTICAL COMPOUNDS

Ftima L. Mota
a
*, Antnio J. Queimada
a
, Simo P. Pinho
b
, Eugnia
A. Macedo
a

a
LSRE - Laboratory of Separation and Reaction Engineering, Departamento de
Engenharia Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr.
Roberto Frias s/n, 4200-465 Porto, Portugal
b
LSRE - Laboratory of Separation and Reaction Engineering, Departamento de
Tecnologia Qumica e Biolgica, Instituto Politcnico de Bragana, Campus de Santa
Apolnia, Apartado 1134, 5301-857 Bragana, Portugal
*fatima.mota@fe.up.pt, fax: +351225081674

Solubility is an important property
which affects the release, transport and
absorption of drugs. Solubility data
involving new drug molecules and their
precursors are frequently unavailable
hampering drug formulation. Although
some thermodynamic models can be
used, the existence of some
experimental data is still fundamental
for an appropriate model development
and evaluation.
In this work, solubilities of some
drugs, such as paracetamol,
budesonide, allopurinol and
furosemide were measured as a
function of the temperature in several solvents, namely water, ethanol and
acetone. Solubilities were determined by the analytical shake-flask method,
using constant temperature jacketed glass cells for generating the saturated
solutions, followed by composition analysis by HPLC. As the analytical shake-
flask method is an expensive and time consuming procedure, an alternative
method to measure solubility using DSC was also studied [1], with the advantage
of being faster and consuming smaller amounts of sample. Melting data of the
pure drugs were also obtained by DSC.
The NRTL-SAC model [2] was used to represent the measured data. This
model provides a simple and practical thermodynamic framework for phase
equilibria of drug systems. A comparison between experimental and model
results showed that NRTL-SAC is an appropriate tool to represent the solubility
of these complex molecules.
Ftima Mota acknowledges her FCT PhD scholarship SFRH/BD/32372/2006.
[1] R. Mohan, H. Lorenz, A.S. Myerson, Ind. Eng. Chem. Res. 41 (2002) 4854.
[2] C.C. Chen, Y.H. Song, Ind. Eng. Chem. Res. 43 (2004) 8354.
127


MULTIPUMPING AND MULTICOMMUTATED
REVERSED-FLOW SYSTEMS FOR THE
DETERMINATION OF TRIMIPRAMINE

Joo A. V. Prior*, David S. M. Ribeiro, Joo L. M. Santos, Jos L. F.
C. Lima
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha n. 164, 4050-047 Porto, Portugal
*joaoavp@ff.up.pt

This work involves the implementation, in a multi-pumping flow system
(MPFS) [1], of a method for the determination of the antidepressant drug
trimipramine in pharmaceutical formulations, based on the reaction with
ammonium monovanadate in acidic medium yielding a coloured compound
monitored at 620 nm. The improved flow mixing conditions during sample and
reagents insertion and transport, due to the chaotic movement of the solutions
originated by the MPFS pulsed flow, assured a fast reaction zone
homogenization in a reduced residence time, despite the use of highly viscous
solutions, as is the case of the sulphuric acid solution used in the determination
of trimipramine, that can impair the hydrodynamic flow inside the tubing.
A linear working range for trimipramine concentrations of up to 50 mg L
-1
(r
= 0.9998; n = 6) was obtained and the detection limit was about 1.15 mg L
-1
. The
sampling rate was approximately 50 determinations per hour. The comparison of
the obtained results with those furnished by the reference procedure revealed
relative deviations lower than 4.7%.
The analytical figures of merit of the MPFS methodology (Figure 1) were
compared with a MCFS approach (Figure 2) also applied for the trimipramine
determination [2], which was based on the oxidation of the drug by the same
reagent, revealing some improvements of the figures when using the MPFS.

Figure 1: Figure 2:


[1] R.A.S. Lapa, J.L.F.C. Lima, B.F. Reis, J.L.M. Santos, E.A.G. Zagatto, Anal. Chim.
Acta 466 (2002) 125.
[2] J.A.V. Prior, J.L.M. Santos, J.L.F.C. Lima, J. Pharm. Biomed. Anal. 33 (2003) 903.
128


SPECTROPHOTOMETRIC DETERMINATION OF
INDAPAMIDE IN A MULTI-PUMPING FLOW SYSTEM

David S. M. Ribeiro*, Joo A. V. Prior, Joo A. Lopes, Joo L. M.
Santos, Jos L. F. C. Lima
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha n. 164, 4050-047 Porto, Portugal
*dsmribeiro@gmail.com

Indapamide is an oral antihypertensive diuretic agent that was approved by
the U.S. Food and Drug Administration (FDA) in 1983 and is indicated for the
treatment of hypertension and edema.
In the present work, an automatic methodology of flow analysis exploiting
the multi-pumping [1] concept was developed for the spectrophotometric
determination of indapamide in commercially available pharmaceutical
formulations. The flow manifold
(Figure 1) comprised four micro-
pumps, with a capacity to dispense
a volume of 8 L per pulse, each
valve responsible for the transport
of each of the four solutions
involved; P
1
MBTH, P
2
Ce
(IV), P
3
Sulphuric acid, P
4
-
Sample. The determination method was based on the oxidative coupling reaction
of the drug with 3-methyl-2-benzothiazolinone hydrazone (MBTH) in the
presence of cerium (IV) in an acidic medium [2].
The absorbance of the reaction product was measured at the wavelength 601
nm (Figure 1, Detector D). Multivariate experimental design was used to
optimize the chemical and physical parameters of the multipumping flow system
proposed. The optimization of the chemical parameters was performed using a
Plackett-Burman factorial design with 3 center points and 24 randomised runs.
After evaluating the importance of all the variables with the objective of
obtaining the maximum absorbance, the parameters were optimized using a
Central Cubic Faces design. The physical parameters reactor length, pulse time
and number of pulses, were equally optimized using a similar experimental
design approach.
The proposed methodology allowed the rapid quantification of indapamide,
which could represent an advantageous alternative for the pharmaceutical control
at the industrial level, and additionally, required low quantities of reagents and
produced reduced volumes of residues.

[1] R.A.S. Lapa, J.L.F.C. Lima, B.F. Reis, J.L.M. Santos, E.A.G. Zagatto, Anal. Chim.
Acta 466 (2002) 125.
[2] N. F. Youssef. J. AOAC Int. 86 (2003) 935.
129


N
F
N
N
COOH
O
C
2
H
5
Figure 1. Enrofloxacin
N
F
N
N
COOH
O
C
2
H
5
INTERACTION OF ENROFLOXACIN WITH OUTER
MEMBRANE PROTEIN C (OMPC)

Isabel Sousa
a
, Helge Weingart
b
, Mathias Wintherhalter
b
, Paula
Gameiro
a
*
a
Requimte, Faculdade de Cincias, Universidade do Porto, R. do Campo Alegre, 4169-
007 Porto, Portugal
b
Jacobs University Bremen, Campus Ring I, 28759 Bremen, Germany
*agsantos@fc.up.pt

The outer membrane proteins of the cell envelope of gram (-) bacteria
function as a molecular sieve fairly permeable to small solutes below 600 Da.
Several studies with bacteria strains showed that the OmpC porin is important
for the uptake of antibiotics as cephalosporins and fluoroquinolones.
Fluoroquinolones are a series of synthetic
antibacterial agents commonly used in the
treatment of several bacterial infections.
Enrofloxacin (ENR) was the first fluoroquinolone
introduced in Veterinary medicine.
As it has been mentioned, fluoroquinolones use
a transmembranar porin to pass through the outer
membrane of the gram (-) bacteria but the exact
mechanism and the interaction between these drugs
and the lipid composition of the outer membrane remains unknown. Insights
about this mechanism can be obtained from the study of their partition and
location in membrane models such as liposomes, since they can mimic the
chemical/structural environment of cell membranes.
In a first step, partition coefficients between ENR and DMPC and DMPG
liposomes have been studied by fluorescence spectroscopy. In order to
understand the interaction between ENR and OmpC (an E.coli outer membrane
protein) studies with mixed micelles OmpC/DMPC/oPOE have been performed.
It is known that OmpC is a trimer and for each monomer there are 4 tryptophan
residues (Trp57, Trp72, Trp 103, Trp202). Through fluorescence quenching
studies, of mixed micelles and water-soluble quenchers Acrylamide and KI, in
the presence and absence of ENR we may be able determine at which level the
interaction occurs: at a hydrophilic or hydrophobic environment. Our results
show that the permeation mechanism may include an electrostatic interaction at
the interface region and may be the first step that governs the mechanism of
interaction with bacterial natural membranes.

Acknowledgements: Partial financial support for this work was provided by Fundao
para a Cincia e Tecnologia through POCI/SAU-FCF/56003/2004 and EU Marie Curie
Research Training Networks MRTN-CT-2005-019335 Translocation
130


VOLTAMMETRIC BIOELECTRONIC TONGUE FOR THE
DETERMINATION OF PHENOLIC COMPOUNDS

Georgina M. S. Alves*, Adlio A. S. C. Machado, Jlia M. C. S.
Magalhes
LAQUIPAI, Department of Chemistry, Faculdade de Cincias da Universidade do Porto,
R. Campo Alegre n 687, 4169-007Porto, Portugal
*c0773147@alunos.fc.up.pt

Voltammetric electronic tongues [1-4] are analytical devices constituted by
one or more voltammetric sensors and data processing tools. Within this class of
analytical devices Bioelectronic tongues are characterized by use of
voltammetric biosensors.
Phenols are significant and widespread pollutants in the environment. A
biosensor approach, with its inherent advantages of high specificity, high
sensitivity and rapid detection mechanism may provide a solution for in situ
monitoring of phenolic compounds.
Laccase is a type of copper-containing oxidase which can oxidize
polyphenols, anilines, benzenethiols, etc., with the concomitant reduction of
molecular oxygen to water. Coupling this enzyme with amperometric detection
allowed the development of several biosensors for phenolic compounds.
Amperometric signal overlapping in the voltammograms is high and
simultaneous quantification of different compounds is a problem, but Artificial
Neural Networks (ANN) can solve it.
In this communication, the results obtained in the development of a
Bioelectronic tongue for simultaneous quantification of catechol (1 to 28 M), p-
cresol (2 to 70 M) and 2-amino-phenol (1 to 18 M) based on a screen-printed
laccase biosensors and the use of ANN in order to deconvolute the contribution
of each analyte are presented and discussed.

Acknowledgements: This work is part of a project: POCI/QUI/58076/2004 from Fundao
para a Cincia e Tecnologa. Finantial support is gratefully acknowledged.

[1] V. Parra, A. Arrieta, A. Fernndez-Escudero, M. Rodrguez-Mndez, A. De Saja,
Sensor Actuat. B 118 (2006) 448.
[2] J. Olsson, F. Winquist, I. Lundstrm, Sensor Actuat B 118 (2006) 461.
[3] F. Winquist, R. Bjorklund, C. Krantz-Rlcker, I. Lundstrm, K. stergren, T.
Skoglund, Sensor Actuat B 111 (2005) 299.
[4] S. Holmin, C. Krantz-Rlcker, F. Winquist, Anal. Chim. Acta, 519 (2004)39.
131


FRIEDEL-CRAFTS ACYLATION OF HETEROAROMATIC
COMPOUNDS OVER ZEOLITES

Amadeu F. Brigas
a
, Bruna C. S. Santos
a
*, Vasco F. D. lvaro
a
, Eric
G. Derouane
a,b,

a
FCT, CIQA, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
b
Centro de Engenharia Biolgica e Qumica, Departamento de Engenharia Qumica, IST,
Av. Rovisco Pais, 1049-001, Lisboa, Portugal
*abrigas@ualg.pt; deceaced

The chemistry of heteroaromatic compounds is almost as challenging as ever
despite of decades of research [1]. Due environmental pressure, alternative
procedures and adaptations of classical methods are frequent and, among these,
the use of solid microporous materials are common [2].
We which to report our contribution of the Friedel-Crafts acylation of some
heterocyclic compounds, over zeolites. Under the conditions used, the zeolite
provides a simple and smooth method for facile acylation of thiophenes, furans
and pyrroles and also conferring some interesting selectivity. For example, the
acylation of thiophene with acetic anhydride to give 2-acetylthiophene in 90 %
yield occurs in just10 min (eq. 1; X = S, R = H).
X
X =N, O, S
R
X
R
O
O
O
O
HBEA, 60 C
(1)

We have demonstrated that the reaction is, as expected, sensitive to
substituent effects and several zeolites, with and without modification, were
tested. It was found that better results were obtained with zeolite Beta, HBEA, or
zelolite Beta inpreganated with indium, in which case, the increased in activity
tends to be proportional to the ratio of indium. Generally, thiophene derivatives
react faster and more selectively. Furan reacts slightly slower but still producing
only the 2-isomer and, finally, pyrrole derivatives react slower and preferably on
position 3 even when position 2 is available.
Experiments with competitive adsorbants and adequate modification of the
catalyst have been used to prevent the reactions to get to a slow rate or stagnant
point after the initial fast kinetic burst.

[1] C. Schmuck, D. Rupprecht, Synthesis 20 (2007) 3095.
[2] G. Sartori, R. Maggi, Chem. Rev. 106 (2006) 1077; M. Guisnet, F. R. Ribeiro,
Zelitos um nanomundo ao servio da catlise, Fundao Calouste Gulbenkian, 2004,
pp. 203-215; M.L. Kantam, K.V.S. Ranganath, M. Sateesh, K.B.S. Kumar, B.M.
Choudary. J. Mol. Catal. C, 225 (2005) 15; E.G. Derouane. Microporous and
Mesoporous Solid Catalysts, Vol. 4, Wiley, 2007
132


SYNTHESIS AND CHARACTERIZATION OF NOVEL
OCTAHEDRAL [FeH(DPPE)
2
(NCR)][PF
6
] COMPOUNDS

Antnio P. S. Teixeira
a,b
*, Ana Falco
a
, Vnia F. Pais
a
, M. Paula
Robalo
b,c
, M. Helena Garcia
b,d

a
Dep. de Qumica & Centro de Qumica de vora, Universidade de vora, Colgio L. A.
Verney, R. Romo Ramalho, 59, 7000-671 vora
b
Centro de Qumica Estrutural, IST, Av. Rovisco Pais, 1049-001 Lisboa
c
Dep. Engenharia Qumica, ISEL, R. Conselheiro Emdio Navarro 1, 1950-062 Lisboa
d
Faculdade de Cincias da Universidade de Lisboa, Edifcio C8, Campo Grande, 1749-
016 Lisboa
*apsteix@uevora.pt

Organometallic compounds have been extensively studied in search of new
materials with enhanced NLO properties due to their large hyperpolarizabilities,
fast response times and architectural flexibility. Organometallic molecules with a
highly polarisable -conjugated backbone with an electron-donor (D) and an -
acceptor (A) groups attached to opposite ends can a large second-order nonlinear
susceptibility [1].
In the search of new systems, we synthesised iron(II) octahedral complexes
with the general formula [FeX(biphosphine)
2
(NCR)](PF
6
) (X=Cl, I or H;
bisphosphine=DMPE, DPPE, dppen, odppb; NCR=mono- or
dinitrobenzonitriles) with interesting
results towards NLO properties [2,3].
In this communication, we report
the synthesis and characterization of a
series of [FeH(DPPE)
2
(NCR)](PF
6
)
derivatives. The acceptor capacity of
the nitrile chromophore was changed
due to the position (ortho and para) of
the nitro group and with the change in
length of the conjugated backbone. The
results were analysed to evaluate the
electronic richness of the metal centre and the influence of the structural changes
of the coordinated nitrile, which may give some contribution to understand the
relationships between structure and NLO responses.
Acknowledgements: We thank FCT and POCTI (POCTI/QUI/48443/2002), UE (FAIC)
and IPL (IPL/16/2003) for financial support.
[1] E. Goovaerts, W. Wenseleers, M.H. Garcia, G.H. Cross, in Nonlinear Optical
Materials, Vol. 9 (Ed. H. S. Nalwa), Academic Press (2001) 127.
[2] A.R. Dias, M.H. Garcia, M.P. Robalo, A.P.S. Teixeira, "Complexos de Ferro(II) com
benzonitrilos p-substitudos: sntese e caracterizao", O14, 5 Conferncia de Q.
Inorgnica, SPQ, Monte Real, 6-7 Abril 2001.
[3] M.P. Robalo, A.P.S. Teixeira, M.H. Garcia, A.R. Dias, M.T. Duarte, M.F.M. Piedade,
J. Campo, W. Wenseleers, E. Goovaerts, Eur. J. Inorg. Chem. (2006) 2175.
Fe NCR H
P
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
PF
6
133


Figure 1. CMB-TTF [2+2]
derivative
SUPRAMOLECULAR CONTROL OF A SOLID STATE
[2+2] CYCLOADDITION IN CARBOXY-SUBSTITUTED
TETRATHIAFULVALENE DERIVATIVES

M. Teresa Duarte
a
*, Vnia Andr
a
, Claudia C. D. Simo
b
, Marta
Mas-Torrent
b
, Jaume Veciana
b
, Concepci Rovira
b

a
Centro de Qumica Estrutural, Instituto Superior Tcnico, Av. Rovisco Pais, 1049-001 Lisbon
b
Institut de Cincia de Materials de Barcelona - CSIC, Campus de la UAB, 08193
Bellaterra, Spain
*teresa.duarte@ist.utl.pt

Controlling solid state architectures through directional and strong
intermolecular interactions, like hydrogen bonds, has been the basis of
supramolecular solid state chemistry [1,2]. Van der Waals interactions, though
weaker have shown to be of similar importance
when applied to materials chemistry and solid
state reactivity. Tetrathiafulvalene (TTF)
derivatives besides being used as superconductor
salts have also proved to be valuable building
blocks[3] for molecular devices such as
transistors, molecular wires, organic field effect
transistors (OFETs) and sensors[4]. Interestingly,
solid state [2+2] cycloadditions[5] upon
irradiation have been reported regarding TTFs,
but in very few cases of TTF derivatives with one electroactive substituent in the
external double bond[6]. Here we report a new case of tetrathiafulvalene
derivatives that undergo solid state [2+2] cycloaddition upon polychromatic
irradiation. These derivatives are asymmetric TTF units, with a fusioned
benzene ring in one end and bearing an ester (CMB-TTF), or a carboxylic group
(CB-TTF), attached to the other side. Despite the high structural similitude, the
kinetics of reaction of the CMB-TTF and the CB-TTF are extremely different:
while the CMB-TTF reacts immediately with light, the CB-TTF take up to
several weeks long. The supramolecular arrangement and crystal packing of
monomers and products obtained upon reaction as well as a possible reaction
pathway will be presented and discussed.

[1] G.A. Jeffrey, An Introduction to Hydrogen bonding, Oxford Univ. Press, 1997.
[2] G.R.Desiraju, Angew. Chem. 107 (1995) 2505.
[3] C.Rovira, Chem.Rev. 104 (2004) 5289.
[4] J. Becher et al., Pure Appl. Chem. 69 (1999) 465.
[5] S.D.M.Allen et al., Spectrochimica Acta A 56 (2000) 2423.
[6] a)Ya. N. Kreitsberga, Neilands et al, J. Org. Chem. URSS 22 (1986) 367; b) T. Devic,
N. Avarvari et al, Chem. Commun. (2004) 1538; c) O. Jeannin, M. Fourmigu, Chem.
Eur. J. 12 (2006) 2994.
134


PREPARATION, CHARACTERISATION AND
APPLICATION OF ACTIVATED CARBONS PREPARED
FROM DIFFERENT POLYMERS

Isabel P. P. Cansado*, M. R. Carrott, P. J. M. Carrott, F. Gonalves
Centro de Qumica de vora e Departamento de Qumica, Universidade de vora,
Colgio Lus Antnio Verney, 7000-671 vora, Portugal
*ippc@uevora.pt

Emission of organic vapors from industrial and commercial sources is a
cause of photochemical smog and nuisance odors. This certainly needs to be
controlled. Recovery of organic vapors can be achieved by several methods such
as condensation, absorption, adsorption, contact oxidation, and incineration. The
adsorption method using activated carbon (AC) possesses many advantages for
removal and recovery of VOCs in low concentrations. These materials have
been widely used in the separation and purification of gas or liquid streams.
AC can be prepared from a variety of low cost-high availability materials by
either physical or chemical activation. In this work, two series of AC were
prepared, one by the pyrolysis of recycled granulated PET by chemical activation
with KOH, at different temperatures, and another from PEEK by physical
activation with CO
2
at 1173K. All AC obtained were characterised by the
adsorption of N
2
at 77K and the isotherms were analyzed with the BET and os
methods and the DR equation. Some results were previously reported [1-3].
The ACs obtained from PET presented a basic point of zero charge (pzc), a
superficial area varying from 630 to 2651m
2
/g and a micropore volume varying
from 0.23 to 0.75 cm
3
/g. The PET chemical activation with KOH allows us to
achieve AC with excellent properties for bulky adsorbates removal applications.
The ACs produced from PEEK present a very high carbonization yield, a basic
pzc, a superficial area varying from 656 to 2874 m
2
/g and a micropore volume
varying from 0.15 to 1.27 cm
3
/g.
The results obtained show that PET and PEEK are very promising precursors
for obtaining AC with high carbon yield and very high micropore volume when
compared with those obtained by other experimental procedures or other
precursors [4, 5].
The authors are grateful to Flupol and Selenis for the provision respectively of the PEEK
and PET.
[1] I.P.P. Cansado, F.A.M.M. Gonalves, P.J.M. Carrott, M.M.L. Ribeiro Carrott, Carbon
45 (2007) 2445.
[2] P.J.M. Carrott, I.P.P. Cansado, M.M.L.R. Carrott,

Appl. Surf. Sci. 252 (2006) 5948.
[3] I.P.P. Cansado, M.M.L. Ribeiro Carrott, P.J.M. Carrott, P.A.M. Mouro, Materials
Science Forum (2008) in press.
[4] J.B. Parra, C.O. Ania, A. Arenillas, F. Rubiera, J.J. Pis, Appl. Surf. Sci. 238 (2004) 304.
[5] I.Fernandez-Morales, M.C. Almazn-Almazn, M. Prez-Mendonza, M. Domingo-
Garcia, F.J. Lpez-Grazn, Microporous and Mesoporous Materials 80 (2005) 107.
135


MERCURY IN SALT MARSHES ECOSYSTEMS:
HALIMIONE PORTULACOIDES AS BIOMONITOR

M. Vlega
a
*, A. I. Lilleb
a
, I. Caador
b
M. E. Pereira
a
, A. C. Duarte
a
,
M. A. Pardal
c

a
CESAM & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, University
of Aveiro, 3810-193 Aveiro, Portugal
b
IO - Institute of Oceanography, Faculty of Sciences-University of Lisbon, Campo
Grande, 1749-016 Lisboa, Portugal
c
IMAR - Institute of Marine Research, Department of Zoology, University of Coimbra,
3004-517 Coimbra, Portugal
*mvalega@ua.pt

Mercury concentrations were quantified in salt marsh plant H. portulacoides
(roots, stems and leaves) as well as in the sediments of eight Portuguese
estuarine systems, covering seventeen salt marshes with distinct degree of
mercury contamination. The concentration of mercury in the sediments ranged
from 0.06 to 17 g g
-1
. The results show that the accumulation of mercury
differed according to the organ of the plant examined and also with the
concentration of mercury in the sediment. Higher mercury concentrations were
found in the roots (up to 13 g g
-1
) followed by the leaves (up to 0.14 g g
-1
),
while the stems had the lowest concentrations (up to 0.06 g g
-1
). Correlations,
fitting a liner model, explained the relation between the concentrations of
mercury in the diferent plant organs: roots and stems (R
2
adj
=0.75), stems and
leaves (R
2
adj
=0.85) and roots and leaves (R
2
adj
=0.78). The results show that the
variation of mercury concentration in the roots versus mercury concentration in
the sediments fited a sigmoidal model equation (R
2
adj
=0.89). Mercury
accumulation in the roots can be described in three steps: at a low range of
mercury concentrations in the sediments (0.06 up to 2 g g
-1
), the concentration
of mercury in roots is also low reaching a maximum of 1.3 g g
-1
. The highest
rates of mercury accumulation in the roots ocurred in a second step until the
concentrations of mercury in the sediments reach aproximatelly 4.5 g g
-1
; after
the occurrence of this maxiumun the accumulation rate of mercury in the roots
slows down leading to a plateu in the concentration of mercury in the roots of
about 9.4 g g
-1
, which corresponds to a mercury concentration in the sediments
of about 11 g g
-1
. The linear model also explained the response of mercury
accumulation in leaves versus the mercury concentration at the sediments
(R
2
adj
=0.88). Differences in responses of roots and leaves are expplained by the
dynamics of the plant organs: old roots are mineralised in situ close to new roots,
whilst leaves are renewed. Previous studies have shown that H. portulacoides is
a bioindicator for mercury, yet these results sustain that H. portulacoides may be
used as a biomonitor for mercury contamination in salt marshes. Nevertheless
caution should be taken in the aplication of the models, concerning the life cycle
of the species and the spatial variability of the system.
136


REMOO DE BENZO(GHI)PERILENO UTILIZANDO
CASCA DE AMNDOA COMO ADSORVENTE

Sofia L. Silva, Dionzia J. M. Cornlio, A. Alves, L. Santos*
LEP, Departamento de Engenharia Qumica, Faculdade de Engenharia da
Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*lsantos@fe.up.pt

Os hidrocarbonetos policclicos aromticos (PAHs) so compostos orgnicos
vestigiais que apresentam propriedades txicas e cancergenas, sendo bastante
persistentes no meio ambiente. Estas substncias foram classificadas pela US
Environmental Protection Agency (EPA) e pela UE como poluentes prioritrios.
Perante esta grave preocupao ambiental, torna-se imperioso o estudo de
metodologias eficazes de degradao ou remoo destes compostos. A remoo
por adsoro de compostos orgnicos utilizando produtos excedentrios da
agricultura tem sido alvo de estudo com resultados promissores, mostrando que
estes adsorventes constituem uma alternativa de baixo custo. No presente
trabalho estudou-se a remoo de um dos PAHs mais problemticos, o
benzo(ghi)perileno (BghiP), de matrizes aquosas utilizando casca de amndoa
como adsorvente.
Com o objectivo de relacionar os grupos superficiais presentes na casca com
a extenso da adsoro, efectuou-se um estudo preliminar de caracterizao
fsico qumica da mesma. A quantificao do BghiP em meio aquoso foi
efectuada por Cromatografia em Fase Lquida com Detector de Fluorescncia
(HPLC-FL). A optimizao e modelao do processo de adsoro, recorrendo ao
estudo da cintica e dos parmetros de equilbrio entre o BghiP e a casca de
amndoa foram estudados em ensaios por partidas (batch).
A caracterizao da casca de amndoa permitiu concluir que a sua
constituio maioritria so macroporos e mesoporos. Os mecanismos que esto
envolvidos na reteno da molcula de BghiP na superfcie da casca de amndoa
prendem-se com a formao de interaces hidrofbicas com os grupos
funcionais superficiais da casca de amndoa (nomeadamente C=C), identificados
por FTIR.
O tempo de equilbrio atingido foi de 24 horas para os ensaios em batch e,
como esperado, a adsoro do BghiP foi maior para as partculas de menor
dimetro. A cintica de adsoro de BghiP na casca de amndoa foi bem descrita
pelo modelo de 2 ordem, para todos os parmetros estudados. O equilbrio de
adsoro bem representado pela isotrmica de Langmuir, enquanto que a
isotrmica de Freundlich representa melhor o equilibrio de dessoro.
Conclui-se que a casca de amndoa parece ser um excelente adsorvente
alternativo para a remoo de PAHs de matrizes aquosas, dada a sua alta
eficincia e o seu baixo custo.
137


AVALIAO DA CAPACIDADE DE COMPLEXAO DO
CALIX[2]FURANO[2]PIRROL ATRAVS DE CLCULOS
COMPUTACIONAIS

Cludia A. Teixeira dos Santos*, Sheila M. F. dos Santos Aguiar,
Alexandre L. Magalhes
REQUIMTE / Universidade do Porto, Departamento de Qumica, Faculdade de Cincias,
Rua do Campo Alegre, 689, 4169-007 Porto
*claudixteixeira@iol.pt

A aplicao de derivados de calixarenos como novos receptores tem atrado
um interesse considervel na rea da qumica supramolecular
1
. A modificao
destes compostos, com o objectivo de aperfeioar a sua afinidade e selectividade
inicas, resultou em vrias alteraes estruturais da molcula inicial e levou ao
aparecimento de novas molculas estruturalmente semelhantes, tais como o
calix[4]pirrol e consequentemente o calix[2]furano[2]pirrol (1). A aplicao
destas molculas como novos receptores, "building blocks", e/ou plataformas
moleculares, tem sido alvo de um interesse crescente em diversas reas da
qumica, nomeadamente na proteco ambiental, transporte selectivo de ies e
sensores.
Este trabalho apresenta um estudo comparativo da capacidade de
complexao do calix[2]furano[2]pirrol em relao a diferentes caties
metlicos, nomeadamente metais alcalinos, metais alcalino-terrosos e alguns
metais de transio. A semelhana dos calixarenos tambm o
calix[2]furano[2]pirrol apresenta vrias conformaes:
cone, cone parcial, 1,2-alternada e 1,3-alternada
2
. Foram
determinadas as energias do calix[2]furano[2]pirrol em
cada uma das conformaes, e tambm as energias de
ligao dessas conformaes com alguns dos metais.
As caractersticas electrnicas e estruturais
calculadas, foram ainda tratadas graficamente a fim de
facilitar o estudo comparativo dos resultados e explicar
as diferentes afinidades do ligando em relao aos ies.

[1] Lhotk P., Eur. J. Org. Chem. 2004, 1675.
[2] C. D. Gutsche, "Calixarenes," in Monographs in Supramolecular Chemistry, J.
Stoddart, Ed., Royal Society of Chemistry, Cambridge, Mass, USA, 1989.
NH
NH
O
O
(1)
138


PREPARATION AND CHARACTERISATION OF
NANOSTRUCTURED CARBON AND SILICA BASED
MATERIALS FOR TEXTILE APPLICATIONS

I. Rocha
a
, T. Galvo
a
, A. G. Gonalves
b,c
*, H. Gaspar
a
, H. Alves
a
, C.
Pereira
a
, F. Gonalves
b
,

B. Jarrais
c
,

A. Ribeiro
c
, A. Carneiro
c
, J.
Morgado
d
, M. F. R. Pereira
b
, C. Freire
a
a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
4169-007 Porto
b
Laboratrio de Catlise e Materiais(LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, 4200-465 Porto
c
Centro de Nanotecnologia e Materiais Tcnicos, Funcionais, e Inteligentes (CENTI),
4760-034 Vila Nova de Famalico
d
Centro Tecnolgico das Indstrias Txtil e do Vesturio de Portugal (CITEVE), Quinta
da Maia, Rua Fernando Mesquita, n 2785, 4760-034 Vila Nova de Famalico
*eq03020@fe.up.pt

Textiles are probably the most popular of materials since they decorate and
protect our bodies while bringing comfort into our lives. Currently, the consumers
are demanding for textile products with higher performances. Our goal is to
produce functional textiles with improved properties by functionalisation with
clays, silica nanoparticles, and carbon nanotubes (CNT).

Two clays, Montmorillonite (natural clay) and Laponite (synthetic clay), were
functionalised with two organosilanes, 3-chloropropyltrimethoxysilane (ClPTMS)
and 3-bromopropyltrimethoxysilane (BrPTMS), and attached to a previously
deprotonated cotton. In another approach, silica nanoparticles funcionalised with 3-
aminopropyltriethoxysilane (APTES) and 3-mercaptopro-pyltrimethoxysilane
(MPTMS) were covalently bonded to the cotton fibers by in situ methodology. The
samples were characterised, before and after functionalisation, by SEM-EDS and
FTIR. CNTs were functionalised by oxidation in the liquid phase with HNO
3

(introduction of acid groups), oxidation in the gas phase with O
2
(introduction of
neutral and basic groups), and heat treatments at different temperatures to
selectively remove some of the functional groups. Some of these carbon materials
were then functionalised with the organosilanes referred above. These samples
were characterised by TPD, TG and N
2
adsorption isotherms at 77K. The prepared
nanostructured materials were subsequently applied in cotton and polyester based
textiles and their influence in the hydrophobicity and fire retardant properties of the
textiles was assessed.
Acknowledgments: This work was partially funded by Projecto de Investigao Cientfica
na Pr-Graduao 2007, U.P. and C.G.D., IPG63 - NANOTEXTUP.
139


NOVO MTODO DE ANLISE DE COMPOSTOS
ORGNICOS VOLTEIS (COVS) POR SPME-GC/MS

Vera Homem
a
, Rita Arajo
a
, Jos Lus Moreira
b
, Lcia Santos
a
,
Arminda Alves
a
*
a
LEPAE-Laboratrio de Engenharia de Processos, Ambiente e Energia, Faculdade de
Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
b
Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do
Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
*aalves@fe.up.pt

Os compostos orgnicos volteis so contaminantes comuns em guas,
destacando-se pela sua perigosidade ou pela frequncia de deteco, os BTEX
(benzeno, tolueno, etilbenzeno e xilenos), clorobenzenos, diclorometano,
cloroetano, di e tri-cloroetanos, dicloropropano e os di- e tri-cloroetilenos. Entre
as possveis fontes de contaminao incluem-se os efluentes industriais, guas
residuais, solventes, gasolina e resduos de leos, pesticidas e herbicidas usados
na agricultura e processos de desinfeco [1]. Atendendo aos limites mximos
legais fixados para alguns COVs, as metodologias de anlise envolvem
procedimentos de extraco lquido-lquido ou em fase slida com concentrao
do extracto obtido, seguido da anlise cromatogrfica, normalmente por GC/MS,
ou tcnicas de injeco em headspace acopladas a GC/MS. So tcnicas
sensveis, mas no expeditas, no primeiro caso, ou caras, no segundo caso.
Este trabalho teve como objectivo implementar uma nova metodologia de
anlise de COVs atravs da micro-extraco em fase slida (SPME) seguida de
anlise por GC/MS [2]. O mtodo analtico desenvolvido permitiu analisar 12
COVs em matrizes aquosas benzeno, tolueno, etilbenzeno, o/m/p-xileno,
tricloroetileno, tetracloroetileno, 1,2-dicloroetileno, 1,2-dicloroetano e
tricloroetano. Efectuaram-se extraces de 10 ml de amostra em headspace, a
uma temperatura de -5 C (no interior de uma arca de congelao), utilizando
uma fibra de 100 m PDMS e um tempo de extraco de 30 minutos. A anlise
cromatogrfica foi realizada num GC/MS modelo Saturn 2000, marca Varian. A
coluna capilar usada foi uma factorFour, VF-624ms (30 m x 0,25 mm) com fase
estacionria de 1,40 m. O modo de aquisio de ies realizou-se em fullscan.
Os analitos foram quantificados pelo mtodo de padro interno, utilizando o 1-
bromo-2-cloroetano para esse fim.
Os limites de deteco foram calculados a partir da razo sinal/rudo e
variaram entre 0,02 g.L
-1
e 12 g.L
-1
. A preciso, avaliada pelo coeficiente de
variao de ensaios replicados situou-se-se entre 8 e 37%.
O mtodo desenvolvido revelou-se adequado ao objectivo proposto.

[1] V.H. Niri, L. Bragg, J. Pawliszyn, J. Chromatogr. A (2008), in press,
doi:10.1016/j.chroma.2008.03.062.
[2] E. Fries, W. Pttmann, Anal. Bioanal. Chem. 386 (2006) 1497.

140


METODOLOGIA DE ANLISE DE PESTICIDAS
AGRCOLAS POR SPE-LC/MS

Rita Arajo, Vera Homem, Lcia Santos, Arminda Alves
*

LEPAE, Laboratrio de Engenharia de Processos, Ambiente e Energia, Faculdade de
Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
*aalves@fe.up.pt

As anlises multiresduo de pesticidas em guas tm sido uma preocupao
crescente nos laboratrios de controlo de qualidade, nomeadamente se os
compostos alvos forem substncias prioritrias includas na Directiva da gua
(2000/60/CE). Neste tipo de anlises, podem surgir dois problemas principais: a
diversidade fsico-qumica dos compostos alvo e a obrigao de cumprir os limites
mximos legais quando estes existem. Na maioria dos casos podem ser usados
mtodos analticos que envolvam procedimentos de extraco e pr-concentrao,
seguidos de deteco por cromatografia gasosa ou lquida de alta resoluo,
acoplada a espectrometria de massa, permitindo a deteco de um elevado nmero
de compostos numa nica corrida [1].

Os mtodos analticos tm de ser validados e
as incertezas globais correspondentes devem ser determinadas [2].
Foi assim implementado, validado e avaliado, em termos de incerteza global,
um mtodo de anlise de pesticidas usados na agricultura - cimoxanil, bentazona
e diuro - no qual, aps ter sido realizada uma etapa de extraco em fase slida
(SPE), foram efectuadas duas etapas de cromatografia lquida, uma de sreening
por HPLC-UV, seguida de confirmao por LC/MS/MS. O procedimento de
SPE utiliza como etapa de clean-up colunas ENVI
TM
- Carb SPE Tubes. Aps ter
sido realizado o condicionamento das colunas com metanol e gua acidificada
com HCl, a amostra foi feita passar atravs da coluna e a eluio realizada com
metanol e acetona. A optimizao em LC/MS/MS foi efectuada para os
compostos alvo atravs de ionizao presso atmosfrica por electrospray.
Numa fase inicial esta foi realizada por injeco directa de padres individuais e
de mistura e posteriormente repetida recorrendo a padres extrados.
Os limites de deteco foram de 70, 39 e 470 g.L
-1
para o cimoxanil,
bentazona e diuro, respectivamente. Os valores de recuperao mdia foram de
90,1% para o cimoxanil, 52,1% para a bentazona e 91,6% para o diuro. As
incertezas globais associadas ao mtodo analtico foram de 10,8%, 21,8% e
55,8% para o cimoxanil, bentazona e diuro, respectivamente.
A metodologia analtica implementada e validada foi considerada adequada
para os objectivos propostos.

[1] I.R. Pizzutti, A. Kok, R. Zanella, M.B. Adaime, M. Hiemstra, C. Wieckert, O.D.
Prestes. J. Chrom. A 1142 (2007) 123.
[2] N. Ratola, L. S. Santos, P. Herbert, M. A. Alves. Anal. Chim. Acta 573 (2006) 202.

141


METODOLOGIA DE SCREENI NG DE CLOROALCANOS
C
10-13
E TER PENTABROMODIFENLICO EM GUAS
POR SPME-GC/MS

E. Ribeiro
a
, Jos Lus Moreira
b
, L. Santos
a
, A. Alves
a
*
a
LEPAE-Laboratrio de Engenharia de Processos, Ambiente e Energia, Faculdade de
Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
b
Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do
Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
*aalves@fe.up.pt

A recente Directiva Europeia 2006/0129/CE [1] relativa a normas de qualidade
ambiental no domnio da poltica da gua fixa valores-limite para algumas
substncias prioritrias, entre as quais os cloroalcanos de cadeia curta C
10-13
e o ter
pentabromodifenlico. Embora no esteja definida a concentrao mxima
admissvel (CMA) para o ter pentabromodifenlico, este decreto limita o seu valor
mdio anual (VMA) para guas de superfcie, a 2 ng/L. Para os cloroalcanos C
10-13

os valores de CMA e VMA so respectivamente, 1400 e 400 ng/L.
Os cloroalcanos C
10-13
, tambm conhecidos por parafinas cloradas de cadeia
curta (SCCP), so uma mistura complexa de substncias qumicas estreitamente
aparentadas, nomeadamente hidrocarbonetos com 10 a 13 tomos de carbono
dispostos em cadeias, em que 50-70% da massa composta por cloro em cadeia
e contendo 50-70% em peso de cloro. Em virtude das suas propriedades de
resistncia ao fogo, os cloroalcanos (C
10
-C
13
) so usados como aditivos em
borracha, especialmente em correias transportadoras. So tambm usados em
tintas e outros revestimentos, cabedais, txteis e em compostos vedantes. No
existe mtodo de referncia para anlise destes compostos em guas.
O ter pentabromodifenlico pertence ao grupo dos difenilteres
(poli)bromados (PBDE), que contm um total de 209 congneres. O penta-BDE
contm 5 tomos de bromo, e totalmente no inflamvel, sendo usado como
retardante de chama, em espuma flexvel de poliuretano para moblias e estofos,
e menos frequentemente em plsticos rgidos e adesivos. Tambm no existe
mtodo de referncia para este composto em guas.
O objectivo deste trabalho foi implementar um mtodo de anlise de
cloroalcanos e penta-BDE em guas, utilizando a microextraco em fase slida
(SPME) seguida de cromatografia gasosa com espectrometria de massa.
Pretendeu-se avaliar a viabilidade de utilizao deste mtodo para cumprimento
da Directiva Europeia, concluindo-se que os limites de deteco obtidos so
compatveis para a anlise de cloroalcanos, mas no de penta-BDE.

[1] Comunidade Europeia, Bruxelas. Directiva 2006/0129/EC. Official Journal of
European Communities, C97 (2006) 3.

142


DETERMINAO ESPECTROFOTOMTRICA DE
NITRATOS EM DIFERENTES TIPOS DE ALFACE

Ana I. Santos
a
, Sandra Flix
b,c
, Cristina M. R. R. Oliveira
c
*
a
DQB - FCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa, Portugal
b
UATLA, Antiga Fbrica da Plvora de Barcarena, 2730-036 Barcarena, Portugal
c
CCMM - DQB - FCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa, Portugal
*cristina.oliveira@fc.ul.pt

Nos ltimos anos, tem sido dedicada uma ateno especial ao estudo dos
nitratos nos alimentos dado que, embora no sejam prejudiciais para os vegetais,
podem conduzir a um elevado nmero de efeitos indesejveis sade do Homem
e dos animais. As principais formas de azoto absorvidas pelas plantas so os ies
nitrato (NO
3
-
) e amnio (NH
4
+
). De uma maneira geral, as plantas absorvem
predominantemente a forma ntrica, uma vez que, em solos bem arejados e de pH
prximo da neutralidade, esta forma de azoto ocorre em concentraes mais
elevadas [1]. A capacidade de acumulao de cada uma das formas depende de
factores genticos e ambientais. Algumas plantas acumulam nitrato nas razes e
na parte area, quando a absoro excede as suas necessidades metablicas.
Nestes casos, so encontrados altos teores nas folhas, embora os caules sejam os
locais de mxima acumulao [2]. A alface, em particular, possui grande
capacidade para acumular nitrato nas suas folhas. Uma vez que os produtos
hortcolas tm uma funo nutricional importante e que desempenham um papel
essencial para a sade, tornou-se necessrio estabelecer teores mximos de
nitratos nos mesmos. Neste trabalho, determinou-se o teor em nitratos em
diferentes tipos de alface, adquiridas em diferentes locais comerciais no perodo
de Inverno de 2007-2008, atravs do mtodo de Cataldo [3]. Procedeu-se
extraco dos nitratos em amostras secas e amostras frescas efectuando-se,
posteriormente, a respectiva determinao espectrofotomtrica. Compararam-se
os teores em nitratos, obtidos para as diferentes alfaces, com os teores mximos
estabelecidos por lei.

[1] F. C. Boswell, J. J. Meisinger, N. L. Case. Production, marketing, and use of nitrogen
fertilizers. Soil Science Society of America 3 ed. (1985) 229.
[2] D. N. Maynard, A. V. Barker. Nitrate content of vegetable crops. 7 (1972) 224.
[3] D. A. Cataldo, M. Haroon, L. E. Schrader, V. L. Youngs. Communications in Soil
Science and Plant Analysis. 6 (1975) 71.
143


DESIDRATAO DA CEBOLA: INFLUNCIA DAS
VARIVEIS DO PROCESSO SOBRE O PRODUTO FINAL

Ana C. Dias
a
, Maria Joo Barroca
b
, Raquel P. F. Guin
a
*
a
Escola Superior Agrria de Viseu, Quinta da Alagoa, Estrada de Nelas, 3500-606 Viseu
b
Escola Superior Agrria de Coimbra, Bencanta, 3040-316 Coimbra
*raquelguine@esav.ipv.pt

A cebola uma cultura com grande expanso devido s suas mltiplas
aplicaes a nvel alimentar. A desidratao da cebola surge devido, no s
necessidade de ser conservada como alimento, mas tambm devido s suas
caractersticas qumicas que permitem o uso da cebola como condimento/aditivo
numa enorme variedade de alimentos
processados como o Ketchup, molhos,
sopas, saladas, produtos crneos,
batatas fritas ou pickles.
No presente trabalho foi realizado
o estudo da desidratao da cebola,
tendo sido ensaiados diferentes
mtodos de secagem: secagem por
conveco com ar quente a 30, 50 e
70C, secagem combinada de osmose
e conveco a 30C e ainda
liofilizao.
Os produtos obtidos foram sujeitos
a algumas anlises qumicas,
nomeadamente de humidade, gordura, protena, acares, cinza, fibra e acidez.
Dos resultados obtidos possvel constatar que os tratamentos de secagem se
apresentam substancialmente diferentes no que respeita ao tempo de secagem,
com o aumento da temperatura a acelerar consideravelmente o processo.
Contudo, o aumento da temperatura de secagem no influencia grandemente a
composio do produto desidratado.

Tabela 1. Composio das amostras de cebola secadas a diferentes temperaturas.
Propriedade Fresca

Seca
a 30C
Seca
a 50C
Seca
a 70C
Humidade (g/100 g produto) 92.810.54 21.490.04 17.480.51 16.001.87
Gordura (g / 100 g matria seca) 0.560.20 0.240.08 0.130.07 0.300.04
Protena (g / 100 g matria seca) 1.050.04 1.010.01 0.980.05 0.900.05
Cinzas (g / 100 g matria seca) 3.510.25 3.400.40 3.480.12 3.200.13
Fibra (g / 100 g matria seca) 4.410.47 4.300.06 4.430.20 4.580.32
Acares (g / 100 g matria seca) 56.550.10 43.410.10 33.310.50 25.050.20
Acidez (ml / 100 g matria seca) 23.420.29 20.950.21 19.330.30 16.610.23



Tempo (min)
0 10 20 30 40 50
H

(
k
g

g
u
a
/
k
g

a
m
o
s
t
r
a
)
0
20
40
60
80
100
Secagem em estufa a 30 C
Desidratao osmtica (66 Brix)
Estufa a 30 C depois da Osmose
Figura 1. Comparao do tempo de
secagem para secagem convectiva e
combinada.
Tempo (min)
0 10 20 30 40 50
H

(
k
g

g
u
a
/
k
g

a
m
o
s
t
r
a
)
0
20
40
60
80
100
Secagem em estufa a 30 C
Desidratao osmtica (66 Brix)
Estufa a 30 C depois da Osmose
144


CARACTERIZAO QUMICA DO PIMENTO
DESIDRATADO POR DIFERENTES MTODOS

Dulce H. M. Costa
a
, Maria Joo Barroca
b
, Raquel P. F. Guin
a
*
a
Escola Superior Agrria de Viseu, Quinta da Alagoa, Estrada de Nelas, 3500-606 Viseu
b
Escola Superior Agrria de Coimbra, Bencanta, 3040-316 Coimbra
*raquelguine@esav.ipv.pt

A cultura do pimento destina-se principalmente ao fabrico de produtos
congelados ou desidratados. Contudo o pimento muito utilizado como
condimento e como matria-prima para a extraco de corantes alimentares e
oleorresinas, sendo estas usadas nas
indstrias alimentares e farmacutica,
pois so ricas em capsainoides. O seu
p (colorau) muito usado como
corante e aromatizante na culinria e
na indstria alimentar. Para alm da
utilizao alimentar, diettica e
medicinal, alguns pimentos so
cultivados como plantas ornamentais
[1].
No presente trabalho o pimento
verde foi desidratado com ar quente a
30, 50 e 70C, e foi ainda liofilizado e
submetido a osmose seguida de secagem com ar.
No final da desidratao o pimento foi submetido a uma avaliao de certos
parmetros nutricionais: humidade, gordura, protena, cinza e fibra.

Tabela 1. Composio do pimento desidratado por diferentes mtodos.
Propriedade Fresco

Seco
a 30C
Seco
a 50C
Seco
a 70C
Liofilizado
Humidade (g/100 g produto) 92.92 3.73 2.20 2.49 3.16
Gordura (g / 100 g matria seca) 0.15 0.33 0.51 0.47 -
Protena (g / 100 g matria seca) 17.75 14.93 12.45 11.83 15.00
Cinza (g / 100 g matria seca) 6.90 6.98 6.24 6.93 7.16
Fibra (g / 100 g matria seca) 9.85 11.47 11.21 11.23 -

Dos resultados obtidos verificou-se que a protena foi o componente que mais
sofreu a influncia da temperatura de secagem, sendo que os restantes
componentes no apresentaram variaes assinalveis em funo do mtodo de
secagem utilizado.

[1] D. Almeida. Manual de culturas hortcolas. Lisboa, Editorial Presena. Volume II:
72-95, 2006.
Figura 1. Curva de secagem a 30 C.
145


EVALUATION OF THE ANTIOXIDANT CAPACITY OF
EDIBLE WILD MUSHROOMS BY CYCLIC VOLTAMMETRY

Soraia Falco
a,b
, Lillian Barros
a
, Isabel C. F. R. Ferreira
a
, Cristina
Freire
b
, Miguel Vilas-Boas
a
*

a
CIMO-ESAB, Instituto Politcnico de Bragana, Campus de Sta. Apolnia, 1172, 5301-
855 Bragana, Portugal
b
REQUIMTE/Departamento de Qumica, Faculdade de Cincias do Porto, Rua do
Campo Alegre, 4169-007 Porto, Portugal
*mvboas@ipb.pt

The problems of oxygen metabolism in humans constantly attract the
attention, especially now that is obvious that the excess of oxygen and its
reactive species cause radical-chain oxidation processes in cellular tissues,
resulting in fast aging, cell destruction and incurable diseases.

Cells are equipped
with several defense systems which act through a variety of mechanisms, one of
those is the protection through low-molecular weight antioxidants, like phenolic
compounds [1]. Edible plants constitute a major nutritional source of these
natural products. Fruit bodies of mushrooms play an important role as a source
of bioactive compounds with medicinal value [2].

The aim of this work was the evaluation of the antioxidant capacity in six
species of edible wild mushrooms, Agaricus silvaticus, Coprinus comatus,
Lactarius deliciosus, Leucopaxillus giganteus Macrolepiota procera Sarcodon
imbricatus from the region of Trs-os-Montes, through cyclic voltammetry.
Cyclic voltammetry (CV) measurements were performed on an Autolab
PGSTAT 302 with a typical three electrode cell with a platinum or glassy carbon
disk as working electrode. The voltammograms were acquired at 0 to 1.8 V.
In the first stage the experimental conditions used in the voltammetric studies
were optimized, with better results for MeOH / acetate buffer 0.1 mol dm
-3
/
NaClO
4
(70:28:2) solutions, either at pH 4 or 7. For the working electrode glassy
carbon electrode showed a greater current density.
The CV of the mushrooms extracts showed the existence of an irreversible
anodic wave at 0.9 V, similar to all extracts, which indicates analogous
composition in electroactive species. Additionally, some mushrooms presented
anodic waves at 0.4 and 0.6 V, indicative of greater reducing power.
Based on E
p/2
values, which reflects the specific reducing power of
components with similar potencial [1],

it was found that the extract with higher
reducing power was Sarcodon imbricatus.

Acknowledgements: Research Project POCI/AGR/5661/2004 (FCT-Portugal).

[1] S. Chevion, M.A. Roberts, M. Chevion. Free Radical Bio. Med. 28 (2000) 860.
[2] Ferreira, I. C. F. R.; Baptista, P.; Vilas-Boas, M.; Barros, L. Food Chem 100 (2007)
1511.
146


DETERMINAO DO TEOR DE PECTINAS EM
DIFERENTES FRUTOS E BEBIDAS

Manuela M. Moreira
a
*, Lus F. Guido
a
, Jos M. Cruz
b
, Aquiles A.
Barros
a

a
REQUINTE - Departamento de Qumica, Faculdade de Cincias da Universidade do
Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
b
iBeSa - Instituto de Bebidas e Sade, 4466-955, S. Mamede de Infesta, Portugal
*manela_smoreira@hotmail.com

Tradicionalmente, as pectinas so usadas na indstria alimentar como um
agente gelificante e estabilizante na produo de geleias e compotas. No entanto,
tm surgido diversos estudos evidenciado os potenciais efeitos benficos a nvel
da sade, nomeadamente o decrscimo dos nveis de colesterol no sangue, a
reduo dos nveis de glucose em doentes diabticos, assim como a diminuio
do risco de diversos tipos de cancro [1]. A pectina um complexo natural
presente maioritariamente na parede celular das plantas, e consiste numa cadeia
linear de unidades de cido galacturnico parcialmente esterificado com grupos
ster metlicos. Para alm das plantas, os frutos citrinos constituem uma das
maiores fontes de pectina, em particular a poro do albedo que especialmente
rica e usada como principal matria-prima para a produo comercial de pectina.
De acordo com o exposto anteriormente, depreende-se a relevncia do
desenvolvimento de metodologias analticas simples e rpidas que permitam a
sua determinao.
Neste trabalho utilizou-se um kit enzimtico comercial (Mtodo oficial
AOAC 991.43), baseado numa endo-pectato liase recombinante com intuito de
estimar o teor de pectinas em diferentes produtos alimentares [2]. A metodologia
analtica aplicada pode ser dividida em duas etapas: (1) extraco das pectinas
por dissoluo em gua ultrapura e ajuste do pH a 12,0 catalizando assim a
desmetilao com a formao de regies de cido poligalacturnico no polmero,
isto , a converso da pectina em pectato; (2) determinao espectrofotomtrica
aps incubao do produto anterior com a enzima pectato liase ocorrendo a
formao de oligossacridos insaturados que absorvem fortemente a 235 nm.
Desta forma analisou-se o sumo, assim como o respectivo albedo de diferentes
citrinos e outros frutos, tais como laranja (C. sinensis), tangerinas (C. reticulata),
ma (Malus), rom (Punica granatum), etc. Por outro lado, pretendeu-se
tambm verificar se a forma de obteno do sumo (triturador ou espremedor)
teria um efeito significativo na extraco das pectinas dos frutos e bebidas.
Adicionalmente, testou-se a influncia da centrifugao no teor de pectinas do
sumo.

[1] Y. Liu, et al. J. Agric. Food Chem. 49 (2001) 3051.
[2] K.M. Hansen, et al. J. AOAC Int. 84 (2001) 1851.
147


VITAMIN E IN COFFEE BEANS: DEVELOPMENT AND
VALIDATION OF A MICRO-EXTRACTION METHOD

Rita C. Alves*, Susana Casal, Beatriz Oliveira
REQUIMTE, Servio de Bromatologia, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto
*rita.c.alves@gmail.com

Vitamin E encompasses eight naturally occurring and structurally related
vitamers (-, -, - and -tocopherol, and the respective tocotrienols) known as
potent antioxidants.
A solid-liquid micro-extraction method for vitamin E quantification in coffee
beans (raw and roasted) with HPLC/diode-array/fluorescence detection was
developed and validated. Briefly, 150 mg of ground coffee were spiked with
ethanol, BHT (antioxidant), tocol (internal standard), and was left in overnight
maceration (4C) with hexane. After adding NaCl 1%, the organic phase was
separated and the residue re-extracted twice.
The best chromatographic resolution was achieved within 8 minutes with a
normal-phase Supelcosil TM LC-SI (3 m) 75 x 3.0 mm (Supelco, Bellefonte,
PA), using an isocratic elution with hexane/1,4-dioxane (98:2), at a flow rate of
0.7 mL/min. The detection was performed by both the diode-array detector,
connected in series with the fluorescence detector programmed for excitation at
290 and emission at 330 nm. The diode-array detector was a precious tool in the
detection of co-eluting interferences. Quantification was based on the
fluorescence measurements. The linearity range was tested with diluted standard
solutions of the eight vitamin E isomers subjected to the entire extraction
method. The correlation factors (r) were higher than 0.999 and the extraction
method precision was inferior to 5%, with mean recoveries near 100%.
The method was applied to 24 coffee beans samples (6 arabica and 6 robusta,
each one raw and roasted). Only two isomers, - and -tocopherol, were
confirmed and quantified, being the latter generally the major compound,
especially in arabica coffees. The total Vitamin E contents ( + ) found were
10.14 1.53 and 9.04 1.09 mg/100g for arabica raw and roasted coffees,
respectively. For robusta the amounts were lower, with 3.82 0.42 mg/100g for
raw coffees and 3.25 0.47 mg/100g for roasted ones. Mean vitamin E roast
losses of 10% and 15% were found for arabica and robusta coffees, respectively.

Acknowledgments: The authors thank to BICAF for providing the coffee samples. Rita
Alves is grateful to Fundao para a Cincia e a Tecnologia for a PhD grant
(SFRH/BD/22449/2005).
148


CHEMICAL COMPOSITION AND ANTIOXIDANT
ACTIVITY OF FROZEN, DRIED AND COOKED WILD
EDIBLE MUSHROOMS

Lillian Barros, Paula Baptista, Daniela M. Correia, Jorge S Morais,
Isabel C. F. R. Ferreira*
CIMO/Escola Superior Agrria, Instituto Politcnico de Bragana, Campus de Santa
Apolnia, Apartado 1172, 5301-855 Bragana, Portugal
*iferreira@ipb.pt

Wild mushrooms are becoming more and more important in our diet for their
nutritional and pharmacological characteristics.

The high protein and low
fat/energy contents of wild edible mushrooms, reported by many workers
including by our research group, make them excellent foods for use in low
caloric diets. Mushrooms have also become attractive as a functional food and as
source for the development of drugs and nutraceuticals. Edible mushrooms are
characterized by a short shelf life (1-3 days at room temperature), linked to the
occurrence of post-harvest changes. These changes are due to the high moisture
content of the carpophores and to the high activity of enzymes such as protease
or polyphenol oxidase, responsible for protein and sugar decrease and for a
browning reaction during storage. The drying and deep-freezing processes have
been used to increase storage stability and facilitate mushroom consumption
without seasonal constraints. The objective of this study was to evaluate the
modifications induced by different conservation treatments (drying and freezing)
or cooking in the chemical composition and antioxidant properties of four
Portuguese wild edible mushroom species (Lactarius deliciosus, Macrolepiota
mastoidea, Macrolepiota procera, Sarcodon imbricatus). Dried, frozen and
cooked samples were analyzed for proximate constituents (moisture, fat, crude
protein, ash, carbohydrates) and nutritional value. Fatty acid and sugar profiles
were also obtained by gas-chromatography coupled to a flame ionization detector
(GC/FID) and high performance liquid chromatography coupled to a refraction
index detector (HPLC/RI), respectively. The antioxidant properties were
evaluated by several chemical (DPPH radical scavenging capacity and reducing
power) and biochemical assays (inhibition of |-carotene bleaching and inhibition
of lipid peroxidation in brain tissue using thiobarbituric acid reactive
substances). The results of this study [1] show that mushroom specie, and
processing and cooking practices are all effective determinants either for
chemical composition or antioxidant properties. Cooked samples proved to have
lower nutrients concentrations and lower antioxidant activity either than dried or
frozen samples. In what concerns to fatty acids and sugar individual profiles,
only the cooked sample proved to be relevant.
Acknowledgements: Research project PPCDT/AGR/56661/2004 for financial support.
[1] L. Barros, P. Baptista, D.M. Correia, J.S. Morais, I.C.F.R. Ferreira. J. Agric. Food
Chem. 55 (2007) 4781.
149


EFEITO ANTIPROLIFERATIVO DE FLAVONIDES
PRESENTES EM BEBIDAS NUMA LINHA CELULAR DE
CANCRO HUMANO

Daniel O. Carvalho
a
*, Aquiles A. Barros
a
, Alexandre do Carmo
b
,
Jos M. Cruz
c
, Lus F. Guido
a

a
Departamento de Qumica da

Faculdade de Cincias da Universidade do Porto, Rua do
Campo Alegre, 687 4169-007 Porto
b
Instituto de Biologia Celular e Molecular da Universidade do Porto, Rua do Campo
Alegre, 823 4150-180 Porto
c
Instituo de Bebidas e Sade, Apartado 1044, 4466-955 S. Mamede de Infesta
*danielcarvalho.21@gmail.com

Os compostos fenlicos apresentam, para alm da capacidade antioxidante,
importantes actividades anti-virais, anti-alrgicas, anti-inflamatrias e anti-
tumorais [1]. Estes compostos so constituintes sintticos ou naturais de
alimentos, chs e sumos de frutos [2].
O principal objectivo deste trabalho foi a avaliao in vitro do efeito
antiproliferativo de dois polifenis presentes em bebidas (naringenina sumos
de citrinos e xanto-humol cerveja) numa linha celular de cancro da tiride
(TPC-1), atravs do mtodo colorimtrico da sulforodamina B (SRB).
Em clulas expostas durante 48 horas com a naringenina (NARG), esta no
produz efeito antiproliferativo significativo em nenhuma das concentraes
testadas (0,1 a 100 M). O xanto-humol (XN), ao contrrio, produz um efeito
antiproliferativo significativo para a mxima concentrao testada (figura 1). O
XN inibe a sntese de DNA das clulas TPC-1, pelo que poder possuir uma
potencial actividade quimiopreventiva sobre o cancro da tiride em humanos.














[1] A. Russo et al. Cell Biology and Toxicology 10 (2000) 91.
[2] C.L. Miranda et al. Food and Chemical Toxicology 37 (1999) 271.
XN NARG
Figura 1 - Efeito do XN e da NARG no crescimento de clulas de cancro da tiride, aps
2 dias de exposio.
150


DETERMINATION OF PESTICIDES IN IRRIGATION
WATER USING SPE AND GC-ECD

Jos A. N. S. Ferreira
a
*, Valentina F. Domingues
a
, Nuno F. C. B.
Mateus
b
, Cristina F. Delerue-Matos
a
.
a
Requimte, Instituto Superior de Engenharia do Porto, Rua Dr. Antnio Bernardino de
Almeida, 431, 4200-072 Porto, Portugal
b
Centro de Investigao em Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre, 4169-007 Porto, Portugal
*jose.alberto@sapo.pt

The analysis of pesticides in water samples is a problem of primary concern
for Quality Control Laboratories due to the toxicity level of these compounds
and its public health risk. The Council Directive 98/83/EC November 3
rd
of 1998
regarding the quality of water intended for human consumption states a
parametric value of 0.1 g/L for each individual pesticide and 0.5 g/L for the
sum of all monitored pesticides.
The present study was made within a vulnerable zone in Portugal, between
Esposende and Vila do Conde, for irrigation water drawn from the wells [1].
The analyzed pesticides were three fungicides (folpet, iprodion, tolylfluanid)
and one insecticide (chlorpyrifos) that can be applied in lettuce cultures. The
impact of infiltration of this pesticides in groundwater was assessed [1-2], since
this culture is extensively grown in that region.
The extraction was performed with solid-phase extraction columns (SPE).
Several parameters were optimized in order to achieve the best recovery and the
lowest limit of detection, namely: the adequate cartridge, sample pH,
conditioning and elution steps [3].
Gas chromatography with electron-capture detector (GC-ECD) was
employed for the quantification of pesticides and gas chromatography coupled
with mass spectrometry (GC-MS) was used as a mean of confirmation.
This method showed excellent linearity ranges for all pesticides, with
correlation coefficients greater than 0.99. Determination limits, precision,
accuracy and recovery studies in several water samples were also performed.

[1] C.M. Goncalves, J.C.G. Esteves da Silva, M.F. Alpendurada. J. Agric. Food Chem. 55
(2007) 6227.
[2] M.J. Cerejeira et al. Water Res. 37 (2003) 1055.
[3] D. Stajnbaher, L. Zupancic-Kralj. J. Chromatogr., A 1015 (2003) 185.
151


QUANTIFICATION OF ETHYL ESTERS AND ACETATES
IN WINES USING SOLVENTLESS TECHNIQUES:
SBSE AND SPME

Rosa M. Perestrelo
a,b
, Jos S. Cmara
b
*, Jos M. Nogueira
a
a
Departamento de Qumica e Bioqumica, Faculdade de Cincias da Universidade de
Lisboa, Campo Grande Ed. C8, 1749-016 Lisboa, Portugal
b
Departamento de Qumica, Universidade da Madeira, 9000-390 Funchal, Portugal
*jsc@uma.pt

Headspace solid-phase microextraction (HS-SPME) and stir bar sportive
extraction (SBSE) were studied as solventless alternative methods for the
extraction and characterization of higher alcohol acetates, isoamyl esters and
ethyl esters in Terras Madeirenses wines (Madeira island). The best conditions to
extract this type of compounds were determined and methods were validated.
For SPME methodology six fibers were tested and compared, namely, carboxen-
poly(dimethylsiloxane) (CAR/PDMS), carbowax-divinylbenzene (CW/DVB),
divinylbenzene-carboxen-poly(dimethylsiloxane) (DVB/CAR/PDMS),
poly(dimethylsiloxane) (PDMS), poly(acrylate) (PA) and
poly(dimethylsiloxane)-divinylbenzene (PDMS/DVB). The influence of
extraction time, temperature, salt addition and matrix effects were optimized for
better extraction efficiency of the volatiles. Better results were obtained when
extraction was carried out using a divinylbenzene-carboxen-
poly(dimethylsiloxane) (DVB/CAR/PDMS) fiber, in headspace mode, with
stirring at 800 rpm during 60 min at 25 C, after saturating the samples with
NaCl (10 %). The SBSE followed by liquid desorption (LD) methodology was
optimized in terms of extraction time and ethanol content. The LD conditions
were optimized in terms of solvent and extraction time.
Both methodologies showed good linearity over the concentration range
tested, with correlation coefficients higher than 0.984 (SPME) and 0.982 (SBSE)
for all analytes. The detection limits ranged from 0.02 g/L

to 218.8 g/L

for
SPME and from

0.03 g/L to 69.36 g/L

in SBSE analysis. The quantification
limits from 0.06 g/L

to 729.50 g/L

for SPME. The quantification limits for the
SBSE developed method ranged from 0.11 to 231.19 g/L. The recovery
obtained was high for both methods, with good repeatability values. In general,
SBSE presented higher sensitivity than SPME technique for the studied
compounds. A total of 16 and 25 esters were identified in wines by HS-SPME
and SBSE techniques, respectively.

[1] R.F. Alvez, A.M.D. Nascimento, J.M.F. Nogueira. Anal. Chim. Acta 546 (2005) 11.
[2] A. Zalacain, J. Marin, G.L. Alonso, M.R. Salinas, Talanta 71 (2007) 1610.
152


ANALYSIS OF VOLATILES IN COMMERCICAL OLIVE
OIL USING LLE/GC-MS AND HS-SPME/GC-MS

Rosa M. Perestrelo, Catarina G. Lus, Michael M. Caldeira, Jos C.
Marques, Jos S. Cmara*
Centro de Qumica da Madeira, Departamento de Qumica, Universidade da Madeira,
9000-390 Funchal, Portugal
*jsc@uma.pt

Olive oil represents the main source of fats in countries of the Mediterranean
Basin where the olive oil production is concentrated, long known as essential to
their health and diets, it is now widely appreciated around the world for its
nutritional, health and sensory proprieties [1]. Virgin olive oil is extracted from
the fruit of the olive tree (Olea europaea L.) exclusively by mechanical and/or
physical methods without further refining to retain non-volatile and volatile
minor compounds [2]. The volatile profile of one virgin olive oil and four
aromatic olive oils (garlic, rosemary, oregano and thyme) were established using
liquid-liquid extraction (LLE) and headspace solid-phase microextraction (HS-
SPME) followed by gas chromatography-
quadropole
mass spectrometry (GC-
qMSD). The behaviour of six fibre coatings was evaluated for sensitivity,
repeatability and linearity response. The divinylbenzene/carboxen/
polydimethylsiloxane (DVB/CAR/PDMS) fibre achieved the best efficiency for
the analysis of commercial olive oil. Other HS-SPME parameters were also
optimized, like exposure time, extraction temperature, desorption time and
sample amount to reach the best extraction efficiency. Both methodologies
allowed the identification of more than 60 compounds belonging to different
chemical families, such as carbonyl compounds, alcohols, esters, fatty acids,
volatile phenol and hydrocarbons. The HS-SPME method comparatively to the
LLE technique was not suited to the characterization of olive oil volatile
compounds because of low sensitivity. Moreover, the presence of some of these
compounds in virgin olive oil has not been previously reported. Significant
quantitative differences of volatile compounds in different commercial olive oil
studied were detected. Principal components analysis (PCA) of chromatographic
data obtained, in terms of peak areas, was used as suitable tool to differentiate
these samples.

[1] F. Angerosa, M. Servili, R. Selvaggini, A. Taticchi, S. Esposto, G. Montedoro. J.
Chromatogr. A 1054 (2004) 17.
[2] J.F. Garca-Reyes, C. Ferrer, M.J. Gmez-Ramos, A. Molina-Daz, A.R. Fernndez-
Alba. Trends Anal. Chem. 26 (2007) 239.
153


VOLATILES CHARACTERIZATION OF ANNONA
CHERI MOLA MILL. CULTIVARS USING HS-SPME/GC-MS

Liseth Ferreira, Rosa M. Perestrelo, Jos S. Cmara*
Centro de Qumica da Madeira, Departamento de Qumica, Universidade da Madeira,
9000-390 Funchal, Portugal
*jsc@uma.pt

The family of annonaceae that includes Annona squamosa, Annona muricata,
Annona reticulata and Annona cherimola, contains a considerable number of
plants with economic significance because of their edible fruits around the
world, namely tropical America, Australia, Africa, India, Malaysia and
Mediterranean Europe [1]. The edaphoclimatic conditions of the Madeira Islands
are favourable for the production of tropical and subtropical fruits. Annona
cherimola Mill. (cherimoya) production and nowadays have an important role
for the economic development with an annual production around 1000 Ton per
year, exporting to the mainland, France, Spain and England markets. The
analysis of volatile compounds in Funchal, Madeira, Mateus and Perry Vidal
cultivars of Annona cherimola Mill. (cherimoya) were carried out by means of
headspace solid-phase microextraction (HS-SPME) coupled to gas
chromatographymass spectrometry (GCqMSD). HS-SPME technique was
optimized in terms of fibre selection, extraction time, extraction temperature and
sample amount to reach the best extraction efficiency. The best result was
obtained with 2 g of sample, using a divinylbenzene/carboxen/
polydimethylsiloxane (DVB/CAR/PDMS) fibre for 30 min at 30 C under
constant magnetic stirring (800 rpm). After optimization of the extraction
methodology, all the cherimoya samples were analysed with the best conditions
that allowed to identify about sixty volatile compounds. The major compounds
identified in the four cherimoya cultivars were methyl butanoate, butyl
butanoate, 3-methylbutyl butanoate, 3-methylbutyl 3-methylbutanoate and 5-
hydroximethyl-2-furfural. These compounds represent 69.08 5.22 %, 56.56
15.36 %, 56.69 9.28 % and 71.82 1.29 % of the total volatiles for Funchal,
Madeira, Mateus and Perry Vidal cultivars, respectively. This study showed that
each cherimoya cultivars have 40 common compounds, corresponding to
different chemical families, namely terpenes, esters, alcohols, fatty acids and
carbonyl compounds and using PCA, the volatile composition in terms of
average peak areas, provided a suitable tool to differentiate among the cherimoya
cultivars.

[1] M.N. Shashirekha, R. Baskaran, L.J. Rao, M.R. Vijayalakshmi and S. Rajarathnam,
LWT Food Sci. Technol. 41 (2008) 236.
[2] H. Idstein, W. Herres and P. Schreier, J. Agric. Food Chem. 32 (1984) 383.
154


OPTIMIZATION OF MATRIX SOLID PHASE DISPERSION
EXTRACTION FOR THE ANALYSIS OF ISOFLAVONES
IN TRI FOLI UM PRATENSE

Tatiana Visnevschi-Necrasov
a,b
, Sara C. Cunha
b
, Eugnia Nunes
a
*,
M. Beatriz Oliveira
b
a
CIBIO-ICETA, Faculdade de Cincias da Universidade do Porto, R. Padre Armando
Quintas, 4485-661 Vairo, Portugal.

b
REQUIMTE- Servio de Bromatologia, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal.
*enunes@icav.up.pt

Isoflavones have been found to have health benefits in age-related and
hormone-dependent diseases, including cancers, menopausal symptoms,
cardiovascular diseases, and osteoporosis [1]. Thus, identification and structural
determination of these compounds in plant tissues play an important role in
many areas of science, particularly plant science.
In order to obtain a pure extract for the determination of isoflavones in plant
for reversed-phase high-performance liquid chromatography (HPLC) analysis
with UV, fluorescence or diode-array detection [2], the classical procedures
involve multiple extraction, purification and concentrations steps. These
procedures are solvent based and require intensive manipulation of sample,
rendering them too much time- and material- consumption.
The Matrix Solid-Phase Dispersion (MSPD) procedure, simultaneously
disrupt semi-solid and solid samples and extract the target compounds, which
leads to very simple, fast, environmentally friendly and cheap extractions. This
procedure has been successfully applied to the analysis of pesticides and other
residual compounds in plants and foodstuffs [3].
The aim of this work was to develop a MSPD procedure for the quick
extraction of isoflavones in Trifolium pratense leaves and determination by
HPLC-diode array. Several experiments were carried out to access the effect of
several sorbents (C18, aminopropyl or OASIS) and cleaning solvents (methanol,
dichloromethane and chloroform + methanol) on the yield and quality of the
extraction. The results of experiments will be presented as well as sensitivity and
accuracy of the optimized method.

[1] A.Marston, K. Hostettmann. Flavonoids Chemistry, Biochemistry and Applications.
yvind M. Andersen and Kenneth R. Markham Eds, Taylor & Francis Group, Chap.
1, pp 1, 2006.
[2] H. Wiseman. Flavonoids Chemistry, Biochemistry and Applications. yvind M.
Andersen and Kenneth R. Markham Eds, Taylor & Francis Group, Chap. 7, pp
371,2006.
[3] S.C. Cunha, J.O. Fernandes, M.B.P.P. Oliveira. Food Add. Cont. 24 (2007) 156.
155


DETECTION OF SOYBEAN DNA IN COMMERCIALLY
AVAILABLE VEGETABLE OILS

Joana Costa
a
, Isabel Mafra
a
*, Joana Rocha
a
, Joana S. Amaral
a,b
, M.
Beatriz P. P. Oliveira
a

a
REQUIMTE, Servio de Bromatologia, Faculdade de Farmcia, Universidade do Porto,
Rua Anbal Cunha 164, 4099-030 Porto, Portugal.
b
ESTiG, Instituto Politcnico de Bragana, Bragana, Portugal.
*isabel.mafra@ff.up.pt

The soybean is the most important genetically modified crop, from which
60% of words planted area corresponds to Round Ready soybeans [1]. The need
to monitor and verify the presence and amounts of biotechnology derived
material in food products demands analytical methods able to detect, to identify
and to quantify either the introduced DNA or the expressed protein(s) [2].
Although DNA can be detected in crude vegetable oils, due to the physical and
chemical treatments used during refining, its detection is very difficult in the
final product [3]. In the present work we intended to extract soybean DNA from
ordinary commercial vegetable oils and compare the different methods used.
Four methods were tested in order to extract DNA in different commercially
available vegetables oils. Previous work has proved the applicability of
extracting soybean DNA from a wide range of foodstuffs by using the CTAB
and the Wizard methods and the Nucleospin

food kit [2]. Thus, those three


methods were tested and compared, in addition to the Wizard

Magnetic DNA
purification system for food. The DNA extracts were evaluated for their
amplifiability by polymerase chain reaction (PCR) targeting the lectin gene as a
marker for soybean.
The results showed that the Wizard

Magnetic kit following the instructions


of manufacturer and increasing the amount of extracted oil (from 160 to 200 g)
did not allow the detection of ampliable DNA. The pre-concentration of refined
oil by centrifuging 200 g of sample did not allow the detection of soybean DNA
with the CTAB and Wizard methods. However, using the same amount of oil
with the NucleoSpin

kit it was possible to detect of soybean DNA from refined


vegetable oils and soybean oil. This result was never reported and is an
achievement taking in consideration the need to detect genetically modified
DNA.

[1] James, C. (2006). Global status of commercialized Biotech/GM crops: 2006. ISAAA
Briefs No 35 New York Ithaca: ISAAA.
[2] Mafra, I; Silva, S. A.; Moreira, E. J. M. O.; Silva, C. S. F.; Oliveira, M. B. P. P.;
(2008). Comparative study of DNA extraction methods for soybean derived food
products; Food Control; in press.
[3] Gryson, N.; Ronsse, F.; Messens, K.; De Loose, M.; Verleyen, T.; Dewettinck, K;
(2002). Detection of DNA during the refining of soybean oil; J. Am. Oil Chem. Soc.;
79; 171.
156


QUALITY CONTROL OF FRANKFURT SAUSAGES BY
BIOMOLECULAR TECHNIQUES

Snia Soares
a,b
, Joana S. Amaral
a,b
, Isabel Mafra
a
*, M. Beatriz P. P.
Oliveira
a

a
REQUIMTE, Servio de Bromatologia, Faculdade de Farmcia, Universidade do Porto,
Rua Anbal Cunha, 164, 4099-030, Porto, Portugal
b
ESTiG, Instituto Politcnico de Bragana, Campus de Sta. Apolnia, 5301-857
Bragana, Portugal
*isabel.mafra@ff.up.pt

The quality of foods is a subject of great concern not only for assuring their
safety, but also regarding their authenticity. In processed meat products, it is very
important to establish that declared species of high commercial value are not
substituted, partial or entirely, by other lower value species. The misleading
labelling might have also negative implications concerning health, especially for
sensitive consumers to undeclared potential allergens, such as soybean [1].
The analytical methods used for species identification and authenticity of foods
rely mainly on protein and DNA analysis. More recently, DNA molecules have been
the target compounds due their high stability compared to the proteins. Moreover, the
analysis of DNA coupled with polymerase chain reaction (PCR) presents fast,
sensitive and highly specific alternatives to protein-based methods [2].
The aim of the present work was to develop PCR techniques able to identify
and quantify several ingredients (pork, poultry, beef and soybean) in highly
processed meat product, such as Frankfurt sausages. The analysed samples were
acquired in the retail market and reference binary samples, as standards, were
prepared in the laboratory. Samples and standards were extracted by two
different methodologies: the CTAB (cetyltrimethylammonium bromide) method
based on liquid-liquid extraction and the Wizard method based on silica solid
phase extraction. Yield and purity of extracts were assessed by
spectrophotometry. Both extraction protocols enabled high DNA yields with
reasonable purity (A
260
/A
280
1.5). PCR techniques were developed for each
target ingredient by optimisation of Mg
2+
concentration and thermalcycler
temperature program. The established conditions allowed the detection of levels
as low as 0.1% of added pork meat or soybean protein in mixtures of meats. The
results showed the undeclared presence of pork meat in commercial poultry
sausages.
Besides qualitative PCR, quantitative real-time PCR assays based on the
measurement of fluorescence increments by the use TaqMan probes and SYBR
Green I dye were also performed.

[1] M. Lees, B. Popping, Food authenticity and traceability, CRC Press, Florida, 2003.
[2] I. Mafra, I.M.P.L.V.O. Ferreira, M.B.P.P. Oliveira. Eur. Food Res. Technol., in press.
157


VALIDATION OF A MSPD METHOD TO ANALYSE
ACRYLAMIDE IN FOODSTUFFS BY GC-MS

Cristina M. D. Soares*, Jos O. Fernandes
REQUIMTE, Servio de Bromatologia, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto
*cristina.md.soares@gmail.com

GC-MS is one of the first choice techniques employed in the determination of
acrylamide in foodstuffs. This technique imply efficient extractions of the
compound from the food matrix with the condition that the extracts obtained are
clean enough to be suitable for chromatographic analysis. Traditional solvent
extraction techniques such as solidliquid and liquidliquid extractions are still
very popular in the extraction of acrylamide from foodstuffs. However, they are
often time-consuming and labour-intensive, and usually require large volumes of
solvents. Analysts often encounter emulsions and may need to perform several
centrifugations, re-extractions, and complex sample manipulations to render
samples into suitable forms.
Another approach, recently applied by our group in the determination of
acrylamide from potato chips [1], was matrix solid phase dispersion (MSPD).
This technique greatly reduced sample manipulation, solvent usage and disposal,
and working time. It also eliminated emulsification problems enhancing the
extraction yield of the contaminant.
The present work describes the development and optimization of a MSPD
procedure for the analysis of acrylamide in different food matrices with emphasis
in cereal products which generally contains low amounts (< 100 g/kg) of
acrylamide (bread, breakfast cereals, infant food, snacks, toasts, cookies, etc.).
The matrix (1 g) was dispersed in C
18
(4 g) and acrylamide was extracted with
two aliquots of 6 + 6 ml of water holding a soaking step of 5 minutes for each
extraction. The results obtained by using the reported method where compared
with those furnished by a previously developed analytical procedure that resorted
to a liquid extraction approach [2].

The authors are thankful to FCT for financial support in the framework of the project
POCI/AGR/61543/2004 and for the PhD grant of Cristina Soares with the reference
SFRH/BD/39360/2007.

[1] Jos O. Fernandes, Cristina Soares, J. Chromatogr. A 1175 (2007) 1.
[2] Cristina Soares, Jos O. Fernandes, Food Analytical Methods (in preparation).
158


DETERMINAO DE AZOTO AMONIACAL EM
ALFACES POR DIFERENTES MTODOS

Marta Duarte
a
, Cristina M. R. R. Oliveira
b
, Sandra Flix
b,c
*

a
DQB FCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa, Portugal
b
CCMM DQB FCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa Portugal
c
UATLA, Antiga Fbrica da Plvora de Barcarena, 2730-036 Barcarena, Portugal
*sfelix@uatla.pt

Hoje em dia, e ao contrrio do que era habitual at h poucos anos, notria
uma maior ateno e preocupao por parte dos consumidores em geral, no que
diz respeito qualidade dos alimentos que ingerem. Existe um elevado nmero
de contaminantes que podem ser encontrados nos vegetais e que so
indesejveis. No grupo dos nutrientes vegetais que causam contaminao
encontra-se o azoto. A ptima resposta que o adubo azotado induz no
desenvolvimento vegetativo leva a que os agricultores tenham tendncia a
exagerar as quantidades aplicadas [1]. So as suas formas inorgnicas (NO
3
-
,
NH
4
+
e NO
2
-
) que podem causar contaminao susceptvel de ser perigosa para o
homem. Por esse facto, o Decreto-Lei n 236/98 de 1 de Agosto fixa os valores
mximos recomendados (V.M.R.) desses contaminantes, em plantas herbceas,
principalmente com o objectivo de proteger a sade pblica e preservar o meio
ambiente [2]. Diversas metodologias laboratoriais tm sido descritas para a
determinao de azotos inorgnicos [3]. Neste trabalho pretende-se realizar o
estudo do teor em ies amnio (NH
4
+
) em diversos tipos de alface, visto ser um
vegetal com grande facilidade em acumular azoto nessa forma. Foram estudados
dois mtodos para a determinao de azoto amoniacal nas alfaces: o mtodo
espectrofotomtrico, recorrendo a reaco de Berthelot e o mtodo de Kjeldahl.
So considerados os aspectos tericos relacionados com a eficincia de cada
mtodo. Finalmente conclui-se sobre a qualidade das alfaces estudadas,
comparando os valores de teor em NH
4
+
obtidos experimentalmente com os
valores mximos recomendados por lei para este parmetro.

[1] M.A. Rodrigues; J.F. Coutinho. Eficincia de utilizao do azoto pelas plantas. Srie
Estudos, Edio do Instituto Politcnico de Bragana, Portugal, 2000.
[2] Dirio da Repblica I SRIE A Ministrio do Ambiente, Decreto-Lei n 236/98
de 1 de Agosto, 176, 3676-3722. Imprensa Nacional - Casa da Moeda, Lisboa,
Portugal, 1998.
[3] A.O. Prazeres. Comparao de metodologias laboratoriais para determinao de
azoto ntrico e amoniacal em solos e guas. I Congresso Nacional de Rega e
drenagem, Beja, Portugal, 2005.
159


MOLECULAR MOBILITY AND PHYSICAL AGING ON
THE AMORPHOUS PHASE OF GLUCOSE

Joaquim J. Moura-Ramos
a
*, Hermnio P. Diogo
b

a
Centro de Qumica Fsica-Molecular, Instituto Superior Tcnico, Universidade Tcnica
de Lisboa, Av. Rovisco Pais 1049-001 Lisboa, Portugal
b
Centro de Qumica Estrutural, Instituto Superior Tcnico, Universidade Tcnica de
Lisboa, Av. Rovisco Pais 1049-001 Lisboa, Portugal
*mouraramos@ist.utl.pt

Carbohydrates are the principal source of energy in cells and are implicated
in a large variety of biological processes including cell-cell recognition, neuronal
development, and tumor-cell metastasis. Simple saccharides in the amorphous
solid state are believed to protect biomacromolecules and cells during freezing,
dehydration and storage. The study of the evolution of the molecular mobility
from high temperature down to the glassy state is a significant highlight to the
comprehension of the biopreservation capacity.
The study by TSDC of the molecular mobility in the crystalline o-D(+)-
glucose showed a well defined and broad relaxation (activated between -50C
and 90C) that corresponds to localized or non-cooperative motions. The
mobility in the amorphous solid prepared from the crystalline o-D(+)-glucose
showed a broad and complex secondary relaxation revealing a clear structuration
with three kinds of molecular motions, and with activation energies distributed
between 30 and 65 kJ mol
-1
. It was found that the lower temperature components
of this complex secondary mobility are aging independent, while the higher
temperature components are affected by aging. On the other hand, the analysis of
the structural or main relaxation indicated that the activation energy at the glass
transition temperature (T
g
= 30C at 4C min
-1
) is E
a
(T
g
) = 246 kJ mol
-1
, so that
the fragility index is m = 43. This value indicates that glucose is a relatively
strong glass forming liquid. Attention is drawn to the scattering of the fragility
values provided by different experimental techniques and from different
methodologies based on the same technique.
Figure 1. Amorphous glucose: (left) Partial polarisation components of the sub-Tg
molecular mobility; (right) TSDC thermogramme showing the secondary relaxations of
unaged (upper curves) and aged (lower curves).

-0.3
0.3
0.9
1.5
2.1
2.7
3.3
-170 -140 -110 -80 -50 -20 10
T / C
I

x

1
0
1
3

/

A
a
b
c
0
3
6
9
12
15
-170 -130 -90 -50 -10 30
T / C
I

X

1
0
1
3

/

A
160


OCCURRENCE OF OCHRATOXIN A IN WHEAT BREAD
FROM CENTRAL ZONE OF PORTUGAL: WINTER 2007

Sofia C. Duarte, Ana C. Tanello, Celeste M. Lino*, Angelina Pena
Group of Bromatology, CEF, Faculty of Pharmacy, University of Coimbra, Portugal
*cmlino@ci.uc.pt

Ochratoxigenic fungi are natural contaminants of cereal and their toxins are
harmful to humans and animals. Ochratoxin A (OTA) occurs predominantly in
cereal grains and products, cocoa, spices, oilseeds, coffee beans and pulses.
Cereal products contamination is of special interest as they are one of the more
consumed food commodities. The International Agency for Research on Cancer
has placed OTA in Group 2B, a possible human carcinogen [1].
Bread is a product of daily consumption and highly demanded and several
authors have indicated bread as one of the main sources of daily intake of OTA.
The presence of OTA in bread results from the contamination of wheat flour, and
probably only part is destroyed during the bread-making process.
A total of 27 samples of wheat bread, collected during winter 2007 from
central Portugal were tested for OTA, according to the method of Juan et al. [2],
which involved extraction with PBS: methanol and clean-up through
immunoaffinity columns. Separation and identification were carried out by high-
performance liquid chromatography with fluorescence detection at 333 and 464
nm as excitation and emission wavelengths, respectively.
The limits of detection and quantification
were 0.015 and 0.03 ng/g, respectively.
Recoveries ranged from 83.3% to 87% for
fortifications at 0.5 ng/g

and 2.0 ng/g,
respectively, with intra-day RSD of 1.4 and
3.2%, and inter-day RSD of 7.2 and 9.3%.
OTA was found in twenty-one of the
analyzed samples (77.7%).). The detected levels
ranged from 0.05 to 1.51 ng/g, with a mean
concentration of 0.21 ng/g and a standard
deviation 0.30 ng/g (Figure 1). None of the
samples exceeded the maximum limit set by the
European Commission Regulation, 3 ng/g.

Acknowledgments: This study was supported by the FCT through the Project PTDC/AGR-
ALI/65528/2006.

[1] C. Juan, J.C. Molt, C.M. Lino, J. Maes Food Chemistry 107 (2008) 525.
[2] C. Juan, C.M. Lino, A. Pena, J.C. Molt, J. Maes, I. Silveira Talanta 73 (2007) 246.

Figure 1. Mean, SD and limit
levels of OTA in wheat bread
161


EXTRACO DE ANTIOXIDANTES EM BRCOLOS
ATRAVS DE ULTRASSONS

Nair Alua
a
*, Anabela Raymundo
b
, M. Celeste Serra
a,c
a
Departamento de Engenharia Qumica, R. Conselheiro Emdio Navarro,1 1959-007 Lisboa
b
Instituto Piaget,Quinta da Arreinela de Cima, 2800-305 Almada
c
Centro de Investigao em Engenharia Qumica e Biotecnologia, R. Conselheiro Emdio
Navarro,1 1959-007 Lisboa
*nairalua@deq.isel.ipl.pt

A avaliao da capacidade antioxidante de produtos naturais tem sido
alvo de intensa pesquisa nos ltimos anos. O interesse pelos compostos com
propriedades antioxidantes deve-se ao facto de lhes serem reconhecidas
importantes funes na conservao dos alimentos e na proteco da sade.
Os frutos e vegetais so fontes de antioxidantes naturais entre os quais se
destacam as vitaminas, carotenides, flavonides e outros polifenis (1). O
consumo frequente destes produtos, segundo os estudos epidemiolgicos que
tm sido realizados, contribui para uma reduo significativa do risco de doenas
coronrias e de desenvolvimento de cancro. Alis, o World Cancer Research
Fund e o American Institute for Cancer Research alertam, desde 1997,para as
vantagens de uma dieta rica em frutas e legumes, recomendando a ingesto diria
de pelo menos 400 a 800g destes produtos.
Com o objectivo de avaliar o efeito de diferentes tipos de processamento
no teor em polifenis e na actividade antioxidante de diversos legumes foram
preparados extractos vegetais de brcolos, associando tcnica de extraco
com solventes orgnicos uma sonda de ultrassons (2,3). Foram ensaiadas
vrias condies de extraco e analisada a influncia de parmetros como o
tempo e a amplitude de sonicao, a composio do solvente e a massa de
amostra no doseamento dos polifenis e na determinao da actividade
antioxidante dos extractos. O mtodo de Folin-Ciocalteau foi utilizado para a
determinao do teor em polifenis e a actividade antioxidante dos extractos
avaliada com base na capacidade de inibio de radicais de 1,1-difenil-2-
picrilhidrazil (DPPH) (1).
Os resultados permitiram comparar os diferentes mtodos de extraco e
selecionar as melhores condies de ensaio. A extraco em presena de
ultrassons revelou ser mais promissora em termos de rendimento e tempo de
preparao dos extractos.

|1| N.Turkmem, F. Sari, Y. S. Velioglu. Food Chemistry 93 (2005) 713.
|2| N.Alua, I. Godinho, A. Catarino, M.C.Serra. Livro de Actas 8 Encontro de Qumica
de Alimentos, Beja (2007).
|3| A.V.Filgueiras, J.L. Capelo, I.Lavilla, C.Bendicho. Talanta 53 (2000).
162


SINGLE INTERFACE FLOW ANALYSIS LIQUID-LIQUID
EXTRACTION. PRELIMINARY STUDIES

Cristina I. C. Silvestre*, Joo L. M. Santos, Jos L. F. C. Lima
Requimte, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do Porto,
Rua Anbal Cunha, n 164, 4099-030, Porto, Portugal
*cristina.silvestre@gmail.com

Liquid-liquid extraction is one of the most frequently used methods for
sample pre-treatment preceding the measurement of the analyte concentration.
This technique allows enhancing selectivity, since an analyte can be separated
from an interfering matrix or the interfering matrix can be removed from the
sample, and also improving detections limits, as an analyte can be concentrated
when extracted from a large volume of an aqueous sample into a small volume
of an organic phase.
Procedures involving manual liquid-liquid extraction are generally very
tedious and time-consuming. Besides, they demand large amounts of solvents
and chemicals and are susceptible to potential contaminants from the atmosphere
and chemical glassware.
To overcome the mentioned drawbacks several automated flow systems that
connect the liquid-liquid extraction system to the analytical instrument, were
proposed. Although these flow systems significantly reduce the quantities of
solvents/reagents needed and notably increase the determination rates, their
exploitation on extractives processes is restricted, due, in part, to the difficulties
associated to the on-line implementation, and posterior separation, of interfaces
involving two immiscible phases.
In this work, an automated flow methodology based on a single reaction
interface flow analysis (SIFA) system [1] was developed with the purpose of
assessing on-line liquid-liquid extraction without the referred shortcomings. One
of the main advantages of SIFA systems is that they no longer rely on the
utilization of well-defined and compelling sample and reagent volumes, but on
the establishment of a single sample/reagent reaction interface, where the sample
and reagent solutions have no fixed boundaries. This facilitates system
configuration and enhances simplicity and operational versatility.
Therefore, the preliminary studies of the SIFA liquid-liquid extraction system
involved the use of different types of propulsion units (solenoid micro-pumps
and burettes), the evaluation of distinct physical parameters, such as, capacity of
the flow cell, length and shape of the reactors, flow rate, as well as, chemical
parameters, namely concentration of the analyte to be extracted and solvents with
different polarities and miscibilities (pentanol, hexanol, octanol). These initial
results were obtained from a water/solvent system where the analyte
(bromocresol green) was extracted from an aqueous phase to an organic phase.

[1] M.F.T. Ribeiro, J.L.M. Santos, J.L.F.C. Lima, A.C.B. Dias, E.A.G. Zagatto. Talanta
68 (2005) 351.
163


A SPECIATION METHOD FOR THE DETERMINATION
OF THE HYDROXYL CONTENT IN HYDROXYAPATITE

Ricardo G. Simes
a
, Antnio C. L. Conceio
b
, Manuel E. Minas da
Piedade
a
*
a
Departamento de Qumica e Bioqumica, Faculdade de Cincias, Universidade de
Lisboa, 1749-016 Lisboa, Portugal
b
Centro de Qumica Estrutural, Complexo Interdisciplinar, Instituto Superior Tcnico da
Universidade Tcnica de Lisboa, 1049-001 Lisboa, Portugal
*memp@fc.ul.pt, antonio.conceicao@ist.utl.pt

Apatites are a class of compounds of general formula M
10
(PO
4
)
6
X
2
, where M
is a divalent metal cation (primarily Ca
2+
, Sr
2+
, Ba
2+
, Cd
2+
, or Pb
2+
), and X is a
monovalent anion (OH

, F

, Cl

, and Br

). The calcium derivatives are by far the


most abundant, and they constitute one of the principal host phases for
condensed phosphorus and halogens in the solar system at temperatures below
ca. 700 K. Hydroxyapatite is a major constituent of mammalian bone and teeth
enamel, where it occurs as a non-stoichiometric, amorphous, and carbonated
form. Stoichiometric hydroxyapatite Ca
10
(PO
4
)
6
(OH)
2
is normally selected as a
reference model for characterizing the properties of apatitic biominerals. Due to
its good biocompatibility it is also significantly applied as a biomaterial for
medical implants.
It is well-known that the hydroxyapatite structure is very tolerant to ionic
substitutions and that different synthetic procedures can lead to compounds with
deviations from the Ca
10
(PO
4
)
6
(OH)
2
stoichiometry. Therefore, once a sample is
prepared, it is very important to characterize its elemental composition as
accurately as possible.
In this communication, we describe an analytical protocol for hydroxyaaptite,
involving the evaluation of the calcium and phosphorus contents by
potentiometric titration, and the determination of OH

based on speciation
analysis. Although primarily designed for hydroxyapatite this method can also be
used to analyze the H
+
content of acidic calcium phosphates. The algorithm at
the heart of the speciation analysis will be presented.
The validation tests led to Ca and P contents in agreement within the
experimental error with those obtained for the same sample by atomic absorption
spectroscopy and ICP (Ca), and by a standard spectrophotometric method and IC
(P). The analysis of OH

was validated using a reference material.


The obtained results showed that the present protocol is a simple and reliable
alternative for the elemental analysis of hydroxyapatite and, in principle, for
several other calcium phosphates.

Acknowledgments: This work was supported by the GRICES (Portugal) / DAAD
(Germany) bilateral exchange program (Proc. 4.1.1/DAAD).
164


SISTEMA DE FLUXO COM CLULA DE PERCURSO
OPTICO LONGO PARA A DETERMINAO DE FERRO
EM GUAS

Ricardo N. M. J. Pscoa*, Ildik V. Tth, Antnio O. S. S. Rangel
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, Rua Dr. Antnio
Bernardino de Almeida, 4200-072 Porto, Portugal
*rjpascoa@mail.esb.ucp.pt

Nas ltimas dcadas o ciclo geoqumico do ferro bem como a sua
disponibilidade e a forma em que esta presente em recursos martimos, tem sido
alvo de grande interesse [1]. Os nveis de ferro presente em sistemas aquticos
demonstra variao temporal e espacial no intervalo de 0,02 a 100 g/L. Assim
sendo, o desenvolvimento de mtodos automticos capazes de fornecer dados
analticos num curto espao de tempo com elevada preciso e exactido torna-se
um pr-requisito para o estudo dos sistemas geoqumicos dinmicos [2].
Neste trabalho foi desenvolvido um sistema SIA com a utilizao de uma
clula de fluxo de percurso ptico longo para a determinao espectrofotomtrica
de ferro em diferentes tipos de gua. Foram comparados dois reagentes de
desenvolvimento de cor: ferrozina e o-fenantrolina, obtendo-se como limite de
deteco 0,15 0,01 e 0,35 0,08 g/L, respectivamente. O mtodo
desenvolvido com ambos os reagentes tm uma zona de linearidade at 20 g/L
e uma taxa de determinao de 41 amostras por hora. O consumo de reagentes,
embora muito baixo, superior no caso do reagente o-fenantrolina, 0,0013
mmol/ensaio enquanto que no reagente ferrozina, 0,00025 mmol/ensaio. Para
avaliar a exactido do mtodo desenvolvido foram realizados ensaios de
recuperao em diversos tipos de gua (guas do mar, poo, furo) para os dois
reagentes no intervalo de 2 a 20 g/L de ferro. Os resultados obtidos pelo
mtodo desenvolvido na anlise de diferentes tipos de amostra foram tambm
comparados com os resultados obtidos pela anlise por espectrofotometria de
absoro atmica com atomizao electrotrmica. Com o mesmo objectivo foi
analisada uma amostra de referncia SLRS-4 com o valor certificado de ferro de
103 5 g/L. Os resultados obtidos de 98,9 0,7 g/L e 104,7 0,7 g/L para
os reagentes ferrozina e o-fenantrolina, respectivamente, comprovam a exactido
do sistema desenvolvido.

Agradecimentos: R. Pscoa e I. Tth agradecem o apoio financeiro da FCT e FSE (III
Quadro Comunitrio) atravs das bolsas SFRH/BD/30621/2006 e SFRH/BPD/5631/2005
respectivamente. Agradece-se FCT o apoio financeiro atravs do projecto
PTDC/AMB/64441/2006.

[1] W.L. Miller, D.W. King, J. Lin, D.R. Kester, Mar. Chem. 50 (1995) 63.
[2] S. Gray, G. Hanrahan, I. McKelvie, A. Tappin, F. Tse, P. Worsfold, Environ. Chem. 3
(2006) 3.
165


UNVEILING CHEMICAL AND PHYSICAL
INFORMATION FROM CHEMOMETRICS MODELS

Mafalda C. Sarragua, Adriano Fachini*, Joo A. Lopes
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*fachini@ff.up.pt

With the increasing application of multivariate methods in chemical analysis,
uncertainty estimation in multivariate calibration has become a critical subject of
active research. In fact, uncertainty estimation is currently a major trend in the
chemometrics-oriented literature [1]. Multivariate methods for data analysis are
supposed to provide a better insight of a chemical process. However, an efficient
application of a multivariate method requires not only its application to a
particular dataset but a correct interpretation of the results. More precisely,
researchers applying a chemometrics method aim at identifying some patterns
that they can relate with the actual chemical and physical properties of their
systems [2]. This is seldom the case by purely applying chemometrics: the
rotational ambiguity of most chemometrics methods prevents results to have an
immediate and meaningful interpretation. In particular, curve resolution
methodologies such as principal component analysis (PCA), partial least squares
(PLS), multivariate curve resolution (MCR) or wavelet transforms (WT) can be
used to unveil chemical and kinetic information in analytical and process
analytical chemistry [3]. However, the simple application of these methods to
chemical data does provide in general information lacking physical and chemical
meaning.
A survey of the main methods to apply with chemometrics multivariate
resolution methods to extract meaningful chemical composition and to provide
uncertainty estimations is provided and supported with different chemical data.
The chemometrics complementary procedures include resampling strategies to
estimate confidence and prediction intervals, rotational methods to adjust models
to chemical meaningful patterns and using constraints to prevent unreal model
solutions. Implementation is supported with examples from: 1)
chemiluminescence reaction; 2) flow analysis coupled with potentiometry; 3)
heavy-metals pollutants removal with cyanobacteria and 4) pharmaceutical
quality control by near-infrared spectroscopy. By adjusting the chemometrics
methods involved in solving each problem it was possible in all situations to
relate model parameters with chemical/physical properties.

[1] A. Olivieri, N. Faber, J. Ferr, R. Boqu, J. Kalivas, H. Mark, Pure Appl. Chem. 78
(2006) 633.
[2] P.D. Wentzell, D.T. Andrews, D.C. Hamilton, K. Faber, B.R., Kowalski, J. Chemom.
11 (1997) 339.
[3] K. Faber, R. Bro, Chemom. Intell. Lab. Syst. 61 (2000) 133.
166


DETERMINAO DE DIVERSOS PARMETROS EM
GUAS POR ANLISE POR INJECO SEQUENCIAL

Raquel B. R. Mesquita*, Antnio O. S. S. Rangel
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, R. Dr. Antnio
Bernardino de Almeida 4200-072 Porto, Portugal
*raquelb@mail.esb.ucp.pt

A preocupao com a qualidade da gua tem vindo a aumentar e uma
monitorizao frequente e exaustiva o melhor garante dessa mesma qualidade.
A monitorizao deve ser efectuada tanto em guas de nascente como em guas
residuais. Consequentemente, tem-se observado uma procura crescente de
tcnicas de anlise versteis, fiveis, mais rpidas, robustas e econmicas. As
tcnicas de anlise em fluxo apresentam-se como uma excelente ferramenta para
o desenvolvimento de novas metodologias devido s vantagens significativas que
apresentam em relao aos procedimentos convencionais, nomeadamente no que
se refere ao menor consumo de tempo e de reagentes. A anlise por injeco
sequencial (SIA) uma tcnica de fluxo que tem como vantagens adicionais
grande versatilidade e robustez, pelo que foi a tcnica escolhida para o
desenvolvimento do trabalho apresentado. Procurando grande aplicabilidade com
um custo relativamente baixo, desenvolveram-se metodologias SIA com
espectrofotometria de absoro molecular (UV-Vis) como sistema de deteco.
Nesta comunicao pretende-se ilustrar a possibilidade de, utilizando
basicamente o mesmo equipamento, se desenvolver metodologias para a
determinao de diversos parmetros em guas: cloreto, clcio, magnsio,
alcalinidade, chumbo, cloro e alumnio. As metodologias desenvolvidas
apresentam ainda uma vantagem extra que a de permitirem a introduo directa
das amostras de gua, desde gua mineral a gua residual, sem que sejam
necessrios tratamentos prvios.
Tabela 1. Resumo das caractersticas das metodologias desenvolvidas, DPR desvio
padro relativo.

Agradecimentos: R B. R. Mesquita agradece Fundao para a Cincia e a Tecnologia
(FCT) a bolsa SFRH/BPD/41859/2007. Os autores agradecem ainda FCT o apoio
financeiro no mbito do projecto PTDC/AMB/64441/2006.
Metodologia Parmetro
Intervalo de
aplicabilidade (mg/L)
Limite de
deteco (mg/L)
DPR
(%)
Det./h
Sem separao
em linha
cloreto 2,00 400 2,0 3,7 55
clcio 0,5 5,0 0,32 2,0 40
magnsio 0,50 10 0,030 2,1 40
alcalinidade 10 100 5,1 0,4 65
alumnio 0,04 0,50 0,020 3,3 >31
Com separao
em linha
cloro 0,09 4,80 0,080 2,0 >15
chumbo 0,05 1,00 0,025 3,6 >17
167


DURABILIDADE DE GEOSSINTTICOS EXPOSTOS A
AGENTES QUMICOS PROJECTO GEOCHEM

Jos R. Carneiro
a
*, Paulo J. Almeida
b
, Maria L. Lopes
a

a
Departamento de Engenharia Civil, Faculdade de Engenharia de Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto
b
Departamento de Qumica, Faculdade de Cincias da Universidade do Porto, Rua do
Campo Alegre, 687, 4169-007 Porto
*rcarneir@fe.up.pt

Os geossintticos so materiais polimricos amplamente aplicados em
diversas obras de Engenharia Civil, algumas delas de carcter ambiental, como
o caso dos aterros sanitrios de resduos. No entanto, a exposio radiao
ultravioleta e a outros agentes climatricos, a oxidao induzida pela temperatura
e o contacto prolongado com diversas solues cidas e/ou alcalinas podem
afectar a durabilidade destes materiais e, consequentemente, o seu desempenho.
Em algumas aplicaes (como por exemplo no caso dos aterros sanitrios de
resduos), a falha prematura destes materiais poder ter graves consequncias
ambientais. Assim, para uma aplicao correcta dos geossintticos necessrio
prever a degradao dos materiais ao longo do tempo e assegurar valores
mnimos de certas propriedades (fsicas, mecnicas e hidrulicas) durante o
tempo de vida da estrutura onde esto inseridos.
O projecto GEOCHEM (PTDC/ECM/67547/2006) tem como objectivo
principal avaliar a resistncia de vrios geossintticos face aos vrios agentes de
degradao fsicos e qumicos. Este projecto, associando a Qumica Engenharia
Civil, pretende ser um contributo para o estudo da durabilidade dos
geossintticos e, permitir, assim, uma melhor aplicao destes materiais em
estruturas de Engenharia Civil (tendo em conta a extenso da degradao que os
materiais iro sofrer durante o seu tempo de servio).
A durabilidade dos geossintticos (geotxteis, geomembranas e georredes)
foi estudada atravs da exposio dos materiais a vrios agentes de degradao e
posterior avaliao do efeito destes agentes nas suas propriedades fsicas,
qumicas, mecnicas e hidrulicas. Os geossintticos foram sujeitos aco da
radiao ultravioleta (foto-oxidao) e de outros agentes climatricos, expostos
oxidao induzida pela temperatura (termo-oxidao) e imersos em diversas
solues cidas e alcalinas. Os materiais foram expostos a ensaios de degradao
sob condies reais (ensaios longos: vrios meses ou anos) e a ensaios
acelerados em laboratrio (ensaios relativamente curtos: alguns dias ou
semanas).
A degradao sofrida pelos geossintticos foi retardada pela incorporao de
aditivos qumicos (tais como, estabilizadores ultravioleta e antioxidantes) na
composio dos materiais. O projecto GEOCHEM pretende, tambm,
desenvolver estratgias que permitam a monitorizao destes compostos ao
longo do tempo de vida dos geossintticos.
168


MONITORIZAO DE MACRONUTRIENTES EM
AMOSTRAS AMBIENTAIS USANDO ANLISE POR
MULTI-SERINGA

M. Ins G. S. Almeida
a
*, Marcela A. Segundo
b
, Jos L. F. C. Lima
b
,
Antnio O. S. S. Rangel
a

a
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, Rua Dr. Antnio
Bernardino de Almeida, 4200-072 Porto
b
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto
*mialmeida@mail.esb.ucp.pt

A necessidade de aplicao de fertilizantes aos solos e os problemas de
eutrofizao de rios e lagos que da podem advir, entre outras questes, faz com
que a monitorizao de macronutrientes em amostras ambientais, nomeadamente
guas, plantas ou solos, se torne de extrema importncia tanto no mbito agrcola
como ambiental.
Na realidade, este tipo de anlises envolve procedimentos complexos e
morosos, tais como digesto ou extraco. Assim, o desenvolvimento de
procedimentos analticos que permitam uma avaliao rpida e fivel deste tipo
de matrizes, pode constituir um contributo significativo nas reas mencionadas.
A eficincia e versatilidade que caracterizam as tcnicas de fluxo podem
satisfazer este propsito.
Nesta comunicao evidencia-se algumas potencialidades da utilizao de
sistemas de fluxo baseados na anlise por multi-seringa (MSFIA) com o intuito
de automatizar no s a determinao de fsforo e potssio em matrizes
ambientais, mas tambm as operaes prvias medio instrumental.
Apresenta-se um sistema automtico para digesto cida de guas residuais, por
aco de um microondas domstico, previamente determinao
espectrofotomtrica de fsforo total. A aplicao de amostras lquidas a sistemas
de fluxo fisicamente acessvel. No entanto, quando se pretende analisar
amostras slidas, o desafio claramente superior. Para demonstrar esta
possibilidade, apresenta-se um sistema com introduo directa de amostras de
plantas sob a forma de suspenso para posterior determinao de potssio por
fotometria de emisso de chama. Outros desafios podem ainda ser explorados,
como a implementao da preparao de um extracto de solo em linha; aps a
adio de soluo de extraco (Morgan) a uma poro de solo previamente
pesada e sua extraco, feita a filtrao em linha e a determinao
potenciomtrica de potssio.
Todos os sistemas MSFIA desenvolvidos apresentam bons resultados a nvel
de preciso e exactido, bem como uma melhoria significativa em relao
frequncia de amostragem comparativamente aos mtodos de referncia.
Agradecimentos: M.I.G.S. Almeida agradece FCT e FSE (III Quadro Comunitrio de
Apoio) a bolsa de doutoramento (SFRH/BD/8541/2002).
169


SOLID-PHASE EXTRACTION USING BEAD INJECTION
IN LAB-ON-VALVE FORMAT

Hugo M. Oliveira
a
*, Marcela A. Segundo
a
, Jos L. F. C. Lima
a
, Manuel
Mir
b
, Victor Cerd
b

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha 164, 4099-030 Porto, Portugal
b
Department of Chemistry, Faculty of Sciences, University of the Balearic Islands,
Carretera de Valldemossa km 7.5, E-07122 Palma de Mallorca, Balearic Islands, Spain
*hmoliveira@gmail.com

Solid-phase extraction (SPE) is a common tool for sample preparation due to
the ease of application and the wide range of sorbents commercially available.
The automation of this technique using flow injection analysis and related
techniques is well described in the literature, showing how much the
performance of the sample preparation step is enhanced when compared with
traditional batch procedures. Nevertheless, the typical SPE flow manifold
involves the placement of sorbent in a packed bed column whose performance
can be easily impaired when complex matrices are handled.
In this context, Lab-on-valve (LOV), presented as the third generation of
flow injection analysis [1], introduced the possibility of renewing the sorbent
after each extraction. This operation is possible owing to the configuration of the
manifold that comprises a rigid structure, with microchannels engraved on it, that
is coupled to a selection valve and a syringe pump. By this way, it is possible to
handle l volumes of suspensions in an automatic fashion, defined as bead
injection. These features allowed the development of hyphenated methods
coupling SPE and liquid chromatography [2].
In the present work, different commercially available hydrophilic /
hydrophobic copolymeric sorbents (Oasis HLB and Focus) able to perform the
reversed-phase SPE of organic emerging pollutants [3] were evaluated in order
to develop an on-line SPE-LC method. In this evaluation, bead geometry and
size were considered because these aspects directly influence the reproducibility
of consecutive injections and the total amount of sorbent available for each SPE
procedure. On other hand, variables as sample loading flow rate, breakthrough
volume and sorbent capacity that are also dependent of the sorbent nature and
structure, were studied. Finally, different strategies for holding the beads into the
LOV system are also presented.

Acknowledgements: Hugo M. Oliveira thanks Fundao para a Cincia e Tecnologia
(FCT) and FSE (III Quadro Comunitrio) for the grant SFRH/BD/22494/2005.

[1] J. Ruzicka, Analyst 125 (2000) 1053.
[2] J. B. Quintana, M. Mir, J. M. Estela, V. Cerd, Anal. Chem. 78 (2006) 2832.
[3] S. D. Richardson, Anal. Chem. 79 (2007) 4295.
170


ESTUDO DA FOTO-DEGRADAO DE GEOTXTEIS DE
POLIPROPILENO POR FTIR

Ins M. Valente
a
, Paulo J. Almeida
a
, Jos R. Carneiro
b
*, Maria L.
Lopes
b

a
Departamento de Qumica, Faculdade de Cincias da Universidade do Porto, Rua do
Campo Alegre, 687, 4169-007 Porto
b
Departamento de Engenharia Civil, Faculdade de Engenharia de Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto
*rcarneir@fe.up.pt

Os geotxteis so materiais de constituio polimrica amplamente aplicados
na construo de infra-estruturas. Nessas aplicaes, estes materiais podem estar
expostos durante um longo perodo de tempo a diversos agentes de degradao
capazes de afectar negativamente as suas propriedades fsicas, qumicas,
mecnicas e hidrulicas. A exposio prolongada radiao ultravioleta uma
das principais causas responsveis pela degradao prematura dos geotxteis. A
foto-degradao normalmente retardada ou inibida pela incorporao de
aditivos qumicos na formulao dos geotxteis, tais como o Chimassorb 944
(uma amina antioxidante e estabilizadora de luz e radiao ultravioleta).
Neste trabalho, procedeu-se avaliao do grau de foto-degradao de
geotxteis de polipropileno utilizando a espectroscopia de infravermelho com
transformada de Fourier (FTIR). Os geotxteis, fabricados a partir de fibras de
polipropileno estabilizadas com diferentes teores do aditivo Chimassorb 944
(0%, 0,2% e 0,4%), foram expostos radiao ultravioleta num simulador
climatrico o QUV. As fibras dos geotxteis expostos foram analisadas por
FTIR e os espectros obtidos foram comparados com os espectros obtidos para as
fibras intactas (sem qualquer tipo de degradao).
A foto-degradao das fibras de polipropileno originou alteraes nos
espectros de infravermelho dos materiais, causando o aparecimento de uma nova
banda centrada a 1720 cm
-1
. Esta banda, que pode ser atribuda ao grupo
carbonilo, foi utilizada para avaliar a degradao sofrida pelos geotxteis. A
formao de compostos carbonlicos um indicador da ocorrncia de oxidao
em materiais de polipropileno [1].
Paralelamente, o aditivo Chimassorb 944 foi determinado nos geotxteis
estabilizados, aps extraco por ultra-sons, por cromatografia lquida de alta
eficincia com deteco a 244 nm. Desta forma, foi possvel verificar a
existncia de uma relao entre o grau de foto-degradao dos geotxteis e a
diminuio do teor de Chimassorb 944 ao longo da exposio radiao
ultravioleta.

Os autores agradecem o apoio financeiro do projecto PTDC/ECM/67547/2006.

[1] P. Gijsman, A. Dozeman, Polymer Degradation and Stability 53 (1996) 45.
171


DETERMINATION OF COMPOUNDS WITH
PHARMACEUTICAL INTEREST BY OXIDATION
REACTIONS USING A SIA SYSTEM

Marieta L. C. Passos, M. Lcia M. F. S. Saraiva*, Jos L. F. C. Lima
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal.
*lsaraivaf.up.pt

The sequential injection analysis (SIA) [1] technique was used to perform the
determination of two families of compounds with pharmaceutical interest (-
blockers and phenothiazines). The proposed methods are based on the oxidation
of the drugs and were applied to pharmaceutical formulations.
For the determination of -blockers it was used permanganate that was
reduced by this family of drugs to the colourless Mn
2+
. The consequent decrease
of absorbance at 525 nm, is directly proportional to -blockers concentration in
the sample.
For the determination of phenothiazines an enzymatic methodology was
developed, based on the oxidation of these drugs in acidic medium by hydrogen
peroxide, with the formation of colored oxidation product [2] monitored
spectrophotometrically at 527 nm. Peroxidase catalyzes oxidation of the
substrate by hydrogen peroxide, via free-radical intermediate [3]. This enzyme
was stable and active not only in aqueous medium but also in micellar medium.
This was demonstrated with the determination of low water-soluble
phenothiazines that were though solubilized with the aid of a surfactant.
Physical and chemical optimisations were performed for both methodologies
in order to attain the best analytical performances. RSD values lower than 5%
were attained. The statistical comparison between the results obtained with the
proposed methods and the correspondent reference methods showed good
agreement and indicate no significant difference at the 95% confidence level.
The proposed SIA systems are robust, versatile, and simple alternatives,
adapted to the actual demands of sample and reagents economy and reduced
residue production, being in good agreement with the actual recommendations of
green chemistry.

Acknowledgements: Marieta L. C. Passos thanks Fundao para a Cincia e a Tecnologia
and FSE (III Quadro Comunitrio) for the Ph.D. grant (SFRH/BD/22752/2005).

[1] J. Ruzicka, G. D. Marshal. Anal. Chim. Acta 237 (1990) 329.
[2] A. Kojlo, J. Karpinska, L. Kuzmicka, W. Misiuk, H. Puzanowska-Tarasiewicz, M.
Tarasiewicz. J. Trace Microprobe T. 19 (2001) 45.
[3] J. Kulys, K. Krikstopaitis, A. Ziemys. J. Bio.l Inorg. Chem. 5 (2000) 333.
172


SISTEMAS DE EXTRACO COM MEMBRANA
DESCARTVEL: DETERMINAO DE ACETALDEDO

J. P. Pacheco, J. A. Rodrigues*
,
A. A. Barros

Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre, 687, 4169-007,
Porto, Portugal
*jarodrig@fc.up.

Neste trabalho foi desenvolvido um novo mdulo para extraco de
compostos volteis ou semi-volteis com membrana descartvel. O mdulo
criado consiste num tubo de teflon com um suporte para colocao de
membrana. O mdulo inserido na amostra da qual de pretendem extrair os
compostos. No interior do mdulo colocada uma soluo aquosa de recolha,
em contacto com a membrana. O uso de uma membrana hidrofbica microporosa
no permite que exista contacto entre a amostra e a soluo de recolha. Contudo,
os compostos volteis com maior facilidade para se libertarem da amostra podem
ser permeados atravs dos poros da membrana e recolhidos. As vantagens deste
sistema de extraco so: a simplicidade do processo experimental; a utilizao
de uma membrana de dimenses reduzidas e descartvel; a possibilidade de
extraco de compostos volteis a temperaturas reduzidas.
Testou-se a aplicao deste mdulo para a preparao de amostras para
anlise cromatogrfica de acetaldedo em amostras de vinho. O acetaldedo ,
sob o ponto de vista quantitativo, o principal aldedo presente no vinho. Na
indstria de bebidas, importante conhecer as concentraes de acetaldedo, pois
este tem papel central na manifestao da intoxicao alcolica [1]. A
determinao de aldedos pode ser facilmente realizada atravs de um reaco de
derivatizao com a 2,4-dinitrofenilhidrazina, para dar origem a 2,4-
dinitrofinilhidrazonas que podem ser separadas de analisadas por HPLC-UV [2].
A metodologia desenvolvida consiste na extraco de acetaldeido usando o
mdulo de membrana descartvel. O mdulo introduzido na amostra de vinho.
No interior no mdulo coloca-se uma soluo de 2,4-dinitrofenilhidrazina para
promover a derivatizao do acetaldeido recolhido. Esta soluo depois
analisada por HPLC-UV.

[1] D. Bird, Understanding wine technology: The science of wine explained, The Wine
Appreciation Guild, 4 ed., E.U.A., 2005.
[2] K. Fung, D. Grosjean, Anal. Chem 53 (1981) 168.
173


DESENVOLVIMENTO DE UM SISTEMA MULTI-
COMUTADO PARA A DETERMINAO DE SO
2

LIVRE E TOTAL

Sara M. Oliveira*, Teresa I. M. S. Lopes, Ildik V. Tth, Antnio O.
S. S. Rangel
Escola Superior de Biotecnologia, Universidade Catlica Portuguesa, Rua Dr. Antnio
Bernardino de Almeida, 4200-072 Porto, Portugal
*lsoliveira@mail.esb.ucp.pt

A adio de sulfitos como mtodo de preservao dos vinhos tem sido prtica
corrente ao longo dos anos devido s suas propriedades anti-spticas e anti-
oxidantes. O dixido de enxofre pode encontrar-se nos vinhos sob a forma livre
ou combinado.
No entanto, o uso deste composto em excesso confere ao vinho sabor e odor
desagradveis, alm de provocar efeitos indesejveis na sade humana. Por estas
razes tm sido feitos esforos pelas entidades legisladoras de vrios pases no
sentido de diminuir a concentrao deste composto. Actualmente, o mtodo de
referncia de quantificao baseia-se na titulao iodomtrica directa (SO
2
livre)
ou aps hidrlise alcalina (SO
2
combinado). No entanto, este mtodo moroso e
exige elevada participao humana. Torna-se ento necessrio o
desenvolvimento de metodologias fiveis que visem a determinao simples e
rpida deste parmetro.
Neste trabalho, desenvolveu-se um mtodo automtico de fluxo baseado no
conceito de multi-comutao para a determinao espectrofotomtrica de SO
2

livre e total em vinhos. O mtodo baseia-se na adio de cido amostra em
confluncia para converter o sulfito livre em SO
2
, o qual se difunde atravs de
uma membrana hidrofbica colocada numa unidade de difuso de gs. O analito
gasoso reage com o verde de malaquite presente no canal receptor da unidade de
difuso de gs, descolorando-o. O nvel de descolorao, detectado
espectrofotometricamente a 615 nm, relacionado com a concentrao de SO
2

presente na amostra. Para a determinao do SO
2
total, necessrio realizar
previamente uma hidrlise alcalina, de modo a libertar o SO
2
combinado que se
encontra ligado a outras molculas presentes no vinho.
O sistema proposto permite a determinao de concentraes de SO
2
livre e
total num intervalo de concentraes correspondente a 1-40 mg L
-1
e 25-250 mg
L
-1
, respectivamente. Foram obtidos limites de quantificao de 0,6 mg L
-1
para
o SO
2
livre e 5 mg L
-1
para o SO
2
total. O sistema proporcionou a obteno de
ritmos de amostragem de 25 e 29h
-1
para o SO
2
livre e total, respectivamente.

Agradecimentos: Sara Oliveira e Ildik Tth agradecem Fundao para a Cincia e a
Tecnologia (FCT) e FSE (III Quadro Comunitrio) pela atribuio das bolsas
SFRH/BD/23782/2005 e SFRH/BPD/5631/2001, respectivamente.
174


Figure 1. Flow manifold for
methanol determination in
biodiesel
AUTOMATIC FLOW METHODOLOGY FOR METHANOL
DETERMINATION IN BIODIESEL

Andr R. T. S. Araujo
a
*, M. Lcia M. F. S. Saraiva
a
, Jos L. F. C.
Lima
a
, M. Graas A. Korn
b

a
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia da
Universidade do Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
b
Grupo de Pesquisa em Qumica Analtica, Instituto de Qumica, Universidade Federal
da Bahia, Campus de Ondina, 40170-290 Salvador, Bahia, Brasil
*andrearaujo@ff.up.pt

Research in the alternate energy sources field is rising and nowadays the
spotlight is on biodiesel, a promising renewable and alternative diesel fuel to the
conventional one. The quality control of the final product is an important issue
and the European Standard EN 14214 [1] defines
test methods and specifications for quality
parameter assessment. One of these specifications
is the content of methanol whose excess has to be
removed for safety reasons. The maximum
permissible content is 0.2% (m/m) of methanol in
biodiesel. The reference procedure is a gas
chromatography (GC)-based method [2], which
is laborious and time consuming. Then, with the
aim of obtaining a direct, rapid and reliable
determination of methanol content in biodiesel it
was developed an automatic analytical flow methodology. The flow injection
methodology comprises a membrane-based extraction unit which allows the
extraction of the methanol from the biodiesel sample to the aqueous acceptor
solution. The extracted methanol was then determined by the combined use of
immobilised alcohol oxidase, soluble peroxidase and 2,2-azino-bis(3-
ethylbenzothiazoline-6-sulfonic acid) (ABTS). Two dynamic analytical working
ranges were achieved, up to 0.015% and up to 0.200% (m/m) methanol
concentrations. Biodiesel samples from different sources were directly analyzed
without any sample pre-treatment. Statistical evaluation showed good
compliance, for a 95% confidence level, between the results obtained with the
flow system and those furnished by the GC reference method.

Acknowledgments: One of us (A.R.T.S.A.) thanks FCT and FSE for the Ph.D. grant
(SFRH/BD/23029/2005). The authors wish to thank to GRICES (Portugal) and CAPES
(Brazil) for the financial support to the exchange of researches.

[1] European Standard EN 14214, CEN European Committee for Standardization,
Brussels, Belgium, 2003.
[2] Resoluo Agncia Nacional do Petrleo, Gs Natural e Biocombustveis ANP N 42,
Brazil, 2004.
175


Figure 1. Comparison of the
recoveries obtained for triazines with
PDMS and PU normalized to the
polymeric volume.
ADVANCES IN SBSE: NEW POLYURETHANE FOAMS
FOR DETERMINATION OF POLAR POLLUTANTS

Ftima C. M. Portugal*, Moiss L. Pinto, Joo Pires, J. M. F. Nogueira
University of Lisbon, Faculty of Sciences, Chemistry and Biochemistry Department,
Center of Chemistry and Biochemistry, Campo Grande, Ed. C8, 1749-016 Lisboa
*fatimaportugal@fc.ul.pt

Polar organic compounds, such as pharmaceuticals and pesticides, have been
gaining more attention, since some are resistant to degradation during
conventional wastewater treatments,
1
having also high water solubility, and
environmental persistence.
2
Therefore, their monitorization is of great
importance. Stir bar sorptive extraction (SBSE) is a breakthrough technique
developed in the 90s,
3
suitable to monitor several classes of pollutants. This
technique requires low volumes of sample and organic solvents, being easy to
manipulate, and very sensitive. One of its limitations is that the commercial
coating used (polydimethylsiloxane, PDMS) does not have affinity towards the
more polar compounds, difficulting their analysis (e.g. triazines). Therefore, it is
imperative to develop more suitable polymers in order to be able to analyze this
type of compounds by SBSE. In this contribution we propose the application of
polyurethane (PU) foams for SBSE.
The tested formulation showed high
thermal stability till 250-300 C,
excellent resistance to extreme pH
conditions, and to various organic
solvents. The methodologies developed
for the determination of triazines,
pharmaceuticals and steroids in
environmental water and biological
matrices was optimized and validated,
providing remarkable recoveries (2-5
times higher than with PDMS), suitable
detection limits and linear dynamic
ranges, and excellent reproducibility.

Ftima Portugal and Moiss Pinto acknowledge FCT for the PhD (BD/24598/2005) and
Post-Doc (BPD/26559/2006) grants.

[1] J. B. Quintana, I. Rodrguez. Anal Bioanal Chem 384 (2006) 1447.
[2] L. Zarpon, G. Abate, L. dos Santos, J.C. Masini. Analytica Chimica Acta 579 (2006)
81.
[3] E. Baltussen, P. Sandra, F. David, C. Cramers. J. Microcol. Sep. 11 (1999) 737.
176


MICROGRAVIMETRIC QCM AND AFM STUDIES OF
THIN FILMS FOR DNA BIOSENSORS APPLICATIONS

J. F. Borges*, C. M. Pereira, A. F. Silva
CIQ L4, Department of Chemistry, Faculty of Sciences, University of Porto, Rua do
Campo Alegre, 687, 4169-007 Porto, Portugal
*joaofilipeborges@gmail.com

The microgravimetric quartz crystal microbalance (QCM) is a simple, cost
effective, high-resolution mass sensing technique, based upon the piezoelectric
effect [1]. A QCM is an electromechanical transducer that can produce an
electrical signal in response to inertial and viscoelastic changes of a quartz
crystal when a voltage is applied across its faces [2]. The QCM measures the
frequency of oscillation of the crystal and possesses a wide detection range. The
QCM can detect changes in frequency of the crystal due to changes in mass
deposited on the surface of the crystal and the QCM crystal resonance frequency
decreases with an increase in mass on the QCM surface of electrode [3]. The
QCM is a promising candidate for biosensor applications, and its potential for
the detection of DNA has been demonstrated [4]. Atomic force microscopy
(AFM) has various applications for structure characterization of supported films,
for anchoring biomolecules such as DNA and can give information about
regularity of the film [5]. However, in order to understand the effect of
experimental parameters on the surface modification process an imaging
technique is required.
In this work we will present results obtained on the modification of gold
QCM surface with OLA, DNA, and Au NPs. The effect of the experimental
conditions for DNA adsorption and DNA-nanoparticles composite films
deposition will be discussed.

Acknowledgments: The authors are grateful to FCT and FEDER for financial support
under the project POCI/QUI/57679/2004. J. Borges acknowledges the project
POCI/QUI/57679/2004 for a research grant.

[1] A.M. Kenneth, Biomacromolecules 4 (2003) 1099.
[2] R. A. Etchenique, E.J. Calvo, Anal. Chem. 69 (1997) 4833.
[3] G. Sauerbrey, Z. Phys. 155 (1959) 206.
[4] F. Caruso, E. Rodda, D.N. Furlong, K. Niikura, Y. Okahata, Anal. Chem. 69 (1997)
2043.
[5] F. Davis, P. Higson, Biosensors and Bioelectronics 21 (2005) 1.
177


ANLISE DE SISTEMAS COMPLEXOS

J. Costa Pereira, Joana R. Cruz Oliveira
Departamento de Qumica, Faculdade de Cincias e Tecnologia da Universidade de
Coimbra,3004-535 Coimbra
*jcpereira@qui.uc.pt, joana.oliveira@student.qui.uc.pt

A Qumica Analtica o ramo da Qumica que se dedica ao estudo de
materiais e misturas. Sendo os materiais misturas complexas e os respectivos
mtodos analticos pouco especficos, diversas operaes foram desenvolvidas
para tentar ultrapassar estas interferncias (mascarao, isolamento, remoo,
separao, ...). Hoje em dia, tcnicas instrumentais hifenadas permitem realizar
todos os passos do mtodo analtico em contnuo, permitindo efectuar adio de
reagentes, homogeizao, separao, identificao e quantificao. Devido s
suas enormes vantagens em termos de automatizao e sofisticao, estes so em
geral equipamentos de custo elevado.
Com a vulgarizao da informtica e dos computadores portteis, um novo
ramo tem vindo a emergir que consiste em sistemas analticos portteis e de
baixo custo, adequados para realizar anlises in loco, onde os outros
equipamentos no conseguem ainda chegar. Estes sistemas pecam por serem
pouco especficos mas, devido a diversas ferramentas de clculo, que estatsticas
quer Quimiomtricas, conseguem resolver misturas complexas.
A espectrofotometria uma tcnica por excelncia para o estudo e anlise in
loco de misturas relativamente complexas. Sendo esta tcnica utilizada sobre
uma larga janela de frequncias, a interaco sistema-analisador apresenta uma
enorme vantagem no-invasiva - no perturba o sistema e permite sondar a sua
composio e propriedades fsico-qumicas.
Este trabalho exploratrio desenvolve as potencialidades da manipulao
matricial para resolver sistemas de incgnitas. O processo analtico envolve dois
passos: calibrao e quantificao. Na fase inicial de calibrao, so estimados
os coeficientes de extinso molar das espcies qumicas e residual da matriz; na
quantificao so estimadas as concentraes dos analitos nas amostras.
Havendo evidncias para efeito do pH sobre o perfil dos espectros, diferentes
valores de pH foram testados no sentido de encontrar situaes analticas mais
vantajosas em termos de sensibilidade, gama de resposta analtica, limiares
analticos, exactido e preciso, robustez e coerncia.
178


ASSEMBLIES OF GOLD NANOPARTICLES PREPARED
BY USING SUGARS AS REDUCING AGENTS

C. P. Arieira*, C. M. Pereira, A. F. Silva
Department of Chemistry, Faculty of Science, University of Porto,

Rua do Campo Alegre,
687, 4169-007 Porto, Portugal
*carlarieira@gmail.com

The aim of the work is the study of electrodes modified by deposition of gold
nanoparticles for electrochemical sensing. Nanoparticles of gold were prepared
using different reducing sugars, such as glucose, sucrose, sorbitol, manitol and
dulcitol, and stabilized with various ligands such as citrate, lysine and cytosine.
The UV spectra of the Au solution obtained shown in fig. 1 displays a
maximum a 523 nm indicative of the presence of nanoparticles. The invariance
of
maximum
with the sugar reducing agent suggests that the size distribution of the
nanoparticles formed is simila for all sugars. In contrast the intensity of the
maximum points to a higher concentration of nanoparticles when sucrose is used
which suggests that this sugar is the most efficient reducing agent.



Figure 1 UV-vis spectra of solutions
containing gold nanoparticles obtained
using sugars as reducing agents.
Figure 2 voltammetric profile of
reduction/oxidation of a probe [Fe(CN)
6
]
3-/4-

on surface covered with AuNps (----) and in
the absence of AuNPs(----).

AuNPs prepared were deposited on a GC electrode surface and the
voltametric profile of the modified electrode for the oxidation/reduction of
Fe(CN)
6
]
3-/4-
probe is shown in Fig. 2. The redox process becomes more
irreversible in the presence of the AuNPs. The current interpretation of this result
is that it is caused by surface electrostatic repulsions between AuNPs and the
negatively charged probe. Work is in progress to assess this hypothesis.

Acknowledments: Work carried out at CIQ-L4.

[1] A.D. McFarland, C.L. Haynes, C.A. Mirkin, R.P. Van Duyne, H.A. Godwin, J. Chem.
Ed. 81 (2004) 544A.
[2] S. Panigrahi, S. Kundu, S.K. Ghosh, S. Nath, T. Pal, Coll. Surf. A 264 (2005) 133.
Absorvance = f (wavelenght(nm))
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
400 450 500 550 600 650 700
Wavelenght(nm)
A
b
s
o
r
b
a
n
c
e
Glucose
Sorbit ol
Sucrose
Manit ol
Dulcit ol
-1,50E-05
-1,00E-05
-5,00E-06
0,00E+00
5,00E-06
1,00E-05
1,50E-05
-1000 -500 0 500 1000 1500
E / V vs SCE
I

/

A
179


CRITICAL SURVEY ON METHODS FOR IN VITRO
EVALUATION OF ANTIOXIDANT PROPERTIES

Marcela A. Segundo
a
*, Lus M. Magalhes
a,b
, Salette Reis
a
, Jos L. F.
C. Lima
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164,. 4099-030 Porto, Portugal
b
Centre for Rapid and Sustainable Product Development, INDEA (Campus 5), Rua das
Olhalvas, 2414-016 Leiria, Portugal
*msegundo@ff.up.pt

The formation of reactive oxygen species (ROS) and reactive nitrogen
species (RNS) has been clearly implicated in the oxidative deterioration of food
products as well as in the pathogenesis of several human diseases such as
atherosclerosis, diabetes mellitus, chronic inflammation, neurodegenerative
disorders and certain types of cancer [1, 2]. The putative protective effects of
antioxidants against these deleterious oxidative-induced reactions have received
increasing attention lately, especially within biological, medical, nutritional, and
agrochemical fields. This situation demands the existence of simple, convenient,
and reliable in vitro analytical methodologies for the fast determination of
antioxidant capacity of pure compounds or in complex matrices, such as food
and biological samples [3].
In this context, some of the most commonly used methods for in vitro
determination of antioxidant capacity will be critically compared, including the
TEAC (Trolox equivalent antioxidant capacity) assay using ABTS
+
(2,2-
azinobis-(3-ethylbenzothiazoline-6-sulphonate)) and DPPH

(2,2-diphenyl-1-
picrylhydrazyl radical) assay, among others. Several aspects will be focused,
including the following: (i) measurement of the chemistry actually occurring in
potential applications; (ii) utilization of biological relevant molecules; (iii)
technical requirements; (iv) existence of a defined endpoint and chemical
mechanism; (v) existence of readily available instrumentation; (vi) repeatability
and reproducibility; (vii) possibility of assaying of both hydrophilic and
lipophilic antioxidants; (viii) adaptability to high-throughput analysis.

Acknowledgment: This work was financially supported by FCT through project
PTDC/SAL-FCF/67718/2006.

[1] M. Valko, D. Leibfritz, J. Moncol, M.T.D. Cronin, M. Mazur, J. Telser. Int. J.
Biochem. Cell Biol. 39 (2007) 44.
[2] E.N. Frankel, J.B. German. J. Sci. Food Agric. 86 (2006) 1999.
[3] L.M. Magalhes, M.A. Segundo, S. Reis, J.L.F.C. Lima. Anal. Chim. Acta 613 (2008) 1.
180


SISTEMAS DE ANLISE EM FLUXO
COM INTERFACE NICA

Joo L. M. Santos*, C. Silvestre, Jos L. F. C. Lima
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia da Universidade
do Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*joaolms@ff.up.pt

Nas ltimas dcadas assistiu-se ao desenvolvimento de diferentes mtodos de
anlise em fluxo, como a Anlise por Injeco em Fluxo, Anlise por Injeco
Sequencial e os Sistemas de Multicomutao e Multi-impulso. Apesar da sua
diferente configurao, os fundamentos destas tcnicas de fluxo so similares:
insero de um volume definido de amostra num fluxo transportador,
combinao em linha com solues reagentes, e posterior encaminhamento da
zona de reaco, em condies reprodutveis de disperso e temporizao, para o
detector. Independentemente da tcnica de fluxo usada, os volumes de amostra e
reagentes so parmetros fundamentais que requerem uma optimizao
sistematizada, visto que condicionam o estabelecimento da zona de reaco.
Os Sistemas de Anlise em Fluxo com Interface nica (SIFA Single
Interface Flow Analysis) [1] divergem significativamente do conceito tradicional
de anlise em fluxo. Efectivamente, os sistemas SIFA no implicam a insero
de volumes definidos de amostra e reagentes mas o estabelecimento de uma
interface nica de reaco entre a amostra e os reagentes. O desenvolvimento da
reaco fica assim dependente da penetrao de zonas adjacentes
amostra/reagentes e do estabelecimento de gradiente dinmicos de
concentraes. O recurso a mltiplas inverses de fluxo e a utilizao de um
fluxo pulsado so factores que contribuem para aumentar o grau de
interpenetrao obtido. Por outro lado, a localizao do detector no centro da
montagem de fluxo, e no na habitual posio terminal, possibilita a realizao
de multideteces da zona de amostra e a monitorizao contnua do
desenvolvimento da reaco. Estas caractersticas operacionais fazem com que
os sistemas SIFA apresentem um elevado potencial de aplicao, podendo
constituir uma alternativa vantajosa no s aos mtodos discretos mas tambm s
tcnicas de fluxo mais convencionais.

[1] M.F.T. Ribeiro, J.L.M. Santos, J.L.F.C. Lima, A.C.B. Dias, E.A.G. Zagatto, Talanta
68 (2005) 351.
181


DETERMINAO DE IO CLORETO EM VINHOS NUM
SISTEMA DE FLUXO BASEADO EM MULTISERINGA

J. Rodrigo Santos
a
*, Marcela A. Segundo
a
, Jos L. F. C. Lima
a
,
Mauro Korn
b

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
b
NQA, Departamento de Cincias Exatas e da Terra, Universidade do Estado da Bahia,
R. Silveira Martins, 41195-001 Salvador, BA, Brasil
*jrssantos@ff.up.pt

Neste trabalho apresenta-se um sistema automtico baseado em multiseringa,
capaz de pr-condicionar a amostra e realizar sequencialmente quatro adies de
padro. A estratgia adoptada evidencia a comodidade e rapidez de anlise na
realizao do mtodo de adio de padro comummente utilizado em diversas
aplicaes analticas e que moroso e laborioso.
A aplicabilidade da estratgia apresentada foi ensaiada na determinao de
io cloreto em vinhos utilizando um elctrodo tubular selectivo a io cloreto,
cujo processo de construo, orientado para o acoplamento a sistemas de fluxo,
igualmente descrito.
A determinao de io cloreto em vinhos reveste-se de grande interesse uma
vez que a concentrao deste io influi nas propriedades organolpticas desta
bebida. A concentrao de io cloreto em vinhos normalmente inferior a 50 mg
L
-1
, podendo atingir valores da ordem dos 1000 mg L
-1
para vinhas prximas de
zonas litorais. A concentrao deste io depende ainda do processo de fabricao
do vinho, nomeadamente, do uso de aditivos ou de resinas de permuta inica. A
determinao deste io pelo mtodo das adies de padro com elctrodos
selectivos foi referida por diversos autores [1] devido influncia que os
constituintes da matriz do vinho, particularmente o etanol, exercem sobre a
resposta potenciomtrica. A metodologia apresentada pretende ser uma
alternativa vlida quanto a rapidez e custo de anlise, relativamente a outros
mtodos analticos descritos baseados em titulaes potenciomtricas ou em
cromatografia inica.

[1] R. Prez-Olmos, R. Herrero, J. L. F. C. Lima, Journal International des Sciences de la
Vigne et du Vin, 29 (1995) 159.
182


CROMATOGRAFIA INICA DE GUAS DO MAR E DE
OUTRAS SOLUES SALINAS

Natasa Gros
a
, Filomena Cames
b
, Cristina M. R. R. Oliveira
b
*
a
FKKT, Ljubljana University - Slovenia
b
CCMM - DQB - FCUL, Campo Grande, Edifcio C8, 3 piso, 1749-016 Lisboa, Portugal
*cristina.oliveira@fc.ul.pt

O facto de mais de 70% da superfcie terrestre se encontrar coberta por gua
do mar tem levado o Homem a interessar-se pelas suas propriedades,
nomeadamente a variedade e quantidade de sais dissolvidos que, por evaporao
da gua sob a aco do vento e do Sol, constituem importante recurso
econmico. Um quilograma de gua do mar contm, em mdia, cerca de 35 g de
sais. No passado foi assumida proporcionalidade constante entre os ies
maioritrios presentes na gua do mar, a partir do que foi desenvolvida a
primeira equao emprica relacionando salinidade e clorinidade, que era a base
das medies prticas de salinidade, por titulimetria argentomtrica. Actualmente
vigora uma escala prtica de salinidade, PSU, na qual a salinidade expressa
mediante determinao experimental de condutividade elctria. Os salinmetros
so calibrados com uma gua do mar certificada quanto clorinidade. Uma gua
do mar padro de salinidade prtica 35 tem, por definio, uma razo de
condutividade igual a 1, relativamente a uma soluo de KCl contendo 32.4356g
KCl em 1kg de soluo, a 15 C. Consequncia das variaes climticas e de
fenmenos de poluio, as guas do mar vm sofrendo variaes considerveis
na sua composio, surgindo um elevado nmero de situaes em que, o que era
assumido como estabelecido, necessita ser revisto. Neste trabalho procedeu-se
optimizao de uma metodologia prtica para determinar, por cromatografia
inica, a composio aninica e catinica, simultaneamente das espcies
maioritrias e minoritrias presentes em guas do mar e em outras solues
salinas, sendo apresentada uma seleco criteriosa de valores.
183


MULTI-PUMPING FLOW SYSTEM FOR
PHENYLGLYOXYLIC ACID DETERMINATION IN URINE

Karine L. Marques*, Joo L. M. Santos, Jos L. F. C. Lima
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*karine.marques@ff.up.pt

Styrene is one of the most important plastic monomers, widely used in the
production of fibreglass reinforced polyester products. Exposure to styrene
causes toxic effects including alterations in the central and peripheral nervous
systems and irritations to the skin and respiratory tract. Phenylglyoxylic acid
(PGA) and mandelic acid are the major urine metabolites of styrene in human,
which hence are used as biological indicators of occupational exposure to styrene
[1]. Most of the methodologies available for PGA determination are based in
liquid or gas chromatographic procedures which are laborious and time
consuming [2, 3].
The aim of this work was to develop a simple and automated flow
methodology for the determination of PGA in urine samples, based on the
reaction H
2
O
2
with ammonium metavanadate in acidic medium, which results in
the formation of a red-orange color peroxovanadium cation, with maximum
absorbance at 443 nm. The presence of PGA leads to a decrease in the
absorbance by consumption of vanadate.
The developed flow method was based on a multi-pumping flow system

(MPFS) that employs, as exclusive active components, multiple solenoid
actuated micro-pumps that were simultaneously accountable for solutions
insertion, propelling and commutation, assuring an easily controlled and compact
analytical system characterised by high simplicity and versatility [4].
Moreover, MPFS allow the synchronization of the reagent additions to a
precise sample portion establishing a well-defined reaction zone, which in
combination with an improved mixing efficiency provided by the characteristic
pulsed flow, enables the lessening of sample and reagent consumption and
reduces the volume of generated wastes.

Ackowledgements: The authors are grateful to FCT and FSE (III Quadro Comunitrio de
Apoio) for financial support. K.L.M. thanks FCT for a postdoctoral grant.

[1] S.J. Sumner, T.R. Fennell. Crit. Rev. Toxicol. 24 (1994) S11.
[2] J.Z. Wang, X.J. Wang, Y.H. Tang, S.J. Shen, Y.X. Jin, S. Zeng. J. Chromatogr. B 840
(2006) 50.
[3] S. Szcs, L. Tth, J. Legoza, A. Srvry, R. dny. Arch. Toxicol. 76 (2006) 560.
[4] R.A.S. Lapa, J.L.F.C. Lima, B.F. Reis, J.L.M. Santos, E.A.G. Zagatto. Anal. Chim.
Acta 466 (2002) 125.
184


SENSOR FOR AMPEROMETRIC DETERMINATION OF
AMMONIA IN SEAWATER

C. Peixe
a,b
*, C. M. Pereira
a
, F. Silva
a
, M-T Borges
b,c

a
Department of Chemistry, Faculty of Science, University of Porto, R. Campo Alegre,
687, 4169-007 Porto, Portugal
b
Ciimar-University of Porto; Rua dos Bragas 289, 4050-123 Porto, Portugal.
c
Faculty of Sciences (Zoology-Anthropology Dep.)-University of Porto; Praa Gomes
Teixeira, 4099-002 Porto, Portugal.
*carlapeixe@gmail.com

The determination of ammonia in environmental samples is very important
and there is the need for alternative methods that allow a rapid, easy and low-
cost determination for ammonia. Amperometric methods are good candidates to
fulfill all these requirements.
Recently some works report the use of enzyme sensors for ammonia
determination [1].
The use of composite electrodes containing Nafion, polyaniline (Pan) and an
enzyme cocktail showed to be effective for
ammonia determination [2, 3].
In this work, platinum electrodes modified
with a (PAn) layer were used for the ammonia
determination. The electrolyte solution
consisted of a pH 10 buffer solution to which
different amounts of 50mM ammonium sulfate,
were added.
Figure 1 shows the cyclic voltammograms
obtained. In the presence of NH
4
+
a peak at
1300 mV is observed and the peak current
increases with increase of NH
4
+
concentrations.

Acknowledgements: CIIMAR for the project EC-CRAFT/016869/2006, Raceways A
Hypertensive fish farming concept for lasting competitiveness and superior production.

[1] B. Strehlitz, B. Grundig, H. Kopinke. Analytica Chimica Acta 403 (2000) 11.
[2] W. Cho, H. Huang, Anal. Chem. 70 (1998) 3946.
[3] H. Kotte, B. Grundig, K. Vorlop, B. Strehiltz, U. Stottmeister Anal. Chem. 67 (1995)
65.
Fig. 1 CVs of the modified
electrode in an aqueous buffer
pH 10 with different amounts of
(NH
4
)
2
SO
4

-400 -200 0 200 400 600 800 1000 1200 1400 1600
-1.5x10
-5
-1.0x10
-5
-5.0x10
-6
0.0
5.0x10
-6
1.0x10
-5
1.5x10
-5
2.0x10
-5
2.5x10
-5 Buffer solu. pH 10.10
Buffer sol. + 17.28mg/L (NH4)2SO4
Buffer sol. +25.77mg/L (NH4)2SO4
Buffer sol. + 34.15mg/L (NH4)2SO4
I / A
E /mV
185


ELECTRONIC TONGUE FOR QUALITATIVE AND
QUANTITATIVE ANALYSIS OF DRINKS

Jlia M. C. S. Magalhes*, Claudia Silva, Adlio A. S. C. Machado
LAQUIPAI, Department of Chemistry, Faculdade de Cincias da Universidade do Porto,
R. Campo Alegre n 687, 4169-007Porto, Portugal
*jmmagalh@fc.up.pt

Electronic tongues (E-Tongue), chip sensors and taste sensors [1 and
references there in] are devices inspired on the human sense of taste, and
constitute a new generation of analytical instruments based on arrays of chemical
sensors and pattern recognition and/or multivariate analysis methods for data
processing. These devices are intended to provide a fast tool for the analysis of
samples of complex composition and usually are used for qualitative analysis.
An electronic tongue constituted by all-solid-state ion selective electrodes,
including both selective (sodium, potassium, calcium and hydrogen) and
partially selective electrodes, based on crown ethers (dibenzo-18-crown-6 and
benzo-18-crown-6), was assembled and tested for the classification of non
alcoholic drinks, specifically nectars, ice tea, tonic water, sparkling, still and
added flavour mineral waters. PCA models for each class of samples were built
and the capability of the E-Tongue to classify the samples was tested using data
obtained in independent experiments. The results obtained showed that almost all
samples were correctly classified. Furthermore, based on the nominal
concentration in the labels of the mineral water samples, PCR calibration models
were built and tested (see Table 1) for the determination of pH, sodium and the
concentration of calcium and magnesium in the samples.

Table 1. Error analysis for the PCR prediction of the composition of mineral water samples.

pH Na
+
Ca
2+
+ Mg
2+

SEP 0.05 0.043 0.071
r 0.9925 0.9992 0.9991
Slope 1.011 1.018 0937
Intercept -0.054 0.067 -0.219

Acknowledgements: This work is part of a project: POCI/QUI/58076/2004 from Fundao
para a Cincia e Tecnologa. Finantial support is gratefully acknowledged.

[1] P. Ciosek, W. Wrblewski, Analyst, 132 (2007) 963.
186


DETERMINATION OF VANADIUM (V) IN WATER
SAMPLES BY SEQUENTIAL INJECTION ANALYSIS

Eliana S. Silva, Paula C. A. G. Pinto*, M. Lcia M. F. S. Saraiva,
Jos L. F. C. Lima
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia, Universidade
do Porto, Rua Anbal Cunha, 164, 4050-047, Porto, Portugal
*ppinto@ff.up.pt

Vanadium is widely distributed in the earths crust but in low abundance. At
trace amounts represents an essential element for normal cell growth, but can be
toxic when present at higher concentration [1]. The toxicity of vanadium is
dependent on its oxidation state [2], so that vanadium (V) is more toxic than
vanadium (IV). Large amounts of vanadium are release into the environment by
anthropogenic sources, mainly by burning of fossil fuels such as crude oil,
certain types of coal and lignite. Further, vanadium is widely used in industrial
processes including the production of special steels, temperature-resistant alloys,
in glass industry, in the manufacture of pigments and paints and as catalyst [3].
Thus, these activities release large quantities of vanadium into the environment
contributing to water pollution. All these factors justify the increase concern in
monitoring vanadium concentrations in water samples.
Automatic flow methodologies have been employed in the field of
environmental quality monitoring in the last decades. Sequential injection
analysis (SIA) was introduced in 1990 by J. Ruzicka et al. [4] as an evolution of
the flow injection analysis technique (FIA). SIA systems are a powerful and
versatile sample handling approach which enables automation analysis with
relatively simple instrumentation. It provides robustness, sample and reagents
economy and reduced residues production allowing the development of greener
analytical methodologies.
In the present work a SIA methodology for the determination of vanadium
(V) in water samples with spectrophotometric detection was developed. The
chemical reaction was based on the oxidation of dopamine (DPH) by vanadium
(V) in acidic medium and coupling with 4-aminoantipyrine (4-AAP) to yield a
violet product detected at 565 nm.
The analytical cycle begin with the sequential aspiration of 300 l of sample,
125 l of DPH and 125 l of 4-AAP into the holding coil. Then the flow was
reversed and the product was send to the detector. The developed methodology
allows the determination of vanadium (V) between 0.50 and 5.0 mg L
-1
, with a
sampling rate of 10 samples per hour, with a detection limit of 0.39 mg L
-1
.

[1] F. H. Nielsen, Clin. Biochem. Nutr. Aspects Trace Elem. 6 (1982) 379.
[2] B. Patel, G. E. Henderson, S. J. Haswell, R. Grzeskowiak, Analyst 115 (1990) 1063.
[3] K. Pyrzyska, Microchim Acta 149 (2005) 159.
[4] J. Ruzicka, G. D. Marshall, Anal. Chim. Acta 237 (1990) 329.
187


SISTEMAS DE FLUXO CONTNUO BASEADOS EM
NOVOS CONCEITOS DE GESTO DE FLUDOS

Marta F. T. Ribeiro*, Joo L. M. Santos, Jos L. F. C. Lima
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia, Universidade
do Porto, R. Anbal Cunha 164, 4099-030 Porto
*marta.ribeiro@ff.up.pt

Nos ltimos anos assistiu-se ao desenvolvimento de novas estratgias de
gesto de fluidos em fluxo contnuo, como a anlise por injeco em fluxo (FIA),
a anlise por injeco sequencial (SIA), a multicomutao (MCFA) e a multi-
seringa (MSFA), que ao permitirem a implementao de sistemas qumicos de
complexidade variada e tambm o acoplamento de diferentes tipos de detectores,
tm sido utilizadas como suporte de desenvolvimento de novas metodologias.
Estruturadas de uma forma diversificada, estas tcnicas so no entanto
baseadas na utilizao de equipamentos com funes semelhantes,
nomeadamente um sistema de propulso (bomba peristltica, de pisto, seringa,
etc), um sistema de injeco de amostra (vlvula rotativa, solenide, selectora
multi-posio, etc) e um sistema de deteco (espectrofotmetro, fluormetro,
etc). Apesar da sua diferente configurao, os fundamentos so tambm
similares, sendo baseados na preciso na introduo da amostra, na sua disperso
controlada, e no tempo e movimento repetvel desde o ponto de introduo at ao
sistema de deteco.
Neste trabalho so apresentados dois novos conceitos de gesto de fluidos em
fluxo contnuo, a Multi-impulso [1] e a Reaco em Interface nica [2]. A
anlise em sistemas de fluxo multi-impulso distingue-se das estratgias
anteriores por ser baseada num fluxo com caractersticas hidrodinmicas
distintas (fluxo pulsado) e por na concepo e estabelecimento das montagens
no requerer mais do que um tipo de elemento activo (micro-bomba solenide) o
qual poder ser responsvel, em simultneo, pela propulso, insero e
comutao das solues, enquanto que a anlise em sistemas de fluxo de
interface nica se diferencia, ao no implicar a insero de volumes definidos de
amostra e reagentes nas montagens, mas o estabelecimento de uma interface
nica de reaco entre a amostra e os reagentes antes da deteco.

Agradecimentos: M.F.T.R. agradece FCT/FSE (III QCA) a Bolsa de Doutoramento
SFRH/BD/10400/2002.

[1] R.A.S. Lapa, J.L.F.C. Lima, B.F. Reis, J.L.M. Santos, E.A.G. Zagatto, Anal. Chim.
Acta 466 (2002) 125.
[2] M.F.T. Ribeiro, J.L.M. Santos, J.L.F.C. Lima, A.C.B. Dias, E.A.G. Zagatto, Talanta
68 (2005) 351.
188


DETERMINAO DE METAIS PESADOS EM
COSMTICOS

Manuel Matos*, Sofia P. M. Gonalves, Susana I. E. Silva, Nelson A.
F. Silva, Hugo F. A. Silva
ISEL-DEQ, R. Cons. Emido Navarro, 1, 1959-007 Lisboa
*mmatos@deq.isel.ipl.pt

A utilizao de pinturas faciais, nomeadamente nos olhos, remonta aos
primrdios da existncia humana. Uma das primeiras sombras conhecidas foi o
minrio verde malaquite Cu
2
CO
3
(OH)
2
usado desde o ano 5000 aC. As mulheres
egpcias usavam trisulfureto de antimnio (Sb
2
S
3
) modo para escurecerem os
seus olhos [1]. Nos pases rabes e em frica ainda comum o uso de kohl ou
surma, uma perigosa sombra para olhos em cuja composio predominante o
sulfureto de chumbo [2]. Por seu lado, em Portugal assiste-se sem controlo
oficial, comercializao de uma profuso de produtos de origem no extremo
oriente, entre eles os cosmticos.
Neste trabalho procedeu-se
anlise de chumbo, cdmio,
nquel e crmio em diversas
amostras de cosmticos de
diversas origens e diversos tipos.
As amostras foram digeridas em
meio cido atravs de digesto assistida por microondas ou por calcinao
seguida de solubilizao em meio cido. Este segundo procedimento foi utilizado
em amostras com um elevado teor de gordura como os batons. As anlises foram
realizadas num espectrmetro de absoro atmica com cmara de grafite.
Usaram-se padres Merck Certipur para aferio dos resultados e os cidos
utilizados nas digestes foram Merck Suprapur. Os procedimentos analticos
foram realizados de acordo com as boas prticas da anlise qumica.
Os resultados so resumidos qualitativamente na tabela 1 e mostram a
presena de chumbo em todos os produtos analisados. Os maiores teores
encontrados referem-se ao crmio, com um valor mximo detectado de 293
mg/kg. O valor mximo detectado para o nquel observou-se em sombras com
199 mg/kg. Este um valor preocupante atendendo ao alargado espectro
alergnico deste metal e ao local particularmente sensvel (plpebra) onde estes
produtos so aplicados. O desenvolvimento de tcnicas analticas para a anlise
rotineira destes produtos mostra-se assim necessria para garantia da sade
pblica, embora seja dificultado pela variedade e secretismo da composio dos
cosmticos [3].

[1] T. Mitsui, New Cosmetic Science, Elsevier Science BV, Amesterdo, 1997.
[2] R.M. Al-Ashban, M. Aslam, A.H. Shah. Public Health., 118 (2004) 292.
[3] A.D. Hardy, R.I. Walton, K.A. Myers, R. Vaishnav. J Cosmet Sci.; 57 (2006) 107.
Tabela 1. Resultados qualitativos.
Chumbo Cdmio Nquel Crmio
Sombra ++ + ++++ ++++
Blush + + + ++
Batom + +
Rmel + + ++
Bronzeador + +
189


PRODUO DE PADRES PARA ANLISE DE METAIS
PESADOS EM AEROSSIS

Pro M. P. Pedroso
a
, Hugo F. A. Silva
b
, Sandrina Oliveira
b
, Paula
Cantinho
b
, Cristina Oliveira
a
, Filomena Cames
a
, Manuel Matos
b
*
a
FCUL-DEQB, Campo Grande, 1749-016 Lisboa
b
ISEL-DEQ, R. Cons. Emido Navarro, 1, 1959-007 Lisboa
*mmatos@deq.isel.ipl.pt

A presena de aerossis na atmosfera, nomeadamente em ambiente urbano,
um factor de grande influncia para a sade pblica, para o clima e mesmo para a
visibilidade [1]. Conhecer a composio destes aerossis um factor
determinante para o estabelecimento de relaes entre as fontes emissoras e
qualidade do ar bem como para a adequao de medidas de minimizao e
proteco das populaes. Neste contexto o nosso grupo de investigao
desenvolve metodologias de anlise de aerossis visando a sua caracterizao,
nomeadamente o seu teor em metais pesados. A anlise de metais pesados em
aerossis pode ser realizada por digesto dos filtros em meio cido seguida de
determinao dos metais atravs de espectroscopia de absoro atmica. O
procedimento de digesto realizado atravs de processo clssico ou utilizando
processos de acelerao como a extraco assistida por microondas. Novos
procedimentos, nomeadamente os processos de produo de padres de controlo
e o processo acelerado de digesto, necessitam de ser validados para se efectuar
anlises de rotina. A validao poderia socorrer-se de padres certificados [2],
como por exemplo o SRM-2783 (Air Particulate on Filter) do NIST mas o seu
preo elevado o grande inconveniente para uso frequente.
Neste trabalho ensaiou-se contaminao de filtros de papel Whatman n. 41
de 47 mm de dimetro, habitualmente usados na recolha de aerossis, com
solues de Pb, Cd, Cu, Cr e Ni a nvel dos ppb. Estes so metais geralmente
presentes em aerossis urbanos sendo bem conhecidos os seus efeitos
prejudiciais na sade humana. Os filtros foram contaminados com solues
padro produzidas a partir de padres Certipur da Merck. Todo o material foi
sujeito a descontaminao prvia utilizando cidos Suprapur da Merck, cidos
com os quais tambm se realizou a digesto acelerada dos filtros atravs de
microondas. Os teores de metais foram determinados por espectroscopia de
absoro atmica com cmara de grafite (GFAAS). Utilizou-se o mtodo da
recta de calibrao com controlo de qualidade e validao da mesma realizado
atravs de padres de controlo. Os resultados obtidos mostram uma recuperao
mdia de 97 %, validando a aplicabilidade deste procedimento sequencial de
contaminao e digesto para a produo de padres de filtros contaminados
com teores vestigiais de metais.

[1] C.A. Pope, D.W. Dockery, J. Air Waste Manage. Assoc. 56 (2006) 709.
[2] P. Kulkarni, S. Chellam, J. B. Flanagan, R.K.M. Jayanty, Anal. Chim. Acta 599
(2007) 170.
190


DEVELOPMENT OF A HPLC-DAD METHODOLOGY FOR
ANTIBIOTICS SCREENING IN WASTEWATERS

Salom Teixeira
a,b
*, Cristina Delerue-Matos
a
, Arminda Alves
b
,
Lcia
Santos
b

a
REQUIMTE, Departamento de Engenharia Qumica, Instituto Superior de Engenharia
do Porto, Rua Dr. Antnio Bernardino de Almeida 431, 4200-072 Porto, Portugal

b
LEP, Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade
do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*dce06015@fe.up.pt

Pharmaceutical and personal care products (PPCPs) are a diverse group of
chemicals used in veterinary medicine, agriculture practices, human health and
cosmetic care. Due to their continuous introduction into the environment,
biological effect and physico-chemical behaviour the PPCPs are considered a
class of new, so-called emerging contaminants that have raised great concern in
recent years [1]. Antibiotics are among the most frequently detected
pharmaceutical compounds in environmental waters [2]. These compounds have
been widely used in human and veterinarian medicine, as well as in industrial
farming. Although some antibiotics may be significantly metabolized, many are
largely excreted intact. Even those with short half-lives may be of concern,
because they are continually released to the aquatic environment. As a
consequence, residues may be present in the environment for long periods,
promoting the appearance of antimicrobial resistant bacteria [3,4]. These
concerns have led to the need for fast, but sensitive, methods of analysis. A
simple analytical methodology for the simultaneous analysis of five antibiotics
(Amoxicillin, Metronidazole, Cefazolin, Sulfamethoxazole and Chlorampenicol)
in municipal wastewaters by HPLC-DAD is presented in this study. The
developed method enables the fast screening of a large number of samples, with
a total analysis time of 35 minutes and detection limits in the range of 3 - 14 g
L
-1
. The measurement of the method global uncertainty was evaluated by using a
bottom-up approach. The expanded relative uncertainty for the method was in the
range of 1-22% for all compounds.

[1] D. Barcel, M. Petrovic. Anal. Bional. Chem. 387 (2007) 1141.
[2] A. Nikolaou, S. Meric, D. Fatta. Anal. Bional. Chem. 387 (2007) 1225.
[3] A. Iversen, I. Khn, A. Franklin, R. Mllby, Appl. Environ. Microbiol. 68 (2002)
2838.
[4] K. Kmmerer, A. Henninger. Clin. Microbiol. Infect. 9 (2003) 1203.
191


DETERMINAO DA DISTNCIA DE DISPARO DE
ARMAS DE FOGO ATRAVS DA ANLISE DOS
RESDUOS NA SUPERFCIE DE IMPACTO

Joana M. F. Tuna
a
, Agostinho A. Almeida
a
*, Agostinho J. C. Santos
b
,
Teresa M. S. Magalhes
b
, Marisa C. F. Silva
a
, Snia M. Martins
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha 164, 4050-047, Porto, Portugal.
b
Instituto de Medicina Legal, Faculdade de Medicina da Universidade do Porto,
Portugal. Instituto Nacional de Medicina Legal, I.P. Delegao do Norte. Jardim
Carrilho Videira, 4050-167 Porto, Portugal.
*aalmeida@ff.up.pt

A determinao da distncia de disparo de grande importncia no contexto
das percias relativas a incidentes com armas de fogo, uma vez que pode
contribuir decisivamente para distinguir entre um simples acidente, um suicdio
ou um homicdio [1]. Uma das principais evidncias nestes casos a presena de
resduos (gunshot residues GSR) na superfcie de impacto, em redor do orifcio
de entrada do projctil. Estes GSR so essencialmente partculas resultantes da
condensao de vapores do primer que foram conjuntamente transportadas
com o projctil para a superfcie de impacto. No que respeita a elementos
metlicos, contm sobretudo chumbo (Pb), antimnio (Sb) e brio (Ba).
Numa perspectiva balstica, compreende-se que a quantidade (a densidade do
depsito) e o padro de distribuio dos GSR estejam de algum modo
relacionados com a distncia a que o disparo foi efectuado. Na sequncia de
trabalho anterior efectuado com uma pistola de calibre 6.35 mm [2], a arma de
fogo mais frequentemente envolvida em incidentes em Portugal, estudo idntico
foi agora efectuado com uma pistola de calibre 7.65 mm, um tipo de arma
tambm muito frequentemente usado em Portugal. Foram feitos disparos (n=5) a
diferentes distncias (entre 20 e 90 cm, a intervalos de 10 cm) contra um tecido
de algodo. Depois, usando uma metodologia analtica baseada na tcnica de
Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) foi determinada a
quantidade de Pb, Sb e Ba depositada em pequenos fragmentos quadrangulares
(1x1 cm) cortados no tecido-alvo em 4 posies radiais relativamente ao orifcio
de entrada do projctil. Os dados obtidos permitiram estabelecer um modelo
(regresso linear mltipla) que relaciona a distncia de disparo e o teor de metal.

[1] V.J.M. DiMaio, Gunshot Wounds: Practical Aspects of Firearms, Ballistics, and
Forensic Techniques, CRC Press, Boca Raton, 1999.
[2] A. Santos, T. Magalhes, D.N. Vieira, A.A. Almeida, A.V. Sousa. Am. J. Forensic
Med. Pathol 28 (2007) 24.
192


RUBDIO VS POTSSIO NO HUMOR VTREO COMO
PARMETRO ANALTICO PARA ESTIMAR O TEMPO
DECORRIDO APS A MORTE

Catarina A. S. Chaves
a
, Agostinho A. Almeida
a
*, M. Helena A. T.
Andrade
a
, Agostinho J. C. Santos
b
, Teresa M. S. Magalhes
b
, Sofia
M. L. M. Frazo
b
, Daniela P. Monteiro
a
, Susana F. Cruz
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha 164, 4050-047, Porto, Portugal.
b
Instituto de Medicina Legal, Faculdade de Medicina da Universidade do Porto,
Portugal. Instituto Nacional de Medicina Legal, I.P. Delegao do Norte. Jardim
Carrilho Videira, 4050-167 Porto, Portugal.
*aalmeida@ff.up.pt

A estimativa do intervalo de tempo decorrido aps a morte de um indivduo
(postmortem interval PMI) uma das mais importantes tarefas no mbito das
percias forenses e mdico-legais [1]. A maioria dos mtodos habitualmente
usados recorre a algoritmos baseados na temperatura corporal e apresenta uma
considervel inexactido [2].
No decurso das ltimas dcadas foram propostos vrios mtodos para estimar
o PMI com base na alterao da concentrao de parmetros bioqumicos dos
fluidos corporais. Neste contexto, o aumento da concentrao de potssio no
humor vtreo (HV) alterao mais bem estudada e vrias frmulas tm sido
propostas para estimar o PMI com base no mesmo [3]. Contudo, a concentrao
de potssio no HV pode ser afectada por outros factores para alm do tempo
decorrido aps a morte (e.g., a causa da morte, distrbios electrolticos prvios,
etc.), circunstncias em que a exactido da estimativa do PMI fica tambm
afectada.
Usando uma metodologia analtica baseada na tcnica de Inductively Coupled
Plasma-Mass Spectrometry (ICP-MS) foi estudada a alterao da concentrao
de diversos elementos vestigiais (Ag, Al, As, Sb, Cr, Ba, Be, Co, Cu, Cs, Cd,
Mo, Mn, Ni, Li, Fe, Sr, Pb, Rb, Tl, V, Zn, Si, I and Ti) em amostras de HV
colhidas a diferentes intervalos de tempo aps a morte (3-30 h). Alguns dos
elementos estudados mostraram-se promissores relativamente ao objectivo de
ajudar a estimar o PMI com maior fiabilidade. Em particular, o rubdio mostrou
uma tendncia para um aumento consistente, com uma melhor correlao com o
PMI que o potssio, pelo que poder constituir uma alternativa vantajosa.

[1] C. Henssge, B. Madea. Forensic Sci. Int. 165 (2007) 182.
[2] K.L. McDowall, D.V. Lenihan, A. Busuttil, M.A. Glasby. Forensic Sci. Int. 91 (1998)
163.
[3] B. Madea. Forensic Sci. Int. 151 (2005) 139.
193


IRON (II) OPTRODE BASED ON THIONINE
IMMOBILIZED ON A SOL-GEL NET

Joana A. E. Carvalhido*, Alberto N. Arajo, M. Conceio B. S. M.
Montenegro
REQUIMTE, Dep. Qumica-Fsica, Fac Farmcia (U.P) Rua Anbal Cunha 164, 4099-
030 Porto, Portugal
*joanaecarvalhido@gmail.com

Optrodes developed using sol-gel technology are emergent. The mild
conditions of the process, together with the chemical inertia of sol-gel glass,
make these materials ideal for the immobilization of numerous organic,
organometallic and biological molecules. Important advantages of using sol-gel
silica nets resides on how characteristics such as polarity, porosity and ion
exchange capacity can be easily tailored by simple modification of the
polymerisation protocols work the development and evaluation of distal type
iron(II) optrode is described. A sol-gel film containing thionine acetate as
analyte sensitive element was casted by spin coating over a 18 mm square soda
lime glass substrate where surface silanol groups were previously activated. In
acidic medium iron (II) discolours thionine in the presence of light, according the
reversible reaction:

Thio + 2 Fe
2+
+ 2H
+
Thio H
2

+
+ 2Fe
3+
purple incolor

For a particular light intensity and settled acidic conditions the speed of
reaction is dependent of the iron(II) concentration and selective complexing
agents of the iron(III) formed, but can be easily monitored at the wavelength of
596 nm (Fig. 1). Optimal conditions for sol-
gel film were obtained after mixing 2 mL of
ethanol, 0.5 mL of tetraethoxysilane, 213 L
of 0.01 mol/L HCl and 2 mg of thionine for
six hours. From this solution, 100 L are
finnaly spin coated at 2500 rpm during 30 s
over a glass substrate and left to dry over a 5
days period. A flow-through system was
coupled to provide pH adjust of all solutions.
The optrode was applied in monitoring of
iron (II) in waters revealing good performance
characteristics.

Acknowledgments: One of us J.C. acknowledge to FCT for the grant
(SFRH/BD/25992/2005)
0.04
0.08
0.12
0.16
0.20
0 1.5 2.5 3.5 4.5
AAbs/min
mg/L
Fig 1 - Change of thionine
absorption with iron(II)
concentration
194


MTODO MULTIRESDUO PARA ANLISE DE
PESTICIDAS AGRCOLAS EM GUAS POR EXTRACO
EM FASE SLIDA COM DETECO POR GC-MS

Jos Lus Moreira
b
, Maria de Ftima Ferreira
b
, Serafim Pereira
b
,
Arminda Alves
a
*
a
LEPAE, Laboratrio de Engenharia de Processos, Ambiente e Energia
b
Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do
Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto
*aalves@fe.up.pt

A Directiva-Filha (2006/0129/CE) fixa as normas de qualidade ambiental
aplicveis a substncias prioritrias no domnio da poltica da gua.
Relativamente aos pesticidas aplicados na agricultura, esto definidas as
seguintes concentraes mximas para guas de superfcie, apenas para a
atrazina 2 g/L e para o diuro 1,8 g/L.
Neste trabalho foi validado um mtodo multiresduo para anlise simultnea
de 12 pesticidas agrcolas em guas. O procedimento de extraco envolve a
extraco em fase slida com colunas Envi 18 da Supelco, acondicionadas com
diclorometano, metanol e gua. O volume de amostra foi 250 mL e o solvente de
eluio o diclorometano. O extracto, depois de seco em corrente de azoto foi
retomado em etanol. A determinao cromatogrfica realizou-se num GC/MS
4000 da Varian, equipado com coluna DB-5MS da J&W Scientific (30m x
0,25mm ID x 0,25 um filme). A identificao dos compostos realizou-se em
modo Full Scan. A quantificao realizou-se atravs de rectas de calibrao
construidas com padres extrados nas mesmas condies que as amostras. A
Tabela 1 apresenta as principais caractersticas do mtodo analtico, nas
condies optimizadas. Na gama de linearidade, o mtodo revelou-se adequado
aos objectivos.
Tabela 1. Pesticidas agrcolas analisados e principais caractersticas
Nome
Gama de
linearidade
(g/L)
Limite de
deteco
(g/L)
Tempo de
reteno
(min)
Ies
EPTC 10-100 10,0 10.394 128.0, 132.0, 86.0
Desetilatrazina 20-100 20,0 16.280 172.1, 187.1, 429.2
Desetilterbutilazina 1-100 1,0 16.641 186.2, 188.2, 145.2
Atrazina 1-100 1,0 18.153 200.2, 215.2, 216.2
Terbutilazina 0,2-100 0,2 18.694 214.2, 173.2, 216.2
Metalaxil 20-100 20,0 21.031 188.3, 160.3, 238.2
Alacloro 0,2-100 0,2 22.033 160.2, 188.2, 189.2
Linurao 10-100 10,0 22.170 61.2, 160.2, 149.2
S-Metolacloro 0,2-100 0,2 22.479 162.2, 238.2, 163.2
Pendimetalina 0,2-100 0,2 23.803 252.2, 162.2, 191.1
Captana 10-100 10,0 24.535 79.1, 77.1, 107.2
Metidatiao 0,2-100 0,2 24.980 145.2, 85.1, 125.2

195


CARACTERIZAO DOS LENHOSULFONATOS
OBTIDOS A PARTIR DO LICOR DE COZIMENTO AO
SULFITO CIDO DO EUCALYPTUS GLOBULUS

Ana P. S. Marques
a
*, D. V. Evtuguin
a
, A. Prates
b

a
CICECO/Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro
b
CAIMA Indstria de Celulose S.A., Constncia-Sul, 2250-058 Constncia
*apsm@ua.pt

Quando a lenhina da madeira tratada com sais de sulfito ou bissulfito a
temperaturas elevadas (130 170C) ocorre a formao de produtos designados
por cidos lenhosulfnicos ou lenhosulfonatos. Na indstria da pasta e do papel
os lenhosulfonatos so separados da pasta celulsica aps cozimento ao sulfito e
queimados com vista regenerao da base e recuperao de energia. Os
lenhosulfonatos obtidos a partir da madeira do Eucalyptus globulus nunca foram
estudados antes e esto disponveis em Portugal desde que foram produzidos
pela CAIMA Indstria de Celulose S.A., representando uma fonte renovvel
promissora para a produo de produtos de valor acrescentado.
O objectivo principal deste trabalho de investigao foi estudar a composio
qumica e a estrutura dos lenhosulfonatos purificados obtidos a partir do licor de
cozimento ao sulfito cido do Eucalyptus globulus. Este trabalho relevante uma
vez que visa contribuir para o desenvolvimento avanado da
educao/investigao no domnio da caracterizao de materiais polimricos,
assim como, para a criao de uma plataforma tecnolgica integrada que envolve
a indstria portuguesa (CAIMA Indstria de Celulose S.A. - grupo ALTRI) e
instituies acadmicas (CICECO/Universidade de Aveiro).
O licor fino foi fornecido pela CAIMA Indstria de Celulose S.A., tendo
sido, posteriormente, purificado por dilise (isolamento de lenhosulfonatos). O
licor purificado foi analisado em termos do teor de lenhosulfonatos, teor de
cinzas, teor e tipo de acares residuais. Os lenhosulfonatos foram, por sua vez,
analisados em funo dos grupos funcionais, peso molecular, comportamento
trmico e estrutura qumica.
A purificao dos lenhosulfonatos implica uma diminuio do teor de cinzas
(~ 3,5 vezes) e do teor dos grupos sulfnicos (~ 1,7 vezes). A quantidade de
polissacardeos diminui cerca de 4 vezes com a purificao dos lenhosulfonatos,
sendo a percentagem de pentoses muito superior de hexoses. A xilose o
acar mais abundante. Aps a purificao dos lenhosulfonatos estes apresentam
uma distribuio multimodal do peso molecular, assim como, um aumento de
M
w
(~ 1,5 vezes). Os resultados obtidos por tcnicas espectroscpicas (FTIR e
RMN) permitiram a caracterizao estrutural dos lenhosulfonatos purificados.

196


Figura 1. Ligandos
utilizados nas snteses.
SNTESE E CARACTERIZAO DE COMPLEXOS
ORGANOMETLICOS COM HETEROCICLOS - IV

J. L. Ferreira da Silva*, A. Romo Dias, A. P. Ferreira, P. T Gomes,
M. M. Salema
Centro de Qumica Estrutural, Instituto Superior Tcnico, Av. Rovisco Pais, 1049-001,
Lisboa, Portugal
*joo.luis@ist.utl.pt

A preparao de compostos organometlicos anlogos aos de
ciclopentadienilo (Cp) utilizando heterociclos como ligandos continua a ser um
objectivo da Qumica Organometlica. Devido elevada capacidade como base
de Lewis do heterotomo os compostos obtidos
apresentam geralmente coordenao o em lugar
de q
5
como no caso do Cp. Num estudo anterior
1

com Ti e DMP (2,5-dimetilpirrolilo) foram
preparados complexos de forma geral
Ti(DMP)(NMe
2
)
x
Cl
3-x
, verificando-se uma
variao da coordenao do anel de
5
para N-
quando o nmero de amidas presentes passa de
duas para trs, devido maior capacidade doadora
electrnica do NMe
2
.
Neste trabalho apresentada a sntese de 5 compostos em que a coordenao
do pirrolilo N-. Quatro deles so obtidos atravs da reaco de Ti(NMe
2
)
4

com indole, 2-Me-Indole e com dois derivados ansa do pirrole, o [CH
2
(NC
4
H
4
)
2
]
e o {CH
2
[2,5-NC
4
H
2
(CH
3
)
2
]
2
}:
Ti(NMe
2
)
4
+ 2 L Ti(NMe
2
)
2
L
2
+ 2 NMe
2
Ti(NMe
2
)
4
+N N Ti(NMe
2
)
2
(N N) + 2 NMe
2

No caso do indole este tipo de coordenao seria expectvel, devido ao
volume dos ligandos e presena do anel benznico, que retira densidade
electrnica ao anel, reduzindo a probabilidade de coordenao t. J no caso dos
compostos ansa, para alm do efeito do volume, h tambm que ter em conta a
prpria geometria dos ligandos.
Outro factor a ter em conta o reduzido volume do Ti; este efeito sobre o
tipo de coordenao torna-se mais visvel na sntese do complexo Ti(-
DMP)
2
(NMe
2
)
2
, quando comparado com o complexo de Zr com dois ligandos
TMP Zr(-TMP)(
5
-TMP)(NMe
2
)
2
, em que se obtm uma coordenao mista
2
.
Ti(oDMP)(NMe
2
)
3
+ 2 HDMP
Ti(oDMP)
2
(NMe
2
)
2
+ NMe
2

[1] A.R. Dias, A.P. Ferreira, M.M. Salema, J.F. Silva. XVIII Encontro Nacional da SPQ,
Aveiro, 2002.
[2] A.M. Galvo, Tese de Doutoramento, IST, Lisboa, 1999.
N
R R = H, Me L =
N N
N N
Me
Me
Me
Me
N N =
197


METAL-NSAID COORDINATION: STUDY OF
INTERACTIONS BETWEEN IBUPROFEN AND
BIOLOGICALLY ACTIVE METALS

Elisabete Oliveira*, Tiago Silva, Luz Fernandes, Hugo Santos,
Teresa Avils,

Jos Lus Capelo, Carlos Lodeiro
REQUIMTE, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
*e.oliveira@dq.fct.unl.pt

The synthesis of metal complexes with active drugs as ligands, namely non-
steroid anti inflammatory drugs (NSAID), is a field of increasing interest in
inorganic, pharmaceutical and medicinal chemistry. The main reasons are not
only those related to stability, enhanced activity, low hidrophobicity and more
effective membrane trespassing of the active molecule, but also those related to
new administration therapies [1].
Recent studies reported the
formation of pseudo-molecular ion
formation in electrospray ionization
of AIDs containing phenyl-acetic
acid functionality in the presence of
sodium, but these species were never
investigated in the fundamental
state, and the existing
spectrofluorometric characterization
is only of the AID itself [2, 3].
Herein, we describe the synthesis of seven metal-NSAID complexes with the
structure showed above (M= alkali and alkaline earth metals, Zn(II) and Fe (II),
n=1,2). Characterization by EA,
1
H RMN, FTIR, UV-vis and fluorescence
emission spectroscopies, as well as by MALDI-TOF-MS mass spectrometry was
made in order to determine the different binding modes and affinity between the
metal and the drug, which may lead to further studies for the purposes mentioned
above.

Acknowledgements: We are grateful to FCT for financial support to projects
PTDC/QUI/66250/2006 and PTDC/CTM/64288/2006. E. Oliveira and H. Santos thanks
PhD grants numbers SFRH/BD/35905/2007 and SFRH/BD/38509/2007 respectively. T.
Silva thanks BI grant to project PTDC/QUI/66250/2006.

[1] R. Cini, Comments Inorg. Chem 22 (2000) 151.
[2] K. Schug, J. Sep. Sci. 25(2002) 760.
[3] P. Damiani, M. Bearzotti, M. Cabezn, J. Pharm. Biomed. Anal, 25 (2001) 679.
CH
3
H
3
C
O
O
-
n = 1-2
M = Na(I), Li(I), K(I), Ca(II), Mg(II)
Zn(II) and Fe(II)
M
n
198


SYNTHESIS OF COORDINATION COMPOUNDS WITH 2-
MERCAPTONICOTINIC ACID AND 1,10-
PHENANTHROLINE

Penka I. Girginova
a
*, Lus Cunha-Silva
a
, Filipe A. A. Paz
a
, Helena I.
S. Nogueira
a
, Joo Rocha
a
, Vtor Amaral
b
,

Tito Trindade
a
a
Chemistry Department, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
b
Physics Department, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
*girginova@ua.pt

The self-assembly of multifunctional organic ligands with metal centres to
produce novel inorganic-organic hybrid materials is currently of great interest,
due to the possibility to construct multi-dimensional frameworks with peculiar
architectures and exhibiting interesting properties. The synthesis of structural
units which might be used in the design of hierarchically more complex
compounds with specific properties is challenging. In fact, these properties are
frequently modulated by a combination of various factors [1], such as the
coordination geometries of the metal centres, the metal-to-ligand(s) ratio(s) and
the presence of bridging ligands which connect different metal centres. In the
course of our studies on the structure and magnetic properties of transition metal
complexes, a number of new organic-inorganic coordination compounds with
derivatives of pyridinecarboxylic acids have been prepared and characterised [2].
We have focused our attention on the synthesis and magnetic properties of d-
metal complexes of organothiolato carboxylates, in particular on the use of 2-
mercaptonicotinic acid; this ligand has distinct possibilities of coordination and
chelation modes towards d metal ions. Moreover, and compared to the O-bridged
compounds, the presence of a S-donor ligand between d-transition metal sites
might enhance the delocalisation of the spin density around the bridging atom. A
series of new coordination compounds of 1
st
row transition metals with 2-
mercaptonicotinic acid and 1,10-phenantroline will be reported here. This
communication will focus on the synthesis and properties of such compounds. In
particular, the influence of the ligand field and the coordination geometry on the
magnetic susceptibility of the complexes will be discussed.
Acknowledgements: We thank FCT for funding (POCI/QUI/58377/2004 and POCI/QUI/
58887/2004, supported by POCI 2010 and FEDER) and for grants SFRH/BD/17968/2004
(PG) and SFRH/BPD/34895/2007 (LCS).
[1] a) C. Janiak, J. Chem. Soc. Dalton Trans. 14 (2003) 2781; b) O.M. Yaghi, H. Li, C.
Davis, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474; c) M. Eddaoudi,
D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. O'Keeffe, O.M. Yaghi, Acc. Chem.
Res. 34 (2001) 319.
[2] a) P.I. Girginova, F.A.A. Paz, H.I.S. Nogueira, N.J.O. Silva, V.S. Amaral, J. Klinowski,
T. Trindade, Polyhedron 24 (2005) 563; b) P.I. Girginova, F.A.A. Paz, H.I.S. Nogueira,
N.J.O. Silva, V. S. Amaral, J. Klinowski, T. Trindade, J. Mol. Struct. 737 (2005) 221.
199


CHARACTERIZATION OF BIONANOPROBES FROM
CYTOCHROME C/ GOLD NANOPARTICLES COMPLEXES

Ins Gomes
a
*, Nuno C. Santos
b
, Lus M. A. Oliveira
c
, Alexandre
Quintas
c
, Peter Eaton
d
, Ricardo Franco
a

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b
Instituto de Medicina Molecular, Faculdade de Medicina da Universidade de Lisboa, Av.
Prof. Egas Moniz, 1649-028 Lisboa, Portugal
c
Laboratrio de Patologia Molecular, Instituto Superior de Cincias da Sade Egas
Moniz, Campus Universitrio, Quinta da Granja, 2829-511 Caparica, Portugal
d
REQUIMTE and Departamento de Qumica, Faculdade de Cincias da Universidade do
Porto, R. Campo Alegre, 687, 4169-007 Porto, Portugal
*inesgomes@dq.fct.unl.pt

Gold nanoparticles (AuNPs) were coated with two cytochromes c isolated
from horse heart (HCc) and yeast (YCc). In the complexes, HCc is most
probably electrostatically bound to the gold surface through its lysine patch,
whereas YCc is probably covalently bound to the gold surface by the sulfur atom
of its cystein-102 residue [1].
The complexes were characterized by UV-visible and Circular Dichroism (CD)
spectroscopies, Dynamic Light Scattering (DLS) and Zeta Potential measurements
and Atomic Force Microscopy (AFM). UV/vis data show that both cytochrome c-
AuNP complexes aggregate for low pH of the solution, inducing a color change
from red (non-aggregated complexes, at high pH), to blue (aggregated complexes,
at low pH). This behavior was specific to the cytochrome c-AuNP complexes, as
no variation was observed for either AuNPs or cytochrome c alone.
CD spectroscopy is useful to obtain local information about the conformational
and dynamic changes on the protein layer [2]. The results showed significant
conformational changes on the proteins secondary structure in the YCc-AuNP
complex, whereas the HCc-AuNP complex exhibited no noteworthy alterations.
AFM and DLS confirmed protein layers of ca. 2 nm for the HCc-AuNP complex
and ca. 4 nm for the YCc-AuNP complex. In the case of HCc complex, the protein
layer proved to be easily removed by sample drying, in contrast with the more sturdy
protein layer of the YCc complex. In both complexes, the surface potential was
similar, despite differing from either the AuNPs alone or the proteins alone.
The experimental data agree with the fact that the binding mode of both
proteins to the AuNPs is different, and that different binding mode confer
distinctive properties to the AuNP-cytochrome c complexes. This modulation of
the surface properties of these AuNP-protein complexes is potentially useful
from the point of view of the fabrication of bionanoprobes [3].

[1] M-E Aubin-Tam, K. Hamad-Schifferli, Langmuir. 21 (2005) 12080.
[2] X. Jiang, et al., Biomacromolecules. 6 (2005) 46.
[3] N. Wangoo, et al., Analytica Chimica Acta 610 (2008) 142.
200


STUDY OF THE EFFECT OF THE R GROUP IN CC BOND
RUPTURE PROMOTED BY CUCL IN CAMPHOR ALKYNES

M. Fernanda N. N. Carvalho
a
*, Tiago A. Fernandes
a
, Rudolf Herrmann
b

a
CQE, Complexo I, Instituto

Superior Tcnico, Av. Rovisco Pais 1049-001 Lisboa, Portugal
b
Institut fr Physik, Universitt Augsburg, Universittsstr.1, D-86133 Augsburg Germany
*fcarvalho@ist.utl.pt

Cyclisations, ring-opening/ring-closure cascades and C-H activations are
types of processes identified in reactions of camphor-derived compounds (1)
with a variety of electrophiles. [1-3].
The cleavage of the acetylenic
substituents from the camphor skeleton of
compounds (1), (2) or (3) is a so far unique
process that formally corresponds to the
reversal of the formation of the mono- or di-
alkyne camphor compounds by reaction of
acetylides with keto and/or imino groups of
3-oxo-camphorsulfonylimine (4), Figure 1.
The substituent R at the triple bond drives
the coordination to copper as well as the
reactivity and regioselectivity of the process,
Figure 2.
Quantum mechanical calculations using
DFT support and rationalize the experimental results.




R=H R=Ph R=CH2Ph R=CH2NH2
Figure 2. Models for camphor alkynes coordination to Cu(I)

Acknowledgements: This work was supported by FCT- Fundao para a Cincia e
Tecnologia (Projecto 3599, Medida 005, Programa P002) under Project PPCDT
58119/QUI/2004.

[1] M.F.N.N. Carvalho, Activation of alkynes by camphor complexes in: Advances in
Organometallic Chemistry Research, Cap 4, Ed.: K. Yamamoto, Nova Science
Publishers, Inc. NY, 2007, 81.
[2] M. Lampropoulou, R. Herrmann, G. Wagner, Tetrahedron 60 (2004) 4635.
[3] A.M. Santos, M.F.N.N. Carvalho, A.M. Galvo, A.J.L. Pombeiro, Z. Naturforsch. 57b
(2002) 691.

OH
NH
S
O O
R
R
O
NH
S
O O
R
OH
N
S
O O
R
O
N
S
O O
CuCl
CuCl
CuCl
CuCl
R Li
H
+
H
+
(1)
(2) (3)
(4)
R Li
R Li
H
+
H
+
Figure 1. Formation of species
1, 2 or 3
Cu
O O
Cu
N
201


PTA
NEW RHENIUM (III) COMPLEXES BEARING WATER
SOLUBLE LIGANDS

Gonalo J. O. C. Lopes
a
*, Piotr Smoleski
b
, Elisabete C. B. A.
Alegria
a,b
, Lusa M. D. R. S. Martins
a,b
, Armando J. L. Pombeiro
b

a
Departamento de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa, R.
Conselheiro Emdio Navarro, 1959-007 Lisboa, Portugal
b
Centro de Qumica Estrutural, Complexo I, Instituto Superior Tcnico, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
*goncalopes1@gmail.com

Within the expanding coordination chemistry of rhenium, the synthesis of
complexes that are soluble in ambient friendly solvents, specially water, has not
yet been significantly explored [1]. Thus, the application of hydro-soluble 1,3,5-
triaza-7-phosphaadamantane (PTA), tris(pyrazolyl)methanesulfonate,
SO
3
C(pz)
3
-
(Tpms) and their derivatives as ligands would be particularly
promising in view e.g. of the interesting catalytic, medicinal or photoluminescent
properties of some complexes with such ligands.








Herein we report the synthesis of new water-soluble rhenium (III) complexes
bearing PTA, e.g. |ReCl
2
(N
2
COPh)(PTA)
3
|, or the N
3
tripodal anionic tris(1-
pyrazolyl)methanesulfonate SO
3
Cpz
3
-
ligand.
The new complexes have been characterized by IR and multinuclear NMR or
EPR spectroscopies, FAB-MS spectrometry and elemental analysis.

This work has been partially supported by the Fundao para a Cincia e Tecnologia
(FCT).

[1] a) A.D. Philips, L. Gonsalvi, A. Romerosa, F. Vizza, M. Peruzzini, Coord. Chem.
Rev. 248 (2004) 955; b) P. Smolenski, A.J.L. Pombeiro, Dalton Trans. (2008) 87; c)
E.C.B.A Alegria, L.M.D.R.S. Martins, M. Haukka, A.J.L. Pombeiro, Dalton Trans.
(2006) 4954; d) T.S. Silva, E.C.B.A. Alegria, L.M.D.R.S. Martins, A.J.L. Pombeiro,
Adv. Synth. Catal. (2008) in press.
N N
CSO
3
-
Li
+ N N
N N
P
N N
N
Tpms
202


SYNTHESIS OF ZnO/POLY-{TRANS-[RuCl
2
(VPY)
4
]/STY}
NANOCOMPOSITES

Karen Segala
a,b
*, Rosilene L. Dutra
a
, Csar V. Franco
a
, Angela S.
Pereira
b
, Manuel A. Martins
b
, Protima Rauwel
b
, Tito Trindade
b

a
Departmento de Qumica, Universidade Federal de Santa Catarina, Campus Trindade,
88040-900, Florianpolis, SC, Brasil
b
Departmento de Qumica, Universidade de Aveiro, CICECO, 3810-193, Aveiro, Portugal
*karen@ua.pt

Nanosized particles are of great scientific and technological interest because
they have properties different from those of bulk solids of the same composition.
Because of their size-dependent electronic and optical properties, semiconductor
nanocrystals have been intensely investigated in the last two decades as
promising materials in the field of Nanotechnology [1].
We wish to report for the first time results concerning the synthesis of
nanocomposites made of ZnO nanocrystals (NCs) incorporated in the co-
polymer poly-{trans-[RuCl
2
(vpy)
4
]/sty}. In a first step, this polymer was
prepared through the reaction of trans-[RuCl
2
(vpy)
4
]
and styrene (sty), using methodologies previously
described [2].The ZnO NCs were then prepared by the
drop-wise addition of an ethanol solution containing
tetramethylammonium hydroxide to a DMSO solution
of Zn(CH
3
COO)
2
2H
2
O; the ZnO NCs were then
organically capped with trioctylphosphine oxide.
These components, ZnO NCs and poly-{trans-
[RuCl
2
(vpy)
4
]/sty}, were mixed in CH
2
Cl
2
to produce
cast films by the evaporation of the solvent. In this
communication, we will report the properties of these
materials as compared to those of the nanocomposites
analogues obtained from the in situ polymerization in
the presence of ZnO NCs.

[1] T. Trindade, P. OBrien, N.L. Pickett, Chem. Mater. 13 (2001) 3843.
[2] K. Segala, R.L. Dutra, E.N. de Oliveira, L.M. Rossi, J. R. Matos, M.M.S. Paula, C.V.
Franco, J. Braz. Chem. Soc., 17 (2006) 1679.
Figure 1. TEM image
of a nanocomposite
sample
203


SNTESE E CARACTERIZAO DE COMPLEXOS DE
FERRO(II) E RUTNIO(II) COM LIGANDOS NITRILO E
ACETILETO: POTENCIAIS FIOS MOLECULARES?

V. Pacheco
a
*, S. Soares
a
, M. P. Robalo
a,b
, M. Ftima M. Piedade
c
a
Dep. de Engenharia Qumica, ISEL, R. Conselheiro Emdio Navarro 1, 1959-007 Lisboa
b
Centro de Qumica Estrutural, Complexo I, IST, Av. Rovisco Pais, 1049-001 Lisboa
c
Dep. de Qumica e Bioqumica, FCUL, Ed. C8, Campo Grande, 1749-016 Lisboa
*vpacheco@sa.isel.ipl.pt

Os compostos envolvendo unidades bimetlicas de valncia mista ou grupos
organometlicos ligados atravs de sistemas orgnicos conjugados podem ser
utilizados como fios moleculares na rea da electrnica molecular ou como
componentes optoelectrnicos [1, 2].
Os fios moleculares envolvendo centros metlicos podem ser constitudos por
um sistema orgnico deslocalizado que estabelece a ponte entre os centros
metlicos terminais, sendo ambas as partes responsveis pelo desempenho final
do fio molecular. Os espaadores orgnicos so responsveis pelas propriedades
electrnicas e pelo comprimento do fio; enquanto que os centros metlicos, ao
introduzirem electres no sistema, aumentam a condutividade.
Os ligandos nitrilo e acetileto tm sido extensamente utilizados na sntese de
complexos de metais de transio electronicamente ricos e com uma extensa
conjugao [3, 4]. A sua contribuio tem sido igualmente til na construo
de fios moleculares envolvendo complexos bimetlicos, na medida em que
permitem a comunicao electrnica entre fragmentos metlicos terminais
atravs das ligaes deslocalizadas.
Nesta comunicao apresentaremos, a sntese de diversos complexos de
ferro(II) e rutnio(II) com ligandos nitrilo e acetileto baseados em diferentes
sistemas deslocalizados, tais como o N C-CH
2
C N, N C-C
6
H
4
C N,
N C-CH=CH-C N e N C-C
6
H
4
-C CH, e diferentes fragmentos metlicos
[CpFe(dppe)]
+
, [CpRu(dppe)]
+
, [CpFe(CO
2
)]
+
, [(Dppe)
2
FeH]
+
, etc.. Os
complexos obtidos foram caracterizados utilizando as tcnicas espectroscpicas
usuais: UV-VIS, IV e RMN. A eficincia da interaco electrnica entre os
centros metlicos, ao longo dos sistemas , foi avaliada por estudos
electroqumicos (voltametria cclica) e por anlise de difraco de raios X em
compostos seleccionados.

[1] F. Paul, C. Lapinte, Coord. Chem. Rev. 178-180 (1998) 431.
[2] A. Ceccon, S. Santi, L. Orian, A. Bisello, Coord. Chem. Rev. 248 (2004) 683.
[3] M. H. Garcia, M. P. Robalo, A. M. Galvo, M. F. M. Piedade, A. R. Dias, E.
Gooovaerts, W. Wenseleers, J. Organomet. Chem 619 (2001) 252.
[4] M. H. Garcia, M. P Robalo, A. R Dias, et al, Organometallics, 21 (2002) 2107.

204


INFLUENCE OF THE PREPARATION METHOD IN FINAL
PRODUCTS OF THE SERIES CO
X
Fe
3-X
O
4
(X = 1; 2)

Teresa Ferreira
a,b
*, M. Helena Mendona
b
, Fernanda M. A. Costa
b

a
University of vora, Chemistry Department and CQE, R. Romo Ramalho, 59, 7000
vora, Portugal
b
University of Lisbon,

Faculty of Sciences, Chemistry and Biochemistry Dept.,CCMM,
Campo Grande, Ed. C8, Piso 5, 1749-016 Lisboa, Portugal
*tasf@uevora.pt

Homogeneous highly crystalline powders are needed for materials with a
wide range of technical applications. Preparation methods play a fundamental
role in the characteristics of the final products. Spinel-type mixed oxides
containing Co and Fe have been intensively studied due to their electrical,
magnetic and electro catalytic properties and wide practical applications [1, 2].
For magnetic thin films or bulk materials, self-organization can be induced by
spontaneous crystalline transformations, being the spinodal decomposition
among them. The spinodal decomposition is a phase segregation mechanism,
which can occur in a miscibility gap of a phase diagram [3, 4].
The Co
x
Fe
3-x
O
4
system presents, for 2.5 x < 1, spinodal decomposition
when heat for several hours at temperatures below 973 K. Members of the series
Co
x
Fe
3-x
O
4
(x = 1; 2) have been prepared by three different ways: the ceramic
method, a wet chemistry route and a sol-gel type process. Some parameters, such
as starting materials, stages in characterization corresponding to distinct
annealing treatments and cooling process, were changed. Synthesis was followed
by X-ray powder diffraction (XRD) which was also used to characterize final
products and in conjunction with Rietveld refinement of XRD patterns allowed a
cationic distribution proposal for single-phase samples. Scanning electron
microscopy (SEM) studies have made evident the morphological difference of
the products prepared by distinct methods. Chemical analysis by Atomic
absorption spectroscopy (AAS) and Atomic emission spectroscopy (ICP-AES)
were combined with data obtained by X-ray microanalysis (EDS).
The wet chemistry route has provides excellent reproducibility and a
straightforward and rapid way for powder preparation. Moreover, the samples
present good stability and chemical and morphological homogeneity.
Acknowledgements: This work was supported by Fundao para a Cincia e Tecnologia.
[1] F. Bensebaa, F. Zavaliche, P. LEcuyer, R.W. Cochrane, T. Veres, J. Colloid
Interface Sci. 277 (2004) 104.
[2] E. Manova, T. Tsoncheva, Cl. Estourns, D. Paneva, K. Tenchev, I. Mitov, L. Petrov,
Appl. Catal. A: Gen. 300 (2006) 170.
[3] H. Le Trong, A. Barnabe, L. Presmanes, Ph. Tailhades, Sol. State Sci., DOI:10.1016/
j.solidstatesciences.2007.10.004.
[4] T.A.S. Ferreira, J.C. Waerenborgh, M.H.R.M. Mendona, M.R. Nunes, F.M. Costa,
Sol. State Sci. 5 (2003) 383.
205


ANISOTROPIC GOLD NANOPARTICLES: A
CONTROLLED APPROACH TO OBTAIN
NANOTRIANGLES

Maria Adelaide Miranda
a
*, Patrcia A. Carvalho
b
, Peter Eaton
a
,
Baltazar de Castro
a
, Eullia Pereira
a

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto,
Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
b
Departamento de Engenharia de Materiais, Instituto Superior Tcnico, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
*mariaadelaidemiranda@gmail.com

In the last decade, there has been a huge development in the ability to design
materials at the nanoscale, with different shapes and controlled sizes.
Anisotropic metallic nanoparticles are a class of nanostructures that open new
possibilities applications in fields ranging from medicine, biomedical diagnosis
till physics.
In the last years, we have developed a
new method to prepare gold and silver
nanoparticles concerning this abstract to
gold nanotriangles. Gold nanotriangles
were obtained by the photocatalytic
reduction of hydrogen tetrachloroaurate
(III) by triethanolamine using Sn (IV)
meso-tetra(N-Methyl-4pyridyl)porphine
tetratosylate chloride as the photocatalyst,
and CTAB as the capping agent, in
aqueous medium (pH = 6.5-8.0). pH and the concentration of CTAB and
SntMepyP have a strong influence on the morphology of the nanoparticles.
These factors were optimized for the preparation of nanotriangles with length
147 nm and 15-19 nm height.
The combination of transmission electronic microscopy, atomic force
microscopy and electron diffraction analysis allowed a thorough investigation of
the nanotriangles morphology, resulting in further insight on the dependence of
morphology on growth conditions, as well as the mechanisms of crystal growth.

Acknowledgements: Financial support from Fundao para a Cincia e a Tecnologia
through project POCTI/QUI/45145/2002. Adelaide Miranda thanks FCT for a Ph.D. grant
(SFRH/BD/17566/2004).
206


UV-Vis-NEAR-IR AND EPR STUDIES OF METAL
COMPLEXES OF 15-MEMBERED MACROCYCLES

N. Torres
a
*, M. F. Cabral
a
, J. Costa
a
, R. Delgado
b,c

a
CBT/iMed.UL, Fac. de Farmcia de Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa,
Portugal.

b
I.T.Q.B, UNL, Apartado 127, 2781-901 Oeiras, Portugal
c
I.S.T, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.
*nasltorres@ff.ul.pt

Following our previous studies [1] we now report
some thermodynamic and structural studies with a 15-
membered macrocycle, the dioxo-tetraamine L1 and its
derivative containing two N-carboxymethyl sidearms L2
(cf. Fig. 1).
L1 was synthesized using a high dilution method. L2
was obtained by condensation of L1 with potassium
bromoacetate in aqueous basic solution. The compounds
were characterized by
1
H and
13
C NMR spectroscopies.
The stability constants of complexes of the ligands
with Co
2+
, Ni
2+
and Cu
2+

were determined by potentiometric methods using
the HYPERQUAD program [2].
UV-Vis-near-IR spectroscopic studies with
Co
2+
, Ni
2+
and Cu
2+
complexes were also
performed. The X-band EPR spectra of Cu
2+

complexes of L1 and L2 in aqueous solution were
measured at different pH values (5.5, 7 and 9,
respectively). The parameters obtained by
simulation of the spectra [3] of both complexes
(cf. Fig. 2) indicated three different g values,
which are characteristic of copper(II) complexes
in rhombic symmetry with elongation of the axial
bonds and a d
x
2
-y
2 ground state, consistent with
elongated rhombic octahedral or distorted square
pyramidal stereochemistries.

Acknowledgements: The authors acknowledge the financial support from FCT and POCTI
(Project POCTI/49114/QUI/2002).

[1] R. Delgado M.F. Cabral, R. Castanheira, A. Zhang, R. Herrmann. Polyhedron 21
(2002), 2265.
[2] P. Gans, A. Sabattini, A. Vacca. Talanta 43 (1996) 1739.
[3] F. Neese, Diploma Thesis, University of Konstanz, Germany, 1993.
Fig. 2. EPR spectra of the
Cu
2+
complexes with L1
(a) and L2 (b).
Fig. 2. EPR spectra of the
Cu
2+
complexes with L1
(a) and L2 (b).
Fig. 1. Macrocycles
L1 and L2.
N
S
N
N
N
O
O
L1 = R = H
H
R R
H
COOH L2 = R =
Fig. 1. Macrocycles
L1 and L2.
N
S
N
N
N
O
O
L1 = R = H
H
R R
H
COOH L2 = R =
207


N-ALKYLOXYSULFAMOYLPHENYLPORPHYRINS:
SYNTHESIS AND PHOTODYNAMIC EFFECT AGAINST
COLON CARCINOMA CELLS

A. C. Serra
a
, Nelson A. M. Pereira
a
*, M. Pineiro
a
, A. M. dA. Rocha
Gonalves
a
, M. Abrantes,
b
M. Laranjo,
b
A. C. Santos
b
, M. F. Botelho
b

a
Chymiotechnon, Departamento de Qumica, Universidade de Coimbra, 3049-535,
Coimbra, Portugal
b
Instituto de Biofsica/Biomatemtica, IBILI, Faculdade de Medicina de Coimbra, 3000-
354 Coimbra, Portugal
*nelsonampereira@gmail.com

5,10,15,20-tetraphenylporphyrins sulfonated at the meta position of the
phenyl rings have been reported as potential photodynamic therapy (PDT)
sensitizers [1], catalysts for oxidation reactions [2], studied for their anti-HIV
activity [3]. For the application of this type of compounds as PDT sensitizers, a
specific photochemical and amphiphilic characteristic are requested: high
absorption coefficient at the therapeutic window, high singlet oxygen formation
quantum yield, and amphifilicity. In order to incorporate these characteristics we
synthesized ortho-halogen-meta-N-alkyloxysulfamoylphenylporphyrins, scheme
1. The halogen atom at the ortho position was reported to increase the singlet
oxygen formation quantum yield trough the heavy atom effect [4] and the
sulfamoyl group is adequate to modulate the amphiphilic properties. The results
of the in vitro studies of these compounds against WiDr cells will be presented.

Scheme 1
Acknowledgments: The authors thank to Chymiotechnon, Ministrio da Economia/
POE/Prime/Proj 3/293/CLARO, Faculdade de Medicina de Coimbra and CIMAGO for
financial support and Servio de Gastroenterologia dos HUC for equipment facilities.

[1] K. Lang, J. Mosinger, D.M. Wagnerov Coord. Chem. Rev. 248 (2004) 321.
[2] R. Song, A. Robert, J. Bernadou, B. Meunier Inorg. Chim. Acta 272 (1998) 228.
[3] D.W. Dixon, A.F. Gill, L. Giribabu, A.N. Vzorov, A.B. Alam, R.W. Compans J.
Inorg. Biochem. 99 (2005) 813.
[4] E.G. Azenha, A.C. Serra, M. Pineiro, M.M. Pereira, S.J. Seixas de Melo, L.G. Arnaut,
S.J. Formosinho, A.M.d'A Rocha Gonsalves. Chem. Phys. 280 (2002) 177.
N
NH N
HN
R
X = H or Cl or Br
R
R
R
X
S
O
O NH O
HO
X
R =
208


FUNCTIONAL DESYMMETRIZATION OF 1,3-DIOXIMES
FOR THE OBTENTION OF 1,2,3-TRISUBSTITUTED
CARBOCYCLES

Valdemar B. C. Figueira, Arantxa G. Esqu, Sundaresan Prabhakar,
Ana M. Lobo
Chemistry Department, REQUIMTE/CQFB, Faculty of Sciences and Technology, New
University of Lisbon, 2829-516 Monte de Caparica, Portugal
aml@fct.unl.pt

Enehydroxylamines are useful compounds that can be involved in 3,3-
sigmatropic rearrangements, thus providing a functionalization methodology for
the -carbon [1]. With the purpose of expanding the ambit of this reaction it
would be of interest to remove the N-substituent at the end of the rearrangement
[2]. In this communication we present our results with carbocylic 1,3-dioximes
1, which react with strong electrophiles giving systems 3, that may,
spontaneously or through heat, suffer [3,3]-sigmatropic rearrangements in high
yields, and giving rise to 1,2,3-trisubstituted carbocycles 4 (Scheme 1). Possible
routes for the final deprotection are discussed.


Acknowledgments: We thank Foundation for Science and Technology for partial financial
support and for a research fellowship (to V. B. C. F.). The bilateral PortugalSpain
Cooperation Agreement AI/E-59/06 is also thanked for financing the stay in the
Portuguese Laboratory of A. G. E. It is a pleasure to record our gratitude to Ms Luz
Fernandes and Ms Carla Rodrigues of REQUIMTE Analytical Services Laboratories for
mass spectra and elemental analyses respectively.

[1] L.V. Reis, A.M. Lobo, S. Prabhakar, M. P. Duarte, Eur. J. Org. Chem., 2003, 190 and
references therein.
[2] E. Vedejs, J.D. Little, L.M. Seaney, J. Org. Chem, 2004, 69, 1788.
Scheme 1
NOH
NOH
base
NOH
NOH
X O
NO
N
XO
O
X
O
XO
NO
NH
XO
O
X O
XO
Electrophiles: R(CO)Cl, (RO)
2
P(O)Cl, ArSO
2
Cl
1 2 3 4
209


OH
H
OH
O
OH
OH
OH
ESTUDO QUMICO DA BULNESI A SARMI ENTOI

Snia C. Nabais*, Jesus M. Rodilla, Carla Gaiolas, Arlindo Gomes,
Lcia Silva
Universidade da Beira Interior, Rua Marqus dvila e Bolama, 6201-001 Covilh
*sonia_quimica@mail.pt

Com este trabalho pretendeu-se fazer o estudo qumico de uma planta
denominada de Bulnesia sarmientoi, da famlia Zygophyllaceae mais
conhecida por Pau santo que existe essencialmente no Paraguai, mas que est
em vias de extino.
Uma das maiores qualidades desta planta
o facto da sua madeira ser muito pesada,
resistente, de grande dureza, beleza e
durabilidade natural, possui um aroma
agradvel, um brilho suave, e esverdeada em
tons de castanho que tanto a caracteriza, a sua
resina utilizada nas fbricas de vernizes,
lacas e maquilhagem. Pela destilao por
arraste de vapor da sua madeira, obtm-se o
leo essencial desta espcie, composto por
terpenos. Este leo vendido no mercado,
para as indstrias de perfumaria, cosmtica, entre outras, uma vez que ele tem
um alto teor de guaiol. Assim, este leo transformado em produtos de alto
valor acrescentado. A Bulnesia sarmientoi uma rvore cujas folhas e cascas so
usadas na medicina popular.
Este trabalho consistiu no isolamento e caracterizao de diferentes
compostos do extracto da Bulnesia sarmientoi, tendo-se extrado o leo atravs
de dois mtodos, a destilao a vapor e a extraco por solvente.
Separaram-se por cromatografia em coluna 4 compostos, o o-guaiol, o
bulnesol e o criptomeridiol extrados do extracto da madeira de hexano a quente
e o hanamiol extrado do leo obtido por destilao por arraste de vapor, todos
eles sesquiterpenos.
A determinao das estruturas dos compostos foi efectuada por GC-MS e
pela anlise dos seus espectros de infravermelho, massa e de ressonncia
magntica nuclear de proto e carbono 13.






o - guaiol Bulnesol Criptomeridiol Hanamiol

Figura 1. Bulnesia sarmientoi
210


Figure 1. Structure of
benzoxazoles 1.
SYNTHESIS OF NEW PUSH-PULL (OLIGO)THIENYL-
BENZOXAZOLES AS EFFICIENT NLO CHROMOPHORES

Rosa M. F. Batista
a
, Susana P. G. Costa
a
, Michael Belsley
b
, M.
Manuela M. Raposo
a
*
a
Center of Chemistry, University of Minho, Campus de Gualtar

4710-057 Braga,
Portugal
b
Department of Physics, University of Minho, Campus de Gualtar

4710-057 Braga,
Portugal
*mfox@quimica.uminho.pt

Benzoxazoles are a very versatile group of heterocyclic compounds due to
their widespread applications such as ligands in coordination chemistry, in
organic electroluminescent devices and materials for optical applications [1]. Our
recent work on the synthesis and characterization
of chromophores in which the donor moiety is
represented by a t-excessive five-membered
heterocycle (pyrrole or thiophene) and the
acceptor group is a deficient heterocyclic benz-X-
azole ring (benzothiazole and benzimidazole)
have shown that they exhibit excellent
solvatochromic, fluorescence and nonlinear
optical (NLO) properties [2-6].
We now report the synthesis and
characterization of the thermal, solvatochromic and NLO properties of a series of
heterocyclic chromophores of the benzoxazole type. Therefore, benzoxazoles 1
were synthesized, in good to excellent yields, through the condensation of o-
aminophenol and formyl-(oligo)thiophenes in the presence of lead tetraacetate
(Figure 1). The hyperpolarizabilities of chromophores 1 were measured using
hyper-Rayleigh scattering and thermogravimetric analysis (TGA) was used to
evaluate their thermal stability. The experimental results indicate that good
nonlinearity-thermal stability is well balanced specially for chromophores 1,
making them good candidates for NLO applications.
Thanks are due to FCT for financial support through a PhD grant to R.M.F. Batista
(SFRH/BD/36396/2007).
[1] V. Bruno, A. Castaldo, R. Centore, A. Sirigu, F. Sarcinelli, M. Casalboni, R.
Pizzoferrato. J. Polym. Sci. Part A 40 (2002) 1468.
[2] R.M.F. Batista, S.P.G. Costa, M.M.M. Raposo. Tetrahedron Lett., 45 (2004) 2825.
[3] S.P.G. Costa, R.M.F. Batista, P. Cardoso, M. Belsey, M.M.M. Raposo. Eur. J. Org.
Chem. 17 (2006) 3938.
[4] R.M.F. Batista, S.P.G. Costa, E.L. Malheiro, M. Belsley, M.M.M. Raposo.
Tetrahedron 63 (2007) 4258.
[5] R.M.F. Batista, S.P.G. Costa, M. Belsley, M.M.M. Raposo. Tetrahedron 63 (2007) 9842.
[6] J. Pina, J. Seixas de Melo, H.D. Burrows, R.M.F. Batista, S.P.G. Costa, M.M.M.
Raposo. J. Phys. Chem. A 111 (2007) 8574.
N
O
S
R
R = H, alkoxyl
n
1
n = 1-3
211


SYNTHESIS OF SULFONAMIDE HALOGENATED
PORPHYRINS AND K
OW
EVALUATION

Carlos J. P. Monteiro
a
*, Mariette M. Pereira
a
, Sara M. A. Pinto
a
,
Ana V. C. Simes
a
, Gonalo F. F. S
a
, Lus G. Arnaut
a
, Sebastio J.
Formosinho
a
, Srgio Simes
b

a
Chemistry Department, University of Coimbra, 3004-535 Coimbra, Portugal
b
Bluepharma SA, So Martinho do Bispo, 3045-016 Coimbra, Portugal
*cmonteiro@qui.uc.pt

Porphyrins are key compounds for development of photosensitizers for
photodynamic therapy (PDT). They are synthetic precursors of other sensitizers,
such as chlorins and bacteriochlorins[1] which have strong absorptions at longer
wavelengths. With the expectation of improved photodynamic activity, the
introduction of halogen atoms in this class of sensitizers will increase singlet
oxygen quantum yield[2] and the introduction of amphiphilic properties will
combine high singlet-triplet intersystem crossings with enhanced lipid
bioavailability. A new series of ortho
halogenated tetraarylporphyrins with
sulfonamide substituents have been synthesized
via chlorosulfonation reaction followed by
nucleophilic reaction with water or the desired
amine.[3] To predict their partition properties,
1-octanol/water partition coefficients (K
OW
) of
a selected range of the synthesized halogenated
amphiphilic porphyrins is described. A
significant effect of the number and type of halogen group as well as on the
number of sulfonamide side chain was observed. The determination of K
OW

showed that is possible to obtain compounds with a wide range of lipophilicities,
from log K
OW
= -2,71 till log K
OW
> 4, which are suitable to optimize the biological
efficacy of this class of sensitizers for PDT application.

Ackowledgements: The authors thank Cmara Municipal de Coimbra, CCDRC,
Bluepharma SA, Programa Operacional da Regio Centro, Medida 1.5 Feder and FCT
(PTDC/QUI/66015/2006) for financial support. C.J.P. Monteiro thanks FCT for a PhD
grant SFRH/BD/37652/2007.

[1] M.M. Pereira, L.G. Arnaut, S.J. Formosinho, C.J.P. Monteiro WO Pat. 053707, 2006.
[2] J.M. Dabrowski, M.M. Pereira, L.G. Arnaut, C.J.P. Monteiro, A.F. Peixoto, A.
Karocki, K. Urbanska, G. Stochel Photochem. Photobiol. 83, (2007) 897.
[3] C.J.P. Monteiro, M.M. Pereira, S.M.A. Pinto

A.V.C. Simes, G.F.F. S, L.G. Arnaut,
S.J. Formosinho, S. Simes. Tetrahedron, in press, doi: 10.1016/j.tet.2008.03.055.

X = Cl or F
X' = Cl or H
N
NH N
HN
X
X
X'
X
X'
X'
X'
X
R
R
R
R
-SO
2
N
-SO
2
NHCH
3
-SO
2
NHCH
2
CH
3
-SO
2
NH(CH
2
)
2
CH
3
-SO
2
NH(CH
2
)
6
CH
3
R =
-SO
3
H
212


SNTESE DE NOVOS IMIDAZOLIL[1,2,4]TRIAZOLES

Sandra M. Nobre, A. Sofia Vila-Ch, Alice M. Dias*, M. F. Proena
Departamento de Qumica, Universidade do Minho, 4710-057 Braga, Portugal
*ad@quimica.uminho.pt

Compostos heterocclicos contendo anis de 1,2,4-triazole possuem
importantes propriedades farmacolgicas como antifngicos e antivirais [1].
Por outro lado, heterociclos contendo o anel de imidazole so descritos como
importantes antibiticos. Em particular, o metronidazol um antibitico que est
em uso clnico h mais de 35 anos e est includo nos 100 medicamentos mais
usados globalmente, devido potente actividade demonstrada sobre um largo
espectro de microorganismos [2]. Mais recentemente, o nitroimidazopirano PA-
824 apontado como um importante candidato a ter xito no tratamento da
tuberculose [3, 4].

No mbito de um projecto de
investigao que visa a sntese de
anlogos do nitroimidazopirano foi
desenvolvido, pelo nosso grupo de
investigao, um mtodo simples e
eficiente para gerar os imidazolil
[1,2,4]triazoles 3, que so estruturas
heterocclicas novas que combinam
uma unidade de imidazole ligada a
um ncleo de 1,2,4-triazole.
Neste mtodo, os imidazoles 1,
so convertidos em imidazolil
[1,2,4]triazoles (3) de acordo com o
esquema apresentado na figura 1 e
as reaces ocorrem temperatura
de 0-8C com bons rendimentos. O
mecanismo ser discutido posteriormente.

Agradecimentos: Agradece-se Universidade do Minho, Centro de Qumica e Fundao
para a Cincia e Tecnologia (POCTI/QUI/45391/2002) o apoio financeiro.

[1] A Al-Masoudi, Y. Al-Soud, N.A. Al-Masoudi, Chemistry of Heterocyclic Compounds
42 (2006) 1377.
[2] C.E. Barry, H. Boshoff, C. Dowed, Current Pharmaceutical Design 10 (2004) 3239.
[3] C.K. Stover, P. Warrener et al., Nature 405(2000) 962.
[4] Ballell et al., Antimicrob. Agents. Chemother. (2005) 2153.
N
N
NH
2
R
1
NH
CN
1
N
N
NH
2
R
1
N
CN O
R
2
N
N
NH
2
R
1
N
N
H
N
R
3
ClCOOEt
ou
Ac
2
o
NH
2
NH
2
2
3
Figura 1. Esquema reaccional
213


N
R
4
R
3
Pr
3: R
3
= R
4
= I
4: R
3
= I; R
4
= H
5: R
3
= R
4
= -CCH
6: R
3
= -CCH; R
4
= H
O O
O O
H H
R
1 R
2
1: R
1
= R
2
= I
2: R
1
= R
2
= -CCH
Figure 1 Monomer
units
CALIX[4]ARENE -BASED POLYMERS: HOMO
AND COPOLYMERIZATION WITH
CARBAZOLE DERIVATIVES

Patrcia D. Barata, Alexandra I. Costa, Jos V. Prata*
Laboratrio de Qumica Orgnica, Departamento de Engenharia Qumica and Centro de
Investigao de Engenharia Qumica e Biotecnologia, Instituto Superior de Engenharia
de Lisboa, Instituto Politcnico de Lisboa, R. Conselheiro Emdio Navarro, 1, 1959-007,
Lisboa, Portugal.
*jvprata@deq.isel.ipl.pt

Research in the area of conjugated polymers has attracted significant interest
recently in view of their exciting prospects applications in a range of electronic
devices. As part of our ongoing research aiming to produce well-defined
calixarene-based conjugated polymers as new materials for use in sensing
chemistry, the homo and copolymerization of carbazole derivatives (3-6) with
calix[4]arene units (1-2) was examined.
Appropriate calix[4]arene derivatives were successfully functionalized in the
lower rim affording the compounds 1 and 2.
1
The synthesis of carbazole
derivatives (3-6) was prepared according to reported methods.
2

The homopolymerization
of 2 and 6 and
copolymerization of 1 and 5,
2 and 3, 3 and 5 and 2 and 6
were tested under different
conditions.
The syntheses were
accomplished through
palladium-catalyzed cross-
coupling reactions (7 mol %
of Pd(PPh
3
)
2
Cl
2
, 7 mol % of
CuI and Et
3
N in toluene) and
Rh(I) as catalyst (2 mol % of
[Rh(nbd)Cl]
2
, 4 eq. Ph
3
P in THF) affording soluble polymers and oligomers
with variable conversions. Gel permeation chromatography (GPC) profiles
showed multimodal and unimodal distributions. A tentative interpretation of the
obtained results will be discussed.

Acknowledgements: We thank Fundao para a Cincia e a Tecnologia/MCIES (Portugal)
for partial financial support. A. I. Costa thanks ISEL for a doctoral fellowship.

[1] A.I. Costa, J.V. Prata, J. Polym. Sci. Part A: Polym. Chem. 44 (2006) 7054.
[2] Y. Zhang, T. Wada, L. Wang, H. Sasabe, Chem. Mater. 9 (1997) 2798.
214


SYNTHESIS OF SINGLE BRIDGED DOUBLE
CALIX[4]ARENES

Alexandra I. Costa, Jos V. Prata*
Laboratrio de Qumica Orgnica, Departamento de Engenharia Qumica and Centro de
Investigao de Engenharia Qumica e Biotecnologia, Instituto Superior de Engenharia
de Lisboa, Instituto Politcnico de Lisboa, R. Conselheiro Emdio Navarro, 1, 1959-007,
Lisboa, Portugal
*jvprata@deq.isel.ipl.pt

Calixarenes are well known in supramolecular chemistry for their ability to
form host-guest complexes with ionic and neutral molecular species.
1
The
synthesis of double (and triple) calixarenes has been attempted by several groups
on the expectation that the two (three) binding sites of each calixarene unit could
act in cooperativity thus enhancing the molecular/ionic recognition capabilities
of all the entity. The connection between the calixarene units have been done
through their narrow and wide rims.
1


For the single bridged double calix[4]arene compounds here presented,
luminophore properties are expected, which in turn may allow their use as
luminescent molecular devices. 3 could be obtained in very good yield (74%) by
the oxidative coupling (Glaser type homo-coupling) of 1,
2
while the Sonogashira
cross-coupling reaction between 1 and 2 furnished 4 in 56%. Their structures
were established by FT-IR,
1
H/
13
C NMR, MS and elemental analysis.
Acknowledgements: We thank Fundao para a Cincia e a Tecnologia/MCTES (Portugal)
for partial financial support. A. I. Costa thanks ISEL for a doctoral fellowship.
[1] Z. Asfari,, V. Bhmer, J. Harrowfield. Calixarenes 2001, Vicens, J., Eds.; Kluwer
Academic, Dordrecht, 2001.
[2] A.I. Costa, J.V. Prata, Supramolecular Chemistry 20 (2008) 95.

1
O
O
O
O
3
O
O
O
O
O O O O
i)
O O O O
O
O
O
O
O
O
O
O
H
I
i)
ii)
2
4
Scheme. Synthesis of double calix[4]arenes.
215


COMPLEXAO DE IES LANTANDEOS POR
DERIVADOS HOMOOXACALIXARENOS CONTENDO O
GRUPO CARBONILO

Paula M. Marcos
a,b
*, Jos R. Ascenso
c
, Manuel A. P. Segurado
a,b

a
Faculdade de Farmcia da Univ. Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa
b
Centro de Cincias Moleculares e Materiais, FCUL, Edifcio C8, 1749-016 Lisboa
c
Instituto Superior Tcnico, Complexo I, Av. Rovisco Pais, 1049-001 Lisboa
*pmmarcos@fc.ul.pt

No decurso dos estudos sobre complexao e transporte de caties alcalinos,
alcalino-terrosos, de transio e pesados por derivados homooxacalixarenos
contendo o grupo carbonilo no anel inferior [1-4], estendemos o nosso trabalho
ao estudo de ies lantandeos.
Neste trabalho apresentamos as propriedades complexantes de quatro
homooxacalixarenos (1a, 1b, 2a e 2b), todos na conformao cone,
relativamente aos ies lantandeos La
3+
, Ce
3+
, Nd
3+
, Sm
3+
, Eu
3+
, Gd
3+
, Dy
3+
, Er
3+

e Yb
3+
. Estes compostos so derivados do p-ter-butildihomooxacalix[4]areno (1)
e do p-ter-butilhexahomotrioxacalix[3]areno (2) e contm o grupo carbonilo no
anel inferior, nomeadamente o grupo adamantilcetona e etilamida.
Efectuaram-se experincias de extraco de picratos dos respectivos ies de
gua para diclorometano. Foram tambm realizadas titulaes por RMN de
proto para alguns caties. Quantidades variveis de triflatos de La, Eu e Yb
foram adicionadas aos ligandos directamente nos tubos de RMN e os espectros
de proto registados aps cada adio.
Os resultados so comparados em termos do tamanho do macrociclo e
consequentemente da sua flexibilidade conformacional e tambm da natureza do
grupo substituinte.
[1] P.M. Marcos, S. Flix, J.R. Ascenso, M.A.P. Segurado, J.L.C. Pereira, P. Khazaeli-
Parsa, V. Hubscher-Bruder, F. Arnaud-Neu. New J. Chem. 28 (2004) 748.
[2] P.M. Marcos, S. Flix, J.R. Ascenso, M.A.P. Segurado, B. Mellah, R. Abidi, V.
Hubscher-Bruder, F. Arnaud-Neu. Supramol. Chem. 18 (2006) 285.
[3] P.M. Marcos, S. Flix, J.R. Ascenso, M.A.P. Segurado, P. Thury, B. Mellah, S.
Michel, V. Hubscher-Bruder, F. Arnaud-Neu. New J. Chem. 31 (2007) 2111.
[4] P.M. Marcos, J.R. Ascenso, P.J. Cragg. Supramol. Chem. 19 (2007) 199.
216


NEW HYDROXYPYRIMIDINONE-SULFONAMIDES AS BI-
TARGET LIGANDS FOR ENZYME INHIBITION

M. Alexandra Esteves
a
*, Osvaldo Ortet
a,b
, Anabela Capelo
a
, Srgio
M. Marques
c
, Claudiu Supuran
d
, M. Amlia Santos
c

a
INETI-DTIQ, Estrada do Pao do Lumiar, 1649-038 Lisboa
b
Centro de Qumica e Bioqumica , FCUL, C8, Campo Grande, 1749-016 Lisboa
c
Centro de Qumica Estrutural, IST, UTL, Av. Rovisco Pais 1, 1049-001 Lisboa
d
Universit degli Studi di Firenze, Laboratorio di Chimica Bioinorganica, Rm. 188, Via
della Lastruccia 3, I-50019 Sesto Fiorentino (Firenze), Italy
*Alexandra.esteves@ineti.pt, fax:217168100

Hydroxypyrimidinones are endocyclic hydroxamic acids with high affinity
for hard metal ions, with potential application either as metal decontaminants for
environmental and biological purposes or as inhibitors of zinc-containing
enzymes, such as matrix metalloproteinases (MMP), since the hydroxamate is
one of the preferred metal-binding group for the MMP inhibitors (MMPi). On
the other hand, arylsulfonamides are
specific inhibitors of other zinc-
containing enzymes, the carbonic
anhydrases (CAs). Both types of
enzymes have isoforms involved in
carcinogenesis and tumor invasion
processes and they are currently the
target of drug design [1]. Having this in
mind and trying to explore potential
hybrid drugs aimed at combining CA and MMP inhibition roles, we have
designed new inhibitors by attaching a sulfonamide moiety to a
hydroxypirimidone [2]. Recently, we prepared a new hydroxypyrimidinone-
sulfonamide, 4-[2-(4-sulfamoyl-phenyl)-ethylamino]1-hydroxy-2(1H)-pyrimidinone
[3], which showed inhibitory activity in micromolar range against several MMPs.
Following this preliminary work and aiming at further exploring the bi-targeting
ability of these hybrid compounds, we have developed a new series of
hydroxyprimidinone-sulfonamide compounds, having different spacers between
these two functional groups. Herein, we present the synthesis and
characterization of these new compounds as well as some preliminary results of
bioassays to assess the inhibitory activity against several CAs. The results show
that all these sulfonamide-containing compounds present good CA inhibitory
capacity (IC50 in the nanomolar range) for the three isoforms (I, II and IX).

[1] C.M. Overall, O. Kleifield, Natural Rev. Cancer (2006) 227.
[2] M.A. Esteves, A. Cachudo, C. Ribeiro, S. Chaves, A. Rossello, M.A. Santos, Metal
Ions in Biology and Medicine 9 (2006) 35.
[3] S. Chaves, S.M. Marques, A. Cachudo, M.A. Esteves, M.A. Santos, Eur. J. Inorg.
Chem. (2006) 3853.
N
H
H
N
O
S
O
O
NH
2
n
2
n
1
N N
HO
O
n
1
= 3 or 5
n
2
= 0 or 2
217


o,o-DIALKYL GLYCINES DIPEPTIDES OBTAINED
FROM UGI REACTION PRODUCTS

Ana Maria F. Silva, Slvia M. M. A. Pereira-Lima*
Departamento de Qumica, Escola de Cincias, Universidade do Minho, Campus de
Gualtar, 4710-057 Braga
*silviap@quimica.uminho.pt

We have been involved in a study of the application of Ugis reaction to the
synthesis of o,o-dialkylglycines. Using 4-methoxybenzylamine (Pmb-NH
2
) as
the amine component, the N-alkyl group can be removed by TFA cleavage and,
during this process, the C-terminal amide bond of the resulting Ugi adducts (1) is
also cleaved [1]. The reaction mechanism involves an oxazolinium-type
intermediate (2), which allows in situ functionalization of the C-terminus by
reaction with several nucleophiles (HO-, MeO-, NH
2
-), affording different
derivatives such as free acids, esters and amides [2].
Our previous results suggested that a dipeptide could be obtained if an amino
acid ester was used as the nucleophile. Nevertheless, preliminary results
indicated that although a small amount of the required dipeptide is formed (3),
5,5-dialkyl-imidazolin-4-ones (4) are also obtained. These results from
competitive attack at the less hindered C-2 of the oxazolinium intermediate,
followed by rearrangement [3].
We now present new results in the optimization of the reaction conditions in
order to maximize peptide bond formation.
H
3
C N
H
N
C
6
H
11
O
Pmb
R R
O
H
3
C N
H
H
N
R'
O
R R
O
N
N
R
R
CH
3
O
R'
3
4
1
R = Et, Pr, iBu, Bn
NH
2
-R' = Phe-OtBu
N
O
R
R
CH
3
O
2
H
TFA
+
NH
2
-R'

|1| a) S.P.G. Costa, S.M.M.A. Pereira-Lima, H.L.S. Maia. Org. Biomol. Chem., 1 (2003)
1475. b) W.-Q. Jiang, S.P.G. Costa, H.L.S. Maia. Org. Biomol. Chem., 1 (2003) 3804.
[2] Costa, S.P.G., Maia, H.L.S., Pereira-Lima, S.M.M.A. in Benedetti, E. and Pedone, C.
(Eds.), Peptides 2002, Proceedings of the 27th European Peptide Symposium,
Edizioni Ziino, 2002, Naples, p. 250.
[3] Costa, S.P.G., Maia, H.L.S., Pereira-Lima, S.M.M.A. in M. Chorev and T. Sawyer
(Eds.), Peptide Revolution: Genomics, Proteomics & Therapeutics, Proceedings of
the 18th American Peptide Symposium, American Peptide Society/Kluver, USA,
2004, p. 85.
218


REACTIVITY OF C-VINYL-1H-PYRROLES

Maria I. L. Soares, Susana M. M. Lopes, Teresa M. V. D. Pinho e Melo*
Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
*tmelo@ci.uc.pt

We have previously observed that pyrroles with the general structure 1 can
rearrange to give 5-oxo-5H-pyrrolizines 2 or functionalized C-allyl-1H-pyrroles
3 depending on the substitution pattern of the starting pyrrole [1c].

The work has now been extended to the thermolysis of new 1,1-dimethyl-
and 1-methyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxides (e.g. 4 and 8),
precursors of C-vinyl-1H-pyrroles via sigmatropic [1,8]H shift of azafulvenium
methides (e.g. 5), in order to evaluate the scope of the interesting rearrangement
of C-vinylpyrroles to C-allylpyrroles. We could conclude that 2-isopropenyl-
1H-pyrroles require the presence of an aryl substituent at C-5 or a benzyl group
at N-1 in order to rearrange to the corresponding C-allyl-1H-pyrroles. This is not
the case for the 2-ethenyl-1H-pyrroles although the presence of a phenyl group at
C-5 allows the selective synthesis of the C-allyl-1H-pyrrole (e.g. 9). The
reactivity of pyrroles 10 was also studied and the results obtained will be
disclosed.



Acknowledgements: Thanks are due to FCT (Project PTDC/QUI/64470/2006; Grant
SFRH/BPD/26772/2006) and FEDER for financial support.

[1] a) T.M.V.D. Pinho e Melo, M.I.L. Soares, A.M.d'A. Rocha Gonsalves, J.A. Paixo,
A. Matos Beja, M. Ramos Silva, J. Org. Chem. 70 (2005) 6629; b) T.M.V.D. Pinho e
Melo, M.I.L. Soares, C.M. Nunes Tetrahedron 63 (2007) 1833.
[2] a) T.M.V.D. Pinho e Melo, M.I.L. Soares, A.M.d'A. Rocha Gonsalves Tetrahedron
Lett. 47 (2006) 791; b) T.M.V.D. Pinho e Melo, C.M. Nunes, M.I.L. Soares, J.A.
Paixo, A. Matos Beja, M. Ramos Silva, J. Org. Chem. 72 (2007) 4406.
R
1
= Me; R
2
= Ph
R
1
= H; R
2
= Me
R
1
= Me; R
2
= H
R
1
= R
2
= Me
R
1
= R
2
= H
N
R
2
MeO
2
C CO
2
Me
Me
R
1
N
R
1
O
R
2
Me
MeO
2
C
N
H
MeO
2
C CO
2
Me
Me
R
2
R
1
Flash Vacuum
Pyrolysis
Flash Vacuum
Pyrolysis
2
3 1
N O
2
S
CO
2
Me
CO
2
Me
Ph
Me
N
H
MeO
2
C CO
2
Me
Ph
Me
Me
FVP
54%
N
R
1
R
2
10a R
1
= Bn; R
2
= CO
2
Bn; R
3
= H
10b R
1
= Bn; R
2
= CO
2
Me; R
3
= H
10c R
1
= Et; R
2
= CO
2
Bn; R
3
= H
10d R
1
= Bn; R
2
= R
3
= H
10e R
1
= Bn; R
2
= Me; R
3
= H
10f R
1
= Bn; R
2
= H; R
3
= Me
N
R
1
R
2
Ar
H
Me
Me
N O
2
S
R
1
R
2
Ar
Me
Me
Me
4a R
1

= R
2

= CO
2
Me; Ar = C
6
H
4
F-p
4b R
1

= R
2

= CO
2
Me; Ar = Ph
4c R
1

= Ph; R
2

= CO
2
Et; Ar = C
6
H
4
F-p
FVP
N
R
1
R
2
Ar
+
N
H
R
1
R
2
Ar
Me Me
Me
Et
- SO
2
5
6 7
8 9
R
3
219


Esquema 1.
SNTESE DE DERIVADOS DIPEPTDICOS DE
FRMACOS CONTENDO O GRUPO AMIDA

Joana Matos*, Paula Gomes
CIQUP, Departamento de Qumica, Faculdade de Cincias, Universidade do Porto, Rua
do Campo Alegre 687, P-4169-007 Porto, Portugal
*joana_mat@hotmail.com

O desenvolvimento de pr-frmacos tem permitido melhorar o ndice
teraputico de diversos frmacos, por alterao das suas propriedades fsico-
qumicas. Os pr-frmacos por si s so inactivos, mas originam in vivo um ou
mais metabolitos activos, entre os quais o frmaco parental, atravs de activao
enzimtica ou qumica. A maioria dos pr-frmacos so steres derivados de
frmacos contendo grupos carboxilo ou hidroxilo e sofrem essencialmente
activao por via enzimtica. Contudo, a activao enzimtica afectada pela
variabilidade biolgica, o que justifica a procura de estruturas activveis
exclusiva ou preferencialmente por via qumica [1].
O nosso grupo de investigao tem vindo a
trabalhar com derivados dipeptdicos de frmacos
hidroxilados e aminados, activveis atravs de uma
reaco de ciclizao-eliminao que envolve a
libertao do frmaco parental e da dicetopiperazina
derivada do transportador dipeptdico (Esquema 1),
tendo-se observado que a facilidade com que ocorre
esta activao qumica depende do pK
a
do frmaco
enquanto grupo abandonante [2-4].
Recentemente, iniciamos o estudo da aplicao
desta estratgia a frmacos contendo o grupo amida,
nomeadamente, a valpromida, a etosuccimida e a
fenacetina, pretendendo apresentar nesta comunicao
os resultados do estudo da sntese de derivados
dipeptdicos destes trs frmacos. Os resultados
modestos obtidos por aplicao de mtodos clssicos
de condensao peptdica reflectiram a baixa
reactividade das amidas e a necessidade de recorrer a
condies mais drsticas para obteno dos produtos-
alvo com sucesso.

[1] P. Gomes, N. Vale, R. Moreira. Molecules 12 (2007) 2484.
[2] P. Gomes, J.R.B. Gomes, M. Rodrigues, R. Moreira. Tetrahedron 59 (2003) 7473.
[3] C.R. Santos, M.L. Mateus, A.P. Santos, R. Moreira, E. Oliveira, P. Gomes. Bioorg.
Med. Chem. Lett. 15 (2005) 1595.
[4] C.R. Santos, J. Morais, L. Gouveia, E. de Clercq, C. Pannecouque, C.U. Nielsen, B.
Steffansen, R. Moreira, P. Gomes. Chem. Med. Chem., accepted (2008).

H
2
N
H
N
X
R
2
R
1
O
O
HN
NH
R
2
O
R
1
O
HX +
X=RO-, RS-, RNH-, RCONH-
220


ELECTROCHEMICAL EVALUATION OF THE REDOX-
PROPERTIES OF DIARYLAMINES IN THE 2,3-
DIMETHYLBENZO[B]THIOPHENE SERIES

Soraia Falco
a
, Rui M. V. Abreu
a
, Isabel C. F. R. Ferreira
a
*, Miguel
Vilas-Boas
a
*,

Maria-Joo R. P. Queiroz
b
a
CIMO-ESAB, Instituto Politcnico de Bragana, Campus de Sta. Apolnia, 1172, 5301-
855 Bragana, Portugal

b
Centro de Qumica, Campus de Gualtar, Univ. do Minho, 4710-057 Braga, Portugal
*iferreira@ipb.pt; mvboas@ipb.pt

The antioxidant properties of 7-aryl or 7-heteroarylamino-2,3-
dimethylbenzo[b]thiophenes previously reported by us (1) make them very
important as radical scavengers. Powerful electrochemical techniques such as
cyclic voltammetry can provide a deeper insight into the redox-processes of
oxidative stressors and antioxidants. The evaluation of the redox-properties of
the synthesised compounds allows structureactivity relationship (SAR) studies,
concerning the influence of different groups on the phenyl ring.
Cyclic voltammograms were
recorded using an Autolab PGSTAT
302 with a typical three electrode cell.
The electrochemical studies were
performed in acetonitrile/TBAP,
either with platinum or glassy carbon
working electrodes. Voltammogram
of compound 1, collected at 1 Vs
-1

present three irreversible oxidation
processes with E
p/2
at 0.81, 1.1 and
1.6 V, with a higher current density
observed in glass carbon, as expected
for organic compounds due to adsorption phenomena. This redox behaviour is
common to all other chemical species studied, although the anodic processes
have different potential values due to the influence of the substituents in the
phenyl ring: compounds with electron donor groups on the arylamine moiety,
such as 2c, have lower E
p/2
relative to compounds with electron withdrawing
groups like 2d. The position of the methoxy group on the arylamine fragment
also changes the oxidation potential: lower E
p/2
for methoxy group in para
position (2a vs 2b). For heteroarylamino compounds the position of connection
with the benzothiophene structure does not seem to influence significantly the
redox properties (3a vs 3b). Comparing the first peak potential with the patterns
of synthetic antioxidants, BHA and BHT, diarylamine compounds show lower
oxidation potential, and therefore higher reducing power.
Acknowledgements: Research Project POCI/QUI/59407/2004 (FCT-Portugal).
[1] Queiroz et al. Bioorg. Med. Chem. 15 (2007) 1788.
Z
Y
R
2
N
R
1
H S
S
NH
2
1
2a R
1
=H, R
2
=OMe
2b R
1
=OMe, R
2
=H
2c R
1
=R
2
=OMe
2d R
1
=H, R
2
=CN
3a R
1
=R
2
=H, Y=CH, Z=N
3b R
1
=R
2
=H, Y=N, Z=CH
Y=Z=CH
unless stated
221


DOCKING STUDIES OF INDOMETHACIN DERIVATIVES
IN CYCLOOXYGENASE-2 BINDING SITE

Ana M. D. Ramos*, A. Gil Santos, Eurico J. Cabrita, Maria M. B.
Marques
REQUIMTECQFB, Dep. de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
*anamargarida.dr@gmail.com

Cyclooxygenases (COX-1 and COX-2) are enzymes involved in
prostaglandin biosynthesis through the oxidation of arachidonic acid. These
enzymes play an important role in cellular homeostasis and in the mediation of
the inflammatory response [1]. COX-1 is considered a constitutive isozyme,
being important to the maintenance of
vascular homeostasis, while COX-2 is
seen as induced by proinflammatory
states. The selective inhibition of COX-2
is useful for the treatment of
inflammation with low side effects [2].
Therefore, the development of non-
steroidal anti-inflammatory drugs
(NSAIDs) as selective inhibitors of
cyclooxygenase-2 has become a very
interesting area of investigation in
Medicinal Chemistry over the last two
decades [3].
In the present work, molecular
docking studies were applied to several
indomethacin derivatives in order to
evaluate a possible selective activity and understand their binding mode through
the observation of their most favourable interactions in the COX-2 catalytic
domain.
According to the studies the majority of the tested compounds appear to bind
the COX-2 binding site differently from indomethacin, having in some of the
cases the same orientation as the selective inhibitor SC-558 (Figure 1).

Acknowledgements: We thank Fundao para a Cincia e Tecnologia for partial financing
support PTDC/QUI/65187/2006.

[1] Kristina E. Furse; Derek A. Pratt. Biochemistry 45 (2006) 3206.
[2] Afshin Zarghi; Leila Najafnia. Bioorg. Med. Chem. Lett. 17 (2007) 5634.
[3] Hwangseo Park; Jinuk Lee; Sangyoub Lee. Proteins: Structure, Function, and
Bioinformatics 65(2006) 549.
Figure 1.
222


SYNTHESIS AND CHARACTERIZATION OF A PGN
MONOMER WITH BIOLOGICAL INTEREST

Lusa R. Carvalho
a
*, Srgio R. Filipe
b
, M. M. Pereira
a
, Maria M. B.
Marques
a

a
REQUIMTE, Departamento de Qumica, Faculdade Cincias e Tecnologia,Universidade
Nova de Lisboa, 2829-516 Caparica, Portugal
b
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. da
Repblica (EAN), Oeiras, Portugal
*luisa_carvalho@dq.fct.unl.pt

The innate immune system constitutes
the first line of defense against
microorganisms in both vertebrate and
invertebrates, and recognizes invading
pathogens by some associated molecular
patterns. Peptidoglycans (PGNs) are the
major components of the bacterial cell
wall and one of these recognizable
structures. PGNs are large polymers
composed of alternating |(1-4) linked N-
acetylglucosamine (GlcNAc) and N-
acetylmuramic acid (MurNAc) residues,
cross-linked by short peptide chains.
Recent studies revealed that the PGN
minimal structure required to activate the Drosophila Toll pathway is a dimeric
muropeptide (Figure 1), and that the free reducing end of the N-acetyl muramic
acid residue is needed for activity [1].
Our studies towards the total synthesis of 1 are now focused on the PGN
monomer synthesis. Herein, we report the recent developments towards the
synthesis of the monomer unit of 1. The synthetic strategy consists on the
coupling of its three major fragments: the disaccharide unit (A), the peptide
chains (B) and the crossbridge (C).
The disaccharide construction consists on a strategy based on an orthogonal
protection of N-Troc (N-trichloroethoxycarbonyl) glucosamine derivatives [2].
This approach ensures better yields on glycosilation, flexibility for the
attachment of the carboxylic group of MurNAc moiety to the peptide chain, and
the total deprotection is performed at a later stage of the synthesis. Peptide
chains (B) and (C) are prepared using Fmoc SPS (solid phase synthesis)
approach [3].

[1] S. R. Filipe, A. Tomasz, P. Ligoxygakis EMBO reports 6 (2005) 1.
[2] C. Wong et al. J. Am. Chem. Soc. 121 (1999) 734.
[3] S. Kumar et al. J. Biol. Chem. 280 (2005) 37005.
Figure 1.
223


Figure 1. Structure of
tryptophan
SYNTHESIS OF AN INDOLE LIBRARY AND EVALUATION
OF ITS IN VITRO ANTIOXIDANT ACTIVITY

Mnica S. Estevo
a
*, Ana Gomes
b
, Eduarda Fernandes
b
, Lusa P.
Ferreira
a
, Maria M. B. Marques
a

a
REQUIMTE, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia, Universidade
do Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*monica.estevao@gmail.com

Natural products incorporating an indole moiety correspond to a broad
chemical family ubiquitously found in microorganisms, plants and animals. This
type of compounds is mainly related to the tryptophan metabolism. The most
important members of the family are the plant
hormone, indole-3-acetic acid, and the animal
hormone, melatonin. An important characteristic
of indole-containing compounds is that they may
be useful as chemical preventive agents against
inflammation and oxidative stress related diseases,
like cancer and neurodegenerative diseases [1, 2].
In order to study the structure-activity
relationship an indole based library was
synthesised and the antioxidant activity of the
obtained compounds was evaluated by studying their scavenging activity against
the reactive oxygen species peroxyl radical (ROO

).
All except one of the tested compounds demonstrated activity against ROO

.

Acknowledgements: We thank Fundao para a Cincia e Tecnologia for partial financing
support PTDC/QUI/65187/2006.

[1] E. Fernandes, D. Costa, S.A. Toste, J.L.F.C. Lima, S. Reis. Free Rad. Biol. Med. 37
(2004) 1895.
[2] S. Stolc. Life Sci. 65 (1999) 1943.

N
H
NH
2
CO
2
H
224


AVALIAO DA INTERACO DO IBUPROFENO E DA
INDOMETACINA COM MODELOS MEMBRANARES

Diana Gaspar
a
*, Kerstin Wagner
b
, Gerald Brezesinski
c
, Jos L. F. C.
Lima
a
, Marlene Lcio
a
, Salette Reis
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-30 Porto, Portugal
b
MEMPHYS - Center for Biomembrane Physics University of Southern Denmark,
Campusvej 55, 5230 Odense M, Denmark
c
Max Planck Institute of Colloids and Interfaces, Wissenschaftspark, Golm 14424
Potsdam, Germany
*diana.gaspar@gmail.com

A interaco frmaco-membrana de extrema importncia quando se
pretende avaliar ou clarificar aspectos relativos ao mecanismo de aco do
frmaco em estudo. Esta interaco pode surgir porque o frmaco tem aco
sobre um processo que ocorre na superfcie celular ou porque se torna necessrio
atravessar a membrana para atingir um alvo intracelular. Deste modo, a avaliao
do efeito de frmacos sobre a membrana celular pode tambm contribuir para a
explicao de certos efeitos secundrios que ocorrem associados ao tratamento
com o frmaco. Os Anti-Inflamatrios No Esterides (AINEs) tm sido alvos
constantes de modificaes estruturais com o objectivo de reduzir o nmero de
efeitos secundrios que lhes so atribudos, sendo a toxicidade gstrica um dos
mais severos. Esta toxicidade poder resultar da aco do frmaco sobre os
fosfolpidos das membranas celulares.
Assim sendo, foi feita a avaliao da interaco de dois AINEs, o ibuprofeno
e a indometacina, com a bicamada lipdica usando lipossomas e monocamadas
lipdicas como modelos de membranas.
Esta interaco foi investigada, de uma forma directa, por tcnicas de
calorimetria diferencial de varrimento (DSC) que permitem estudar as variaes
dos parmetros termodinmicos decorrentes da interaco frmaco-lpido. Foi
igualmente avaliada, de uma forma indirecta, por fluorescncia resolvida no
tempo, atravs da determinao dos tempos de vida de uma sonda fluorescente
(1,6-difenil-1,3,5-hexatrieno, DPH) incorporada na matriz lipdica de
lipossomas. Foram, ainda, realizados ensaios com base na execuo de
isotrmicas de Langmuir associadas a Brewster Angle Microscopy (BAM) nos
sistemas constitudos por monocamadas de fosfolpidos dispersos numa soluo
de frmaco, o que permitiu captar imagens da estrutura lipdica ao mesmo tempo
que se comprimem as monocamadas.

Agradecimentos: Os autores agradecem FCT e FEDER pelo apoio financeiro obtido no
mbito do projecto PTDC/SAU-FCF/67718/2006. Diana Gaspar agradece FCT a bolsa
de doutoramento atribuda (SFRH/BD/29308/2006).
225


ESTUDO DA ACTIVIDADE E INIBIO DA
FOSFOLPASE A2 POR ACO DO MELOXICAM

Salette Reis*, Diana Gaspar, M. Lcia M. F. S. Saraiva, Jos L. F. C.
Lima, Marlene Lcio

REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-30 Porto, Portugal
*
shreis@ff.up.pt

Os Anti-Inflamatrios No Esterides (AINEs) constituem um dos grupos
teraputicos mais prescritos para o tratamento de inflamaes crnicas e agudas.
O seu mecanismo de aco passa pela inibio da enzima ciclooxigenase (COX)
com a consequente inibio da produo de mensageiros inflamatrios. Para
alm da inibio da COX, alguns AINEs inibem outras enzimas, nomeadamente
a fosfolpase A2 (PLA2), enzima envolvida no primeiro passo da cascata
inflamatria (libertao de cido araquidnico da membrana celular). Em virtude
desta inibio poder contribuir de alguma forma para o mecanismo anti-
inflamatrio destes frmacos, foram efectuados estudos de inibio da PLA2
pelo AINE meloxicam.
O estudo foi realizado usando modelos membranares (lipossomas de
fosfatidilcolina de gema de ovo, EPC, com 20% de dipalmitoil-glicero-fosfato,
DPPG) que pretendem mimetizar as membranas biolgicas e simplificar a
interpretao dos resultados obtidos constituindo, ao mesmo tempo, o alvo de
aco daPLA2. A utilizao de uma sonda fluorescente, ADIFAB (AcryloDated
Intestinal Fatty Acid Binding protein) permitiu avaliar a concentrao de cidos
gordos produzida ao longo do tempo como resultado da hidrlise efectuada pela
PLA2 sobre os lipossomas. Foram igualmente realizados alguns ensaios de
fluorescncia e Brewster Angle Microscopy (BAM) com o objectivo de
esclarecer o mecanismo da inibio da PLA2 por este anti-inflamatrio.
Os resultados obtidos mostram que o meloxicam capaz de inibir a
actividade da PLA2 e que esta inibio aumenta com a concentrao de frmaco
testada.

Agradecimentos: Os autores agradecem FCT e FEDER pelo apoio financeiro obtido no
mbito do projecto PTDC/SAU-FCF/67718/2006. Diana Gaspar agradece FCT a bolsa
de doutoramento atribuda (SFRH/BD/29308/2006).
226


INTERACTION OF NSAIDS WITH DMPC LIPOSOMES:
STUDIES OF PARTITION, LOCATION AND
MEMBRANE FLUIDITY

Cludia Nunes*, Diana Gaspar, Katarzyna Gobska, Micha
Winiewski, Jos L. F. C. Lima, Salette Reis, Marlene Lcio
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-30 Porto, Portugal
*claununes@portugalmail.pt

Non-steroidal anti-inflammatory drugs (NSAIDs) are a group of drugs widely
employed in the treatment of inflammatory diseases, with an effect on the
physical properties of the membrane lipid bilayer [1]. In this study, fluorescence
anisotropy measurements of liposomes labeled with the probe 1,6-diphenil-1,3,5-
hexatriene (DPH) were used to assess the influence of four different NSAID
(nimesulide, tolmetin, acemetacin and indomethacin) in membrane fluidity and
structure.
Unilamellar liposomes (LUV) of dimyristoylphosphatidylcholine (DMPC),
prepared by the thin film hydration method were used as biomembranes models
and the liposome/aqueous phase partition coefficient was determined by
derivative spectrophotometry.
The location of the drugs in the lipid membrane bilayers was also studied by
fluorescence quenching measurements, using the same probe. These studies
revealed that the NSAIDs studied were able to efficiently quench the probe
located in membrane hydrocarbon region and showed an increase in the
membrane fluidity in a concentration dependent manner.
Other factor that affects both order and membrane fluidity is the lipid main
transition phase from gel to the liquid-crystalline state. According to this,
fluorescence anisotropy measurements were also performed in a range of
temperatures (10C 40C) in the absence or in the presence of NSAIDs to
evaluate the influence of the drugs changing the main phase transition
temperature described in literature for DMPC as 23,5 C [2].
Results obtained provide an insight into NSAIDs capacity to be inserted in
lipid bilayers and alter the lipid dynamics. The induced changes in lipid
dynamics may modulate the activity of inflammatory enzymes or may be related
with deleterious topical action of NSAIDs on gastric phospholipid fluidity.

Acknowledgements: Partial financial support for this work was provided by Fundao para
a Cincia e Tecnologia (FCT Lisbon), through the contract PTDC/SAU-
FCF/67718/2006. C.N. Thanks FCT for the fellowship (SFRH/BD /38445/2007).

[1] Lcio M, Reis S, Lima J.L.F.C, Bringezu F, Brezezinski G. Langmuir (2008) in press
[2] Lasic D.D. Liposomes - from Physics to Applications. Elsevier. New York, 1993.
227


INTRAMOLECULAR HYDROGEN BONDING IN 4-
AMINO-3,5-DI-PIRYDYL-4H-1,2,4-TRIAZOLE CRYSTALS

Joana A. Silva
a
*, Cludia T. Arranja
a
, Ana F. P. V. Ferreira
a
, Nuno
D. Martins
b
, Manuela R. Silva
b
, Ana Matos Beja
b
, Ablio J. F. N.
Sobral
a
a
Departamento de Qumica, FCTUC, Univ. de Coimbra, 3004-535 Coimbra, Portugal
b
CEMDRX, Dep. de Fsica, FCTUC, Univ. de Coimbra, 3004-516 Coimbra, Portugal
*joanalmeida.silva@gmail.com

The development of bacteria resistance to current antibacterial therapies is
nowadays the basis for the search for more effective agents. The azole antifungal
family may be regarded as a new class of compounds providing truly effective
fungi inhibition by blocking the biosynthesis of certain fungal lipids, especially
ergosterol, in cell membranes, among other additional mechanisms [1,2].
Triazoles, in particular, substituted-1,2,4-triazoles and the open-chain
thiosemicarbazide counterparts of 1,2,4-triazole, are among the nitrogen
heterocycles that received most attention during the last two decades as potential
antimicrobial agents. Therefore, the exact knowledge of the nature of the
chemical and physical interactions developed between the triazoles and other
species in biological media, namely metal cations and bio-polyelectrolites, is of
upmost importance.



Figure 1. ORTEP diagram of 4-amino-3,5-di-pirydyl-4H-1,2,4-triazole; the ellipsoids are
drawn at the 50% probability level . Packing diagram of the title compound, showing the
intramolecular hydrogen bonds.

An aspect of the study of those interactions which determines their solubility
and coordination ability between triazoles and biological species is related to the
existence of strong intramolecular hydrogen bonds in substituted triazoles. This
aspect is addressed in the present communication, aiming to elucidate the
importance of that process in the real bio-availability of the substituted-1,2,4-
triazoles in biological media.

[1] G. Turan-Zitouni, Z. A. Kaplancikli, M. T. Yildiz, P. Chevallet, D. Kaya. Eur. J. Med.
Chem 40 (2005) 607.
[2] C. Oefner, A. Douangamath, A. DArcy, S. H. D. Mareque, A. M. Sweeney, J. Padilla,
S. P. H. Schulz, M. Thormann, S. Wadman, G. E. Dale J. Mol. Biol. 332 (2003) 13.
228


CRYSTAL STRUCUTRE CHARACTERIZATION OF
ETHYL 3,5-DIMETHYL-1H-PYRROLE-2-CARBOXYLATE

Cludia T. Arranja
a
*, Joana A. Silva
a
, Ana F. P. V. Ferreira
a
,
Manuela R. Silva
b
, Ana Matos Beja
b
, Ablio J. F. N. Sobral
a
a
Dep. de Qumica, FCTUC, Universidade de Coimbra, 3004-535 Coimbra, Portugal
b
CEMDRX, Dep. Fsica, FCT, Universidade de Coimbra, 3004-516 Coimbra, Portugal
*claudiammtavares@mail.pt

Cancer is a group of diseases that has been growing in our society in the last
decades. Its medical and social importance led to the development of several
therapies, which constitute one of the most important fields in the scientific
media. One of those therapies, Photodynamic Therapy (PDT), is based on the
combined action of a photo-sensitizer, light and oxygen and has presented very
promising results on the treatment of different types of cancers. The importance
of porphyrins as therapeutic agents for PDT has been growing in the last years
due to their suitable photochemical and photophysical properties. This has been
the base of a growing applicability of these compounds in PDT. Therefore, its
important to possess the adequate synthetic methods to build libraries of
porphyrins whose structures cover a great range of possibilities in terms of
physical and chemical properties. The synthesis of asymmetric porphyrins with
substituents on the pyrrolic rings is therefore of great interest.

Figure 1. ORTEP II scheme of ethyl 3,5-dimethyl-1H-pyrrole-2-carboxylate: the
ellipsoids are drawn at the 50% probability level. View of the unit cell along b axis:
a=8.1357(2) , b=10.5568(2) , c=12.1428(2) ; o=101.545(1), |=97.879(1),
=110.482(1); the molecules are joined in dimmers through hydrogen bonds

As building blocks, for preparation of asymmetric porphyrins, we
synthesized by the Knorr method and characterized by X-ray crystallography, the
ethyl 3,5-dimethyl-1H-pyrrole-2-carboxylate. This pyrrole is a precursor of
porphyrins without substituents in the meso positions of the macrocycle, similar
in structure to the natural occurring hematoporphyrins and protoporphyrins.

[1] R. Bonnet, Chemical Aspects of Photodynamic Therapy, Gordon and Breach Science
Publishers, Amsterdam, 2000.
[2] S.K. Pushpan, S.Venkatrament, V.G. Anaud, J. Sankar, D. Parmeswararan, S.
Ganesan, T.K. Chandrashekar. Curr. Med. Chem. 2 (2002) 187.
[3] K. Lang, J. Mosinger, D.M. Wagnerov. Coord. Chem Rev. 248 (2004) 321.
229


NEW INDAZOLE AND CONDENSED PYRAZOLE
BISPHOSPHONATES

Ftima C. Teixeira
a
*, Carla Lucas
a
, Ins F. Antunes
a
, M. Joo M.
Curto
a
, M. Neves
b
, M. Teresa Duarte
c
, Vnia Andr
c

a
INETI-DTIQ, Estrada do Pao do Lumiar, 22, 1649-038 Lisboa, Portugal
b
Instituto Tecnolgico e Nuclear, Estrada Nacional, 10, 2686-953 Sacavm, Portugal
c
Centro de Qumica Estrutural, IST, Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal
*fatima.teixeira@ineti.pt

Bisphosphonates (BPs) are synthetic drugs that are effective in treating
benign and malignant skeletal diseases characterized by enhanced osteoclast-
mediated bone resorption (i.e., osteoporosis, Pagets disease, and tumor-induced
osteolysis). In addition, functional BPs have been also used as novel ligands for
well-defined radioactive metal complexes that can be used in imagiology,
scintigraphy and radiotherapy applications [1, 2]. BPs are stable, water-soluble,
synthetic analogues of naturally occurring pyrophosphonates (P-O-P) in which
the central oxygen atom is replaced by a carbon atom (P-C-P), thereby making
BPs resistant to enzymatic degradation and usually with low toxicity [1]. The
biological activities of these compounds are determined by the nature of the
alkyl moiety bound to the bisphosphonic structure as well as the functional
groups located on the alkyl chain, with the nitrogen-containing homologues,
such as risedronate and zoledronate, amongst the most potent BPs.
Herein, we report the synthesis and characterization of a series of new 1-
hydroxybisphosphonates and aminobisphosphonates derived from indazole and
condensed pyrazole with potential biological activities. Crystal structures of
hydroxybisphosphonate and aminobisphosphonates were determined by X-ray
crystallography (Figure 1). The new BPs were evaluated as ligands for
complexation with radionuclides and submitted to studies in vitro
(hydroxyapatite binding studies simulating bone mineral uptake).

Figure 1

Acknowledgements: To FCT (FEDER, POCI) for provision of funding (POCI/QUI/55508/
2004).

[1] R.G.G. Russell, M.J. Rogers. Bone 25 (1999) 97.
[2] S. Zhang, G. Gangal, H. Uludag. Chem. Soc. Rev. 36 (2007) 507.
BP 1 BP 2
230


ESTUDO TERMOQUMICO DE DERIVADOS DO
NITROTIOFENO

Ana Filipa L. O. M. Santos*, Manuel A. V. Ribeiro da Silva
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias
da Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
*ana.santos@fc.up.pt

Nos ltimos tempos tem vindo a ser realizado, no nosso Centro de
Investigao, um vasto estudo termoqumico de compostos derivados do tiofeno,
cujo principal objectivo reside no estabelecimento de correlaes entre a sua
estrutura e reactividade.
Estes heterociclos de enxofre so de extrema importncia, encontrando
aplicaes em reas primordiais como a medicina, cincias farmacuticas ou em
novas tecnologias e desenvolvimento de novos materiais. Neste contexto, o
estudo energtico dos derivados do tiofeno e, neste caso particular dos seus
derivados nitro, assume uma maior relevncia, dado contribuir para uma melhor
compreenso da sua reactividade.
Neste trabalho so apresentadas as entalpias molares de formao padro (p
= 0.1 MPa), em fase cristalina, a T = 298.15K, dos 2-nitrotiofeno, 2-acetil-5-
nitrotiofeno e 5-nitro-2-tiofenocarboxaldedo, calculadas a partir dos respectivos
valores de energias mssicas de combusto padro, obtidas por calorimetria de
combusto em bomba rotativa. Para estes compostos, foram medidas as suas
presses de vapor em funo da temperatura, pelo mtodo de efuso de Knudsen.
Atravs desta dependncia determinou-se, para cada composto, a respectiva
entalpia molar de sublimao padro, a T = 298.15K, a partir da equao de
Clausius-Clapeyron. Os resultados experimentais obtidos permitiram o clculo
das entalpias molares de formao padro (p = 0.1 MPa), em fase gasosa e a T =
298.15 K, as quais so comparadas e discutidas com idnticos parmetros
obtidos em compostos estruturalmente semelhantes.

Agradecimentos: Agradece-se Fundao para a Cincia e Tecnologia (FCT), e ao
FEDER o apoio financeiro prestado ao Centro de Investigao em Qumica da
Universidade do Porto. A.F.L.O.M.S. agradece FCT a bolsa de Doutoramento
(SFRH/BD/12886/2003).

231


Figura 1. Frmula de estrutura
dos compostos 5-bromoindole (A)
e 5-bromoindolina (B)
H
N
Br
H
N
Br
A
B
TERMOQUMICA DOS COMPOSTOS
5-BROMOINDOLE E 5-BROMOINDOLINA

Joana I. T. A. Cabral*, Manuel A. V. Ribeiro da Silva
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias
da Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
*jicabral@fc.up.pt

A determinao dos parmetros termodinmicos e o conhecimento da sua
relao com a estrutura, energia e reactividade das molculas, constitui um dos
aspectos fundamentais para a cincia qumica.
nesse contexto que se insere o presente trabalho, referente aos derivados do
indole, como parte de um estudo mais vasto, relativo termoqumica de
compostos heterocclicos azotados, levado
a efeito pelo nosso grupo de investigao.
Com o objectivo de compreender a
influncia da presena de um substituinte
bromo na energtica destes compostos,
determinaram-se as entalpias molares de
formao padro, (p = 0.1 MPa), em fase
gasosa, do 5-bromoindole (A) e 5-
bromoindolina (B).
Para tal, determinaram-se as respectivas energias mssicas de combusto
padro, por calorimetria de combusto em bomba rotativa, a T = 298.15 K, bem
como as entalpias molares de sublimao padro, mesma temperatura, por
microcalorimetria Calvet.
Os resultados obtidos para as entalpias molares de formao padro, em fase
gasosa dos dois compostos objecto deste estudo, so discutidos em termos de
incremento entlpico e interpretados relativamente sua estrutura molecular.

Agradecimentos: Agradece-se Fundao para a Cincia e Tecnologia (FCT) e ao
FEDER o financiamento concedido ao Centro de Investigao em Qumica da
Universidade do Porto. J.I.T.A.C. agradece FCT a bolsa de ps-doutoramento
(SFRH/BPD/27140/2006).


232


CHEMICAL CALIBRATION OF ISOTHERMAL TITRATION
CALORIMETERS: A TEST REACTION AT 308.15 K

R. Ado
a
*, G. Bai
a
, R. Sassonia
b
, W. Loh
b
, M. Bastos
a

a
Centro de Investigao em Qumica (UP) CI Q (UP), Department of Chemistry,
Faculty of Sciences, University of Porto, Rua do Campo Alegre, 687, P-4169-007, Porto,
Portugal
b
Universidade Estadual de Campina (UNICAMP) - Campinas, SP, Brasil
*radao@fc.up.pt

Calibration protocols are amongst one of the most important procedures in
any accurate calorimetric work. It is well known that in many cases
discrepancies between works from different laboratories can be accounted for by
differences in calibration procedures or standards used.
Titration calorimeters can be calibrated electrically. Since the energy supplied
in this way can be determined in most cases more accurately than the calorimetric
signal itself, it provides an easy and very accurate method. Nevertheless, as it has
been stressed before [1, 2], in most cases the electrical calibration with a permanent
heater provided with the instrument is not good enough for very accurate work,
due to instrument design. The use of insertion heaters is not common, although
providing extremely accurate calibration constants, as they are usually home-
made devices [3]. Therefore, the standardized chemical calibration procedures
tested for different equipments are mandatory.
In our laboratory we have been doing some systematic work in this respect
for a Lund dissolution vessel, nowadays commercialized by Thermometric
AB/TA. In the present work, we did test thoroughly the possibility of two
chemical calibration to be used with Isothermal Titration Calorimeters. These
reaction have been suggested before for solution calorimetry [1, 4] - the dilution
of sucrose and n-propanol aqueous solutions.
Dilution of sucrose was tested in the Thermometrics 1 mL titration cell, by
using 15, 20 and 25% (w/w) solutions, with different injection volumes. Dilution
of a 10% n-propanol solution was used with both the Thermometric 1 mL cell
and the VP-ITC (Microcal).
Since we determined the calibration constant by use of an insertion heater,
we were able to provide a new experimental value for the enthalpy of dilution of
10% n-propanol solution at 308.15 K (35C), a temperature most useful for
biocalorimetric work.
Acknowledgments: Thanks are due to FCT for financial support to CIQ (UP), for a Post-
Doc grant to G.B. (SFRH/BPD/5668/2001) and a PhD grant to R.A. (SFRH/BD/24055
/2005).
[1] L.-E. Briggner, I. Wads J. Biochem. Biophys. Methods 22 (1991) 101.
[2] I. Wads Thermochim. Acta 347 (2000) 73.
[3] M. Bastos, L.-E. Briggner, I. Shehatta I. Wads J. Chem. Thermodynamics 22 (1990)
1181.
[4] G. Olofsson, D. Berling, N. Markova, Mary Molund Thermochim. Acta 347 (2000) 31.
233


APPLICATION OF GENETIC ALGORITHMS IN
CHEMISTRY: FROM FITTING THE POTENTIAL
ENERGY TO THE STUDY OF CLUSTERS

Jorge M. C. Marques
a
*, Francisco B. Pereira
b,c
a
Departamento de Qumica, Universidade de Coimbra, 3004-535 Coimbra, Portugal
b
Instituto Superior de Engenharia de Coimbra, Quinta da Nora, 3030-199 Coimbra,
Portugal
c
Centro de Informtica e Sistemas da Universidade de Coimbra (CISUC), 3030-290
Coimbra, Portugal
*qtmarque@ci.uc.pt

Since the early of last decade genetic algorithms (GAs) have been applied to
solve several optimization problems in chemistry. Indeed, GAs revealed to be a
powerful tool for searching the global optimum in difficult cases such as atomic
clusters geometry optimization (see Ref. [1] and references therein) and protein
folding [2]. There have been also applications to deal with the fitting process of
experimental data (see Refs. [3] and references therein). Recently, a GA using a
binary representation has been applied to fit the potential energy curves of both
H
2
+
and Li
2
[4]; however, these curves cannot reproduce the corresponding
spectra with an accuracy below 1 cm
-1
(discrepancies as large as 5.79 cm
-1
and
31.45 cm
-1
are observed [4] for H
2
+
and Li
2
, respectively). In the same context,
we have obtained spectroscopic accuracy for Ar
2
and NaLi by employing a new
full generational real-valued GA in a direct fit of both ab initio and experimental
vibration data [5]. These results are encouraging in the perspective of applying
GAs for the difficult task of fitting multidimensional potential energy surfaces.
Another important topic of our research is related to the use of GAs for
searching the global minimum structure of atomic clusters. In particular, we have
applied our recently developed GA [6, 7] to study the influence of the potential
energy surface on the global minimum of rare gas clusters [8]; only in a reduced
number of clusters the differences among the model potentials are significant.
The main results will be presented at the conference.
[1] B. Hartke, Struct. Bond. 110 (2004) 33.
[2] G.A. Cox, T.V. Mortimer-Jones, R.P. Taylor, R.L. Johnston, Theor. Chem. Acc. 112
(2004) 163.
[3] W.L. Meerts, M. Schmitt. Int. Rev. Phys. Chem. 25 (2006) 353.
[4] L.F. Roncaratti, R. Gargano, G.M. Silva. J. Mol. Struct. (THEOCHEM) 769 (2006) 47.
[5] J.M.C. Marques, F.V. Prudente, F.B. Pereira, M.M. Almeida, A.M. Maniero, C.E.
Fellows, J. Phys. B: At., Mol. & Opt. Phys. (in press).
[6] F.B. Pereira, J.M.C. Marques, T. Leito, J. Tavares, Proceedings of the IEEE
Congress on Evolutionary Computation (CEC), p. 2270-2277, Vancouver, 2006.
[7] F.B. Pereira, J.M.C. Marques, T. Leito, J. Tavares, Advances in Metaheuristics for
Hard Optimization, Springer Natural Computing Series, p. 223-250, P. Siarry, Z.
Michalewicz (eds), Springer, Berlin, 2008.
[8] J.M.C. Marques, F.B. Pereira, T. Leito, J. Phys. Chem. A (accepted for publication).
234


METASTABLE ZONE WIDTH FOR THE
CRYSTALLIZATION OF NICOTINIC
ACID FROM WATER

Elsa M. Gonalves, Manuel E. Minas da Piedade
Departamento de Qumica e Bioqumica, Faculdade de Cincias, Universidade de
Lisboa, 1749-016 Lisboa, Portugal
*emdgoncalves@fc.ul.pt, memp@fc.ul.pt

The ability of nicotinic acid to strongly rise the plasma concentration of high
density lipoprotein (HDL) cholesterol has in recent years led to an increased
interest in the pharmacological potential of this compound. In most applications
the material is used in the solid state, after crystallization from solution. The
control of the crystallization process normally requires the determination of the
equilibrium solubility and of the metastable zone width as a function of the
temperature. The metastable zone width corresponds to the difference T
max
= T
S

T
N
, where T
S
is the saturation temperature and T
N
represents the nucleation
temperature, which is normally taken as the temperature at which the formation
of crystals is first detected. The metastable zone width results from the specific
characteristics of nucleation in a supersaturated solution. It can be considered as
a characteristic property of crystallization for each system and depends on the
saturation conditions, cooling rate, impurities, and mechanical effects such as the
stirring rate.
In this work the saturation temperature and metastable zone width for the
crystallization of nicotinic acid from water were investigated by the polythermal
method, using a fully automatic crystallization reactor with turbidity detection.
The results showed that for a stirring rate of 380 rpm, T
max
increases with the
increase of the cooling rate from 6 Kh
1
to 30 Kh
1
and decreases with the
decrease of the nicotinic acid concentration. Analysis of the data from a kinetic
point of view using the Nvlt method led to a nucleation order of 10.

Acknowledgments: This work was supported by Fundao para a Cincia e Tecnologia. A
PhD. grant from FCT is also gratefully acknowledged by E. M. Gonalves (SFRH/BD/
28458/2006).
235


Figura 1 Introduo de um grupo
metileno nos derivados do furano:
X = CN, COOH e CHO
ESTUDO TERMOQUMICO DE ALGUNS
DERIVADOS DO FURANO

Lusa M. P. F. Amaral*, Manuel A. V. Ribeiro da Silva
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias
da Universidade

do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
*luisaamaral@gmail.com

Os compostos furnicos so substncias geradas a partir do envelhecimento
de materiais celulsicos. O aumento da concentrao do 2-furaldedo, por
exemplo, utilizado como indicador do envelhecimento do papel de celulose
isolante. Muitos derivados do furano so
libertados para a atmosfera durante a
queima de biomassa e a combusto de
combustveis fsseis.
O nosso laboratrio tem vindo a realizar
um estudo sistemtico de propriedades
termoqumicas de heterocclicos de azoto,
enxofre e oxignio, inserindo-se nesse
mbito o estudo de furanos. Um dos objectivos desse estudo tentar estabelecer
correlaes entre a energtica e a estrutura dos compostos de modo que
permitam a estimativa dessas propriedades para outros compostos no estudados
experimentalmente. Para a obteno desses parmetros necessrio conhecer
valores para as entalpias de formao dos compostos no estado gasoso, onde as
foras inter-moleculares so nulas. Para isso determinaram-se experimentalmente
as entalpias de formao dos compostos, na fase condensada, por calorimetria de
combusto em bomba esttica. Os valores das entalpias de transio de fase
foram medidos por microcalorimetria Calvet de altas temperaturas ou a partir da
medio de presses de vapor a diferentes temperaturas pelo mtodo de efuso
de Knudsen. Os valores das entalpias de formao dos compostos no estado
gasoso so analisados em termos dos efeitos energticos produzidos pela
introduo de um grupo etileno na estrutura molecular.

Agradecimentos: Agradece-se Fundao para a Cincia e Tecnologia (FCT), e ao
FEDER o apoio financeiro prestado ao Centro de Investigao em Qumica da
Universidade do Porto. L.M.P.F.A. agradece FCT a bolsa de ps-Doutoramento
(SFRH/BPD/25490/2005).
O
O X (Z)
X
236


THERMOCHEMISTRY OF DIHYDROXYBENZOIC
ACID ISOMERS

Mariana Vidinha*, Maria D. M. C. Ribeiro da Silva, Manuel J. S. Monte
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias,
Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal.
*c0670143@fc.up.pt

The present work appears in the sequence of previous studies on the
thermodynamic properties of dihydroxybenzoic acid isomers (DHBA) [1, 2], a
group of important compounds that are intermediates in degradation processes of
natural and synthetic molecules by microorganisms yielding acyclic and
inorganic compounds [3]. Some of the isomers of DHBA are also used in
MALDI (matrix assisted laser desorption/ionization - mass spectroscopy)
analysis, being 2,5-dihydroxybenzoic acid one standard matrix [4].
A few years ago, the enthalpies of sublimation of the six dihydroxybenzoic
acids were determined by thermogravimetry, but the accuracy of the published
data is poor [4]. So we decided to measure their vapour pressures using an
accurate method. Complementing the study, we started measuring also the
enthalpies of formation of those crystalline isomers in order to derive the
enthalpies of formation for the gaseous compounds. These data allow the
interpretation of the influence of the functional hydroxyl groups situated in
different positions of the aromatic ring on the energetics of these benzoic acid
derivatives.
This study reports the experimental thermodynamic study of 2,3- and 2,5-
dihydroxybenzoic acids. The standard molar enthalpies of combustion of the two
compounds were obtained by static combustion calorimetry, at T = 298.15 K,
and from them we derived the corresponding standard molar enthalpies of
formation in the crystalline state, at the same reference temperature. The vapour
pressures of purified crystalline samples, at several temperatures, were measured
using the Knudsen effusion method allowing the calculation of the standard
molar enthalpies of sublimation at T = 298.15 K. The values of the standard
enthalpies of formation, in the condensed state and the values of the standard
enthalpies of sublimation were combined to derive the standard molar enthalpies
of formation, in gaseous state, of the 2,3- and 2,5-dihydroxybenzoic acids.
[1] M. Vidinha, M. D. M. C. Ribeiro da Silva, M. J. S. Monte, Thermodynamic Study of
3,5-Dihydroxybenzoic Acid,P2.5 of Abstracts Books of the 8th National Meeting on
Physical Chemistry (Sociedade Portuguesa de Qumica) Coimbra, Portugal, 2007.
[2] M. Vidinha, M. D. M. C. Ribeiro da Silva, M. J. S. Monte, Thermodynamic
properties of 2,4- and 3,4-Dihydroxybenzoic Acid Isomers,P65 of Books of
Abstracts - Medicta 2007 The 8
th
Mediterranean Conference on Calorimetry and
Thermal analysis, Palermo, Italy, 2007.
[3] A. Karaliota, V. Aletras, D. Hatzipanayioti, M. Kamariotaki, M. Potamianou, J. Mass
Spectrometry 37 (2002) 760.
[4] D. M. Price, S. Bashir, P. R. Derrick, Thermochimica Acta, 327 (1999) 167.
237


Figure 1. Optimized structure
for NiCp(PH
3
)CC{SC
4
H
2
}NO
2


FIRST HYPERPOLARIZABILITY OF SOME NICKEL-
ACETYLIDE COMPLEXES: A DFT STUDY

Ana Barrocas*, Paulo J. Mendes, A. J. P. Carvalho
Centro de Qumica de vora, Universidade de vora, Rua Romo Ramalho, 59, 7000-671
vora, Portugal
*ana.filipa.barrocas@gmail.com

The search for new organometallic materials with second-order nonlinear
optical (SONLO) properties is currently the subject of considerable interest due
to their potential technologic applications in photonic devices for
telecommunications and optical computing. Experimental systematic studies
were made on half-sandwich complexes presenting nitrile and acetylide benzene
and thiophene-based chromophores [1-3]. The results revealed that the
combination of acetylide thiophene ligands
with appropriate organometallic fragments
would maximize the SONLO response. Also,
recent TD-DFT studies on q
5
-
monocyclopentadienyliron(II) complexes with
substituted thienyl-acetylide ligands revealed
the fundamental role played by the
organometallic fragment on the corresponding
SONLO properties [4].
In our continuous effort to get a better understanding on the electronic factors
that may dictate the SONLO properties of
5
-monocyclopentadienylmetal
complexes with substituted thienyl-acetylide chromophores, we report herein the
preliminary density functional theory (DFT) and time-dependent DFT (TD-DFT)
results on the complexes [NiCp(PR
3
)(CC{SC
4
H
2
}
n
Y)] (R=H, Ph; Y= CHO, CN,
NO
2
; n=1,2) using the Gaussian03W program package. For instance, Figure 1
shows the optimized structure for NiCp(PH
3
)(CC{SC
4
H
2
}NO
2
. The effect of the
phosphine, the Y-substituent and the conjugated length of the chromophore on
the first hyperpolarizability will be evaluated. Some experimental spectroscopic
data will be also explained on the basis of the TD-DFT calculations.

[1] M. H. Garcia et al, Handbook of Advanced Electronic and Photonic Materials and
Devices 9 (2001) 127.
[2] M. Helena Garcia, Paulo J. Mendes, M. Paula Robalo, A. Romo Dias, J. Campo, W.
Wenseleers, E. Goovaerts, Journal of Organometallic Chemistry 692 (2007) 3027.
[3] Clem E. Powell, Mark G. Humphrey. Coord. Chem. Rev. 248 (2004) 725
[4] Lus Conde, Clculos de hiperpolarizabilidade em complexos organometlicos de
ferro usando o mtodo de DFT. Tese de Licenciatura, U. vora, 2007
238


MONOCYCLOPENTADIENYLRUTHENIUM COMPLEXES
FOR SECOND-ORDER NLO PURPOSES

Paulo J. Mendes
a
*, M. H. Garcia
b
, M. P. Robalo
c,d

a
Centro de Qumica de vora, Universidade de vora, Rua Romo Ramalho, 59, 7000-
671 vora, Portugal
b
Centro de Cincias Moleculares e Materiais, Faculdade de Cincias da Universidade de
Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
c
Centro de Qumica Estrutural, Instituto Superior Tcnico, 1049-001 Lisboa, Portugal
d
Departamento de Engenharia Qumica, ISEL, 1959-007 Lisboa, Portugal
*pjgm@uevora.pt

Organometallic compounds have given rise to a great deal of interest owing
to their application in the field of nonlinear optics (NLO) [1]. For second-order
nonlinear optics (SONLO), strongly asymmetric systems are needed, which led
to the development of typical pushpull systems in which the metal centre,
bound to a highly polarizable conjugated backbone, acts as an electron releasing
or withdrawing group. Among the organometallic compounds presenting this
donor-systemacceptor feature,
5
-monocyclopentadienyliron and ruthenium
moieties were found to be much more efficient donor groups for second-order
NLO purposes than the traditional organic donor groups, leading to higher first
hyperpolarizabilities () [2]. Recent results on
5
-monocyclopentadienyliron
complexes presenting thiophene nitrile chromophores showed an enhanced
SONLO performance when compared to that observed on analogue benzenoid
structures. Also, the first hyperpolarizability of these complexes was found to be
influenced by a compromise between the conjugation length of the
chromophores and the metal-to-ligand charge-transfer [3].
In our continuous effort to understand the role played by the organometallic
fragment on the SONLO properties and to establish detailed structureNLO
activity correlations, we now study a series of complexes of general formula
[RuCp(P_P)(NC{SC
4
H
2
}
n
NO
2
)][PF
6
] (Fig. 1) (P_P=dppe, (+)-diop; n=1-3).
Spectroscopic and electrochemical data will be used in order to evaluate the
effect of the phosphine coligand and the length of the conjugated ligand on the
second-order NLO response of the complexes. The results will be compared to
those found in parent iron derivatives.

[1] E. Goovaerts, W. Wenseleers, M.H. Garcia, G.H. Cross, Handbook of Advanced
Electronic and Photonic Materials and Devices 9 (2001) 127.
[2] W. Wenselers, E. Goovaerts, M.H. Garcia, M.P. Robalo, P.J. Mendes, J.C. Rodrigues,
A.R. Dias, J. Mater. Chem. 8 (1998) 925.
[3] M. Helena Garcia, Paulo J. Mendes, M. Paula Robalo, A. Romo Dias, J. Campo,
W. Wenseleers, E. Goovaerts, Journal of Organometallic Chemistry 692 (2007) 3027.
239


ROTATIONAL MOTION OF FULLERENE C
70

DERIVATIVES FROM FLUORESCENCE ANISOTROPY
MEASUREMENTS

Filipe Menezes*, Alexander A. Fedorov, Carlos Baleizo, Mrio N.
Berberan-Santos
Centro de Qumica-Fsica Molecular, Instituto Superior Tcnico, 1049-001 Lisboa,
Portugal
*filipemmenezes@gmail.com

The photophysics of fullerenes has been the subject of extensive studies in
the last fifteen years. The photophysical properties exhibited by fullerenes are in
some aspects unique. Specially remarkable is the strong thermally activated
delayed fluorescence (TADF) displayed by fullerene C
70
[1].
From the point of view of symmetry, C
70
is also an interesting molecule. It
belongs to the D
5h
point group, thus having two equivalent axes (x and y). The
electronic transition moment for S
1
S
0
occurs along the xy plane. For this
reason, the fundamental anisotropy of C
70
takes values between 0.1 and -0.2,
depending on the excitation wavelength [2].
In fluid media, the fluorescence anisotropy correlation time, t
r
, characterizes
the rotational motion of the molecule and is dependent on the viscosity and
temperature. Fullerene C
70
and its derivatives are good models for testing
rotational motion theories, as they have relatively simple shapes.
In this communication, we present the fluorescence anisotropy correlation
times of various C
70
derivatives in several solvents and temperatures. These
values are compared with those obtained for anthracene and pristine C
70
under
the same conditions. The effect of the type of functionalization is also discussed.

[1] C. Baleizo, M.N. Berberan-Santos, Ann. N. Y. Acad. Sci. xxx (2008) xxx.
[2] A. Fedorov, M.N. Berberan-Santos, J.P. Lefvre, B. Valeur. Chem. Phys. Lett. 267
(1997) 467.
240


ENERGETICS OF THE FORMATION OF CALCIUM
PHOSPHATE NANOPARTICLES

Miroslav Leskiv
a
, Ana L. C. Lagoa
a
, Henning Urch
b
, Janine
Schwiertz
b
, Manuel E. Minas da Piedade
a
*, Matthias Epple
b

a
Departamento de Qumica e Bioqumica, Faculdade de Cincias, Universidade de
Lisboa, 1749-016 Lisboa, Portugal
b
Inorganic Chemistry, University of Duisburg-Essen, Universittsstrasse 5-7, 45117
Essen, Germany
*memp@fc.ul.pt

Hydroxyapatite and related calcium phosphates are important biomaterials.
This is mainly due to their good biocompatibility, which results from the
structural similarity with the mineral phase of the hard tissues of vertebrates
(bones and teeth). Recently, calcium phosphate nanoparticles (CaP
nano
) have
been successfully used as transfection agents. The thermochemistry of the
synthesis of these nanoparticles according to the following reactions:

10 Ca(NO
3
)
2
(aq) + 6 (NH
4
)
2
HPO
4
(aq) CaP
nano
(s)

10 Ca(CH
3
CHOHCOO)
2
(aq) + 6 (NH
4
)
2
HPO
4
(aq) CaP
nano
(s)

was studied in this work, using a LKB 10700-1 flow microcalorimeter. A clear
dependence of the reaction enthalpy on the pH of the (NH
4
)
2
HPO
4
solution was
found, which could be correlated with changes in the Ca and P composition of
the particles as determined by elemental analysis and thermogravimetry.

Acknowledgment: This work was supported by the GRICES/DAAD scientific
collaboration programme (Proc. 4.1.1/DAAD). Post Doctoral grants from FCT are
gratefully acknowledged by M. Leskiv (SFRH/BPD/26494/2006) and A. L. C. Lagoa
(SFRH/BPD/35053/2007).
241


Figure 1. Norbornane
CH BOND DISSOCIATION ENTHALPIES IN
NORBORNANE

Paulo M. Nunes
a
*, Slvia G. Estcio
a,b
, Gustavo T. Lopes
a
, Benedito J.
Costa Cabral
b
, Rui M. Borges dos Santos
a,c,d
, Jos A. Martinho
Simes
a,c

a
Centro de Qumica e Bioqumica, Faculdade de Cincias, Universidade de Lisboa, 1749-
016 Lisboa, Portugal
b
Grupo de Fsica Matemtica da Universidade de Lisboa, Av. Professor Gama Pinto 2,
1649-003 Lisboa, Portugal
c
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. da
Repblica, 2780-157 Oeiras, Portugal
d
Institute for Biotechnology and Bioengineering, Centro de Biomedicina Molecular e
Estrutural, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
*panunes@fc.ul.pt

Organic strained molecules, such as
bicyclohydrocarbons, have long been the object of
thermochemical studies [1,2]. One of these molecules
is norbornane (bicyclo[2.2.1]heptane), a key
compound in revealing how structural and energetic
parameters are affected by a strained geometry [3].
Despite of this interest, the uncertainties in the
experimental CH bond dissociation enthalpies
(BDEs) for this molecule are higher than the usual
chemical accuracy limit (ca. 4 kJ mol
-1
) [4].
In this communication we report the gas-phase CH bond dissociation
enthalpies (BDEs) in norbornane determined by quantum chemistry calculations
and the C2H BDE obtained for the first time by time-resolved photoacoustic
calorimetry. The trend
o
(C1 H) DH >
o
(C7 H) DH >
o
(C2 H) DH is
explained using geometric features, spin densities, and hybridization.

Acknowledgment: P. M. N. and S. G. E. thank Fundao para a Cincia e a Tecnologia,
Portugal for a postdoctoral (SFRH/BPD/26677/2006) and a Ph.D. (SFRH/BD/10200/
2002) grant, respectively

[1] J.F. Liebman, A. Greenberg. Chem. Rev. 76 (1976) 311.
[2] Y. Feng, L. Liu, J.-T. Wang, S.-W. Zhao, Q.-X. Guo. J. Org. Chem. 69 (2004) 3129.
[3] S.P. Verevkin, V. N. Emel'yanenko. J. Phys. Chem. A 108 (2004) 6575.
[4] Y.-R. Luo. Handbook of Bond Dissociation Energies in Organic Compounds, CRC
Press, Boca Raton, 2003.
242


THERMODYNAMIC STUDY OF
ANTITUBERCULOSTATIC DRUGS

Alfa U. S*, Guangyue Bai, Filipa Abrunhosa, Margarida Bastos
CIQ (UP), Department of Chemistry, Faculty of Sciences, University of Porto, Rua do
Campo Alegre, 687, P-4169-007, Porto, Portugal
*c0103155@alunos.fc.up.pt

Tuberculosis is the principal cause of infectious pulmonary diseases and still
a major health concern - in 2006 about 1,6 million persons died because of this
disease. In the last decades an increase in the prevalence of tuberculosis was
observed, in spite of the enormous efforts in its prevention and treatment. The
synergism of tuberculosis and AIDS and the appearance of strains resistant to
conventional anti-tuberculostatic drugs have been destabilizing the effective
control of this disease world-wide. Therefore, the development and test of new
anti-tuberculostatic drugs is still a primary task for researchers [1].
Calorimetry has proved to be very useful in the characterization of solids by
their dissolution behaviour [2], providing data with interest for the
pharmaceutical area, where characteristics like the degree of cristallinity or the
existence of polymorphism have to be adequately evaluated. Isothermal Titration
Calorimetry (ITC), and Differential Scanning Calorimetry (DSC), on the other
hand, allows the study of their interaction with model membranes, fundamental
for prospective drug applications [3].
In the present work, we used an isothermal dissolution microcalorimeter [2]
for the determination of the enthalpies of dissolution,
sol
H, of two
antituberculostatics drugs, Rifampicin and Isoniazid, in phosphate buffer, pH 7.4
(with adjusted ionic strength), and in octanol, at 298.15 K.
The liposome/drug interaction was studied by DSC and ITC. The effect of
the drug on the membrane can be acessed from the DSC results, and the
energetics derived from ITC.
The obtained results from the various techniques will be presented and
discussed in detail.

Aknowledgements: Thanks are due to FCT for finantial support of CIQ (UP).

[1] TB Alliance Annual Report 2007 (http://new.tballiance.org/downloads/publications/
TBAlliance_AnnualReport_2007.pdf)
[2] M. Bastos, G. Bai, E. Qvarnstrm, I. Wads. A new dissolution microcalorimeter:
calibration and test. Thermochim. Acta 405 (2003) 21.
[3] C. Matos, J.L.C. Lima, S. Reis, A. Lopes, M. Bastos, Biophys. J. 86 (2004) 946.
243


THE ELECTRICAL DOUBLE LAYER AT THE BMIMPF
6
IONIC LIQUID/SOLID ELECTRODE INTERFACE

Cristiana Gomes*, Ana Martins, Fernando Silva
Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007
Porto, Portugal
*cristianagoms@gmail.com

Room temperature ionic liquids (RTILs) have been investigated intensively,
in the last decade, due to their unique chemical, physical and green properties
[1]. A large number of experimental and theoretical studies [2] have already been
carried out to understand the nature and dynamics of these compounds, but very
few studies have been dedicated to the properties and structure of the
RTILs/solid electrode interface.
This work report a study of the differential capacitance at the interface
between BMIMPF
6
ionic liquid and two different materials solid electrodes,
Platinum and glassy carbon, using cyclic voltammetry and electrochemical
impedance spectroscopy (EIS).
The differential capacitance-potential curves obtained show a small
dependence of the applied potential range, which could reflect weak interactions
between the ions and electrode surface. However, the different values of
capacitance obtained for BMIMPF
6
/GC and BMIMPF
6
/Pt interfaces suggest that
the structure of the interface at both electrodes surfaces is different.
The effect of temperature on the differential capacitance was also measured.
The results show than an increase of temperature causes an increase in
differential capacitance, similarly to what has been known for high temperature
inorganic melts [3].

Acknowledgments: This work was carried out under Project IONMET contract n NMP2
CT 2005 515743 at CIQ line 4.

[1] J. Zhang, A. M. Bond, Analyst 130 (2005) 1132
[2] M. Galinski, A. Lewandowski, I. Stepniak, Electrochim. Acta 51 (2006) 5567
[3] M.A.V. Devanathan , B. V. K. S. R. A. Tilak, Chem. Rev. 65 (1965) 635
244


CALCULATING CONVENTIONAL STRAIN ENERGIES IN
PARENT MOLECULES AND THEIR RADICALS

Rui M. Borges dos Santos
a,b,c
*, Filipe Agapito
d
, Paulo M. Nunes
a
,
Benedito J. Costa Cabral
d
, Jos A. Martinho Simes
a,c

a
Centro de Qumica e Bioqumica, Faculdade de Cincias, Universidade de Lisboa, 1749-
016 Lisboa, Portugal
b
Institute for Biotechnology and Bioengineering, Centro de Biomedicina Molecular e
Estrutural, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
c
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. da
Repblica, 2780-157 Oeiras, Portugal
d
Grupo de Fsica Matemtica da Universidade de Lisboa, Av. Professor Gama Pinto 2,
1649-003 Lisboa, Portugal
*rmsantos@ualg.pt

Strain is a fundamental concept in structural organic chemistry [1]. How the
magnitude of the strain energy (SE) is measured and its effect upon chemical
reactivity, namely its relation with bond dissociation enthalpies (BDEs), is still a
subject of much research [2]. Recently, we investigated the effect of strain on
CH BDEs, by studying the five- and six-membered ring hydrocarbons using
experimental (time-resolved photoacoustic calorimetry) and theoretical
chemistry methods. Since strain can affect parent molecules and radicals
differently, a comprehensive discussion must discriminate between these two.
But while quantifying strain in the parent molecules is straightforward [3], the
situation for the radicals is much more complex. In this work we propose an
extension of the s-homodesmotic model [4] to address both, and a way to assess
the results by comparison with experimental data.
The s-homodesmotic methodology is a rather convenient way to design
chemical reactions whose enthalpies can be identified with the SE of a given
molecule. However, to obtain correct estimates, different order s-homodesmotic
models might be needed. The systematization of the structural features provided
by group additivity methods helps selecting the adequate s-homodesmotic model
for a given molecule. The rules to choose a suitable model will be presented and
explained along with illustrating examples.

P.M.N. and F.A. thank Fundao para a Cincia e a Tecnologia, Portugal, for a post-
doctoral (SFRH/BPD/26677/2005) and a Ph.D. (SFRH/BD/22854/2005) grant,
respectively.

[1] A. Greenberg, J.F. Liebman. Strained Organic Molecules, Academic Press, New
York, 1978.
[2] R.D. Bach, O. Dmitrenko. J. Am. Chem. Soc. 126 (2004) 4444.
[3] J.D. Cox, G. Pilcher. Thermochemistry of Organic and Organometallic Compounds,
Academic Press, New York, 1970
[4] L.L. Lewis, L.L. Turner, E.A. Salter, D.H. Magers. THEOCHEM 592 (2002) 161.
245


TRANS CINNAMIC ACID DERIVATIVES INCLUDED IN
CYCLODEXTRINS: A RAMAN SPECTROSCOPIC STUDY

Mariela M. Nolasco
a
*, Ana M. Amado
b
, Paulo A. Ribeiro-Claro
a

a
Departamento de Qumica, Universidade de Aveiro, P-3810-193 Aveiro, Portugal
b
Qumica-Fsica Molecular, Faculdade de Cincias e Tecnologia, Universidade de
Coimbra, P-3004-535 Coimbra, Portugal
*mnolasco@ua.pt

Cyclodextrins (CDs) are among the most frequently used host molecules in
supramolecular chemistry [1]. They are cyclic oligosaccharides composed of six
(-CD), seven (-CD), eight (-CD) or more, D-(+)-glycopyranose units linked
by (1-4) linkages, with the overall shape of a short, hollow, truncated cone with
primary and secondary hydroxyl groups crowning the narrower rim and wider
rim, respectively [2]. The central cavities of these molecules are hydrophobic
and form inclusion complexes with various guest molecules based on physical fit
and chemical affinity. This property has enabled CDs to be good models for
enzyme action, combining the cage effects with the conformational control of the
guest molecule [3].
There is currently a great deal of interest in the health benefits of the phenolic
acid derivatives, through their potential antioxidant, pro-oxidant, anti-
inflammatory and anti-mutagenic properties, or even anti-tumoral activity in
different human cancer cell lines [4, 5]. By this fact, phenolic acid derivatives in
supramolecular cyclodextrin complexes present an interesting example system.
In this work, the Raman spectra of guest molecules trans-cinnamic acid, 3-
hydroxy-trans-cinnamic acid, 4-hydroxy-trans-cinnamic acid and 3,4-dihydroxy-
trans-cinnamic acid, included in o-,|- and -CD are presented. The effects of the
inclusion process on the conformational equilibrium and on the hydrogen bond
interactions of the guest, observed in sensitive vibrational modes such as C=O,
C=C and ring CH stretching modes [3, 6, 7], are discussed.

[1] J. Szejtli, Chem. Rev. 98 (1998) 1743.
[2] W. Saenger, J. Jacob, K. Gessler, D. Hoffmann, H. Sanbe, K. Koizni, S.M. Smith, T.
Takaha, Chem. Rev. 98 (1998) 1787.
[3] P.J.A. Ribeiro-Claro, A.M. Amado, J.J.C. Teixeira-Dias, J. Raman Spectros. 27
(1996) 155.
[4] E. VanBesien, M.P.M. Marques, J. Mol. Struct. 625 (2003) 265.
[5] C. Castelluccio, G.P. Bolwell, C. Gerrish, C. Rice-Evans, Biochem. J. 316 (1996) 691.
[6] A.M. Amado, P.J.A. Ribeiro-Claro, J. Raman Spectros. 31 (2000) 971.
[7] P.J.A. Ribeiro-Claro, A.M. Amorim da Costa, M.L. Vueba, M.E. Pina, A.M. Amado,
J. Raman Spectros. 37 (2006) 472.
246


A QSAR STUDY OF ANTITUBERCULAR
THIOBENZANILIDE DERIVATIVES:
PREDICTION OF LIPOPHILICITY

Susana M. Borges
a
, Joo Manso
b
, Cristina Ventura
a,c
, Susana Santos
a
,
Filomena Martins
a
*
a
Departamento de Qumica e Bioqumica, FCUL, CQB, Ed. C8, Campo Grande 1749-016
Lisboa, Portugal

b
Departamento de Engenharia Qumica, CIEPQPF, FCTUC, Polo II - Pinhal de
Marrocos 3030-290 Coimbra, Portugal
c
Instituto Superior de Educao e Cincias, Alameda das Linhas de Torres, 174, 1750
Lisboa, Portugal
*filomena.martins@fc.ul.pt

According to the most recent WHO reports [1], in 2006 there were almost 9.2
million new cases of tuberculosis (TB) worldwide and 1.7 million deaths due to
this disease. In line with the latest estimates [2, 3], 10% of all new TB infections
are resistant to at least one anti-TB drug. Also, recent reports on multi-drug
resistant (MDR) and extensively drug-resistant tuberculosis (XDR-TB) indicate
that rates of drug resistance may be far higher than previously described [2].
These facts have raised much interest in the scientific community towards the
development of new active antitubercular compounds and several efforts, in
general not very successful, have been made towards the understanding of the
mechanisms of action of active compounds against Mycobacterium tuberculosis.
In the process of screening and pre-formulation of potential new drugs it is of
the utmost importance the knowledge of certain physicochemical properties,
such as their hydrophilic/hydrophobic character which determines their ability to
penetrate a biological membrane.
In this work we have analyzed 46 active thiobenzanilide compounds, taken from
literature [4], and have investigated the correlation between their lipophilicity, as
given by their n-octanol/water partition coefficient values - P
oct/water
-, and several
molecular descriptors of physicochemical, geometrical, steric and electronic nature.
The established MLR-QSARs models showed that the key factors responsible for the
lipophilicity of these compounds are their hydrophilic surface area and van der
Waalss energy, the compounds H-bond basicity and the length of substituents.
In order to test the robustness and predictive ability of the developed QSARs,
we have synthesized 7 potentially active thiobenzanilide derivatives, and
determined their experimental log P
oct/water
values by the shake flask method.
Acknowledgements: FCT/SFRH/BPD/2074/2004, C. Ventura; Scientific Sponshorsip of
the Portuguese Health Ministry.
[1] Global Tuberculosis Control, WHO Report, 2008.
[2] Anti-tuberculosis Drug Resistance in the World, WHO, 2004.
[3] Vicent, V. et al. Emerg. Inf. Dis. 13 (2007) 380.
[4] Waisser et al. Collect. Czech. Chem. Commun. 62 (1997) 1503; Waisser et al.
Collect. Czech. Chem. Commun. 58 (1993) 205.
247


THE INFLUENCE OF AROMATIC SUBSTITUENTS ON
THE SOLVOLYSIS OF TERTIARY ALKYL HALIDES: A
GRUNWALD-WINSTEIN ANALYSIS

Marina Reis
a
, Lus Moreira
a
, Ruben Leito
b
, Filomena Martins
a
*

a
Departamento de Qumica e Bioqumica, Faculdade de Cincias, Universidade de
Lisboa, CQB, Campo Grande, 1749-016 Lisboa, Portugal
b
Departamento de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa,
IPL,CQB, R. Conselheiro Emdio Navarro, 1950-062 Lisboa, Portugal
*filomena.martins@fc.ul.pt

The study of solvolytic reactions of tertiary alkyl halides has deserved
particular attention from the scientific community since they are good model
systems for monitoring solvent and solvation effects.
1
In the present work we
have studied solvent effects on substrates with aromatic substituents, aiming to
probe the influence of such groups in the reactivity of these compounds. With
this purpose we have determined the solvolytic rate constants for 2-chloro-2-
phenyl-propane and 2-bromo-2-methyl-1-phenyl-propane at 25,00 C in pure
solvents and binary solvent mixtures.
This study was performed through the extended Grunwald-Winstein equation
(Eq. 1)
2
or through a truncated version of this equation:

log k = mY
X
+ lN
OTs
+ hI + c (1)

In this equation, Y
X
represents the solvents ionizing power, N
OTs
its
nucleophilic assistance and I is an aromatic ring parameter. The sensitivity of the
substrate to the variations of Y
X
, N
OTs
and I is represented respectively by m, l
and h. The independent parameter, c, depends on the rate constant of the
substrates solvolysis in a reference solvent, usually 80% (v/v) aqueous ethanol.
The analysis of the obtained data in conjunction with previously reported
results allowed the rationalization of the effect of aromatic substituents in these
solvolyses.

Acknowledgements: SFRH/BD/23867/2005 (M. Reis), SFRH/BD/6190/2001 (L. Moreira).

[1] H. C. Brown, R. S. Fletcher. J. Am. Chem. Soc. 71 (1949) 1845.
[2] D. N. Kevill, N. H. J. Ismail, M. J. DSouza. J. Org. Chem. 59 (1994) 6303.
248


Figure 1. (a) Terpinolene
(b), -Terpinene and (c)
-Terpinene
TRENDS IN CH BOND DISSOCIATION ENTHALPIES:
DELOCALIZATION, CONJUGATION, AND STRAIN

Filipe Agapito
a,b
, Paulo M. Nunes,
a
Benedito J. Costa Cabral,
b
Rui M.
Borges dos Santos
a,c,d
*, Jos A. Martinho Simes
a,d

a
Centro de Qumica e Bioqumica, Faculdade de Cincias, Universidade de Lisboa, 1749-
016 Lisboa, Portugal
b
Grupo de Fsica Matemtica da Universidade de Lisboa, Av. Professor Gama Pinto 2,
1649-003 Lisboa, Portugal
c
Institute for Biotechnology and Bioengineering, Centro de Biomedicina Molecular e
Estrutural, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
d
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. da
Repblica, 2780-157 Oeiras, Portugal
*rmsantos@ualg.pt

Bond dissociation enthalpies (BDEs) are fundamental to discuss molecular
structure-reactivity relationships. For instance, some terpenes (fig. 1) exhibit
antioxidant properties comparable to those of o-
tocoferol [1], without the pro-oxidant effects of this
latter compound at higher concentrations [2]. Since
this property is linked with the carbonhydrogen
BDE in the terpene, the knowledge of the CH BDEs
in these and other structurally related compounds is
of great interest to understand which structural
factors influence their antioxidant properties.
Surprisingly, we found that the literature values
for CH BDEs even in simple hydrocarbons, despite
their fundamental importance, have considerable
uncertainties (typical error bars were well above chemical accuracy, ca. 4 kJ mol
-
1
) [3]. To try to improve matters we used experimental (time-resolved
photoacoustic calorimetry) and theoretical chemistry methods to determine the
CH BDEs in selected hydrocarbons with chemical accuracy. Our data allowed a
detailed discussion of the observed trends in terms of hyperconjugation and t-
delocalization (in the radicals), the importance of conjugated double-bonds (in
the parent molecules), and the effect of strain (in both).

P.M.N. and F.A. thank Fundao para a Cincia e a Tecnologia, Portugal, for a post-
doctoral (SFRH/BPD/26677/2005) and a Ph.D. (SFRH/BD/22854/2005) grant,
respectively.

[1] G. Ruberto, M.T. Baratta. Food Chem. 69 (2000) 167.
[2] M.C. Foti, K.U. Ingold. Agric. Food Chem. 51 (2003) 2758.
[3] F. Agapito, P.M. Nunes, B.J. Costa Cabral, R.M. Borges dos Santos, J.A. Martinho
Simes. J. Org. Chem. 72 (2007) 8770.

(a)

(b)

(c)
249


Figura 1. Heme pocket
of CYP3A4CO.
ENERGETIC AND CONFORMATIONAL CHANGES OF
CYP3A4 FOLLOWING CO HOMOLYSIS

Ana Frangolho
a,b
, Paulo M. Nunes
b
, Vtor H. Teixeira
a
, Paulo J.
Martel
a
, Lus F. M. Rosa
a
, Guilherme N. M. Ferreira
a
, Rui M. Borges
dos Santos
a,b,c
*
a
Institute for Biotechnology and Bioengineering, Centro de Biomedicina Molecular e
Estrutural, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
b
Centro de Qumica e Bioqumica, Faculdade de Cincias, Universidade de Lisboa, 1749-
016 Lisboa, Portugal
c
Instituto de Tecnologia Qumica e Biolgica, Universidade Nova de Lisboa, Av. da
Repblica, 2780-157 Oeiras, Portugal
*rmsantos@ualg.pt

CYP3A4, the most abundant cytochrome P450 found in human liver,
catalyses the oxidative metabolism of clinically, physiologically and
toxicologically important compounds being involved in the inactivation of 60%
of therapeutical drugs [1]. Therefore, elucidation of
factors controlling CYP3A4 activity is of extreme
importance. To understand the mechanism by which
CYP3A4 exerts its catalytic activity, detailed
knowledge on its structure as well as identification
of reaction intermediaries is required. As classical
techniques are often limited to resolutions of a few
milliseconds a common practice is to kinetically
trap short-lived species in a low temperature
matrix. However, this leads to studies under
extremely non-physiological conditions [2].
Time-resolved photoacoustic calorimetry (TR-PAC) is a valuable technique
to probe conformation and dynamics of proteins in the nano- to the micro-second
regime and under physiologic conditions [3]. In our study, CO was used as the
ligand since its complex with the heme iron is readily photodissociable (fig. 1).
This method allowed to study the energetic and conformational change during
protein activity, and to search for the transient molecular species formed. The
results were then complemented with molecular modelling studies concerning
the energetics of binding and the dynamics of the ligand-CYP3A4 complex.

This work was supported by POCI/QUI/63166/2004, Fundao para a Cincia e a
Tecnologia (FCT), Portugal. V.H.T. and L.F.M.R. thank FCT for a post-doctoral
(SFRH/BPD/27680/2006) and a Ph.D. (SFRH/BD/36294/2007) grant, respectively.

[1] S.A. Wrighton, M. Vanden, B.J. Branden. Ring. J Pharmacokinet Biopharm 24
(1996) 461.
[2] A. Ostermann, R. Waschipky, F.G. Parak, G.U. Nienhaus. Nature 404 (2000) 205.
[3] T. Gensch, C. Viappiani Photochem. Photobiol. Sci. 2 (2003) 699.
250


ION SPECIFIC EFFECTS IN THE LIQUID-LIQUID PHASE
EQUILIBRIA BETWEEN WATER AND IONIC LIQUIDS

Mara G. Freire
a
*, Pedro J. Carvalho
b
, Lus M. N. B. F. Santos
c
, Lus
P. N. Rebelo
a
, J. A. P. Coutinho
b
, I. M. Marrucho
b

a
Instituto de Tecnologia Qumica e Biolgica, ITQB2, Universidade Nova de Lisboa, Av.
Repblica, Apartado 127, 2780-901 Oeiras, Portugal
b
CICECO, Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro,
Portugal
c
CIQ, Departamento de Qumica, Faculdade de Cincias da Universidade do Porto, R.
Campo Alegre 687, 4169-007 Porto, Portugal
*maragfreire@ua.pt

The design of safe and environmentally benign separation processes perform
a key role in the exponential increasing interest observed in the past few years
for ionic liquids (ILs). The ILs particular physicochemical characteristics,
especially their large solvation ability and their negligible vapour pressures,
make them suitable candidates for a broad range of greener applications
substituting the usual volatile organic solvents [1]. Moreover, the chemical
versatility of ILs, by both adjusting the cation and/or the anion, makes their use
attractive for the extractive separation of metabolites in the biotechnology field.
Despite the importance of a detailed understanding of the phase behaviour of
ILs aqueous systems - crucial for instance for the optimization of the extraction
and purification of metabolites in bioprocesses - data on the mutual solubilities
between aqueous media containing inorganic or organic salts and ILs are quite
scarce, and the interpretation of the phenomena occurring in those systems is far
from being well established.
In this work, the effect of inorganic and organic salts on the mutual
solubilities between water and hydrophobic imidazolium-based ILs was
evaluated. The magnitudes of the salting-in and salting-out effects were assessed
by changing both the cation and the anion for a large series of chloride and
sodium-based salts as well as the salt concentration, at 298.15 K and atmospheric
pressure. Both salting-in and salting-out effects were observed and showed to be
dependent on both the water-structuring nature of the salt and its concentration.
The pH influence was also evaluated and it was found to have only a trivial
effect through the IL solubility in water and the results are in agreement with the
IL cation acidity and the IL anion basicity.
Spectroscopic studies on these ternary systems have also been carried
providing further insight on the solvation mechanism of ionic liquids in aqueous
saline solutions and on the molecular-level by which both IL and inorganic salt
ions operate.

[1] M.J. Earle, J.M.S.S. Esperana, M.A. Gilea, J.N.C. Lopes, L.P.N. Rebelo, J.W.
Magee, K.R. Seddon, J.A. Widegren. Nature 439 (2006) 831.
251


SURFACE TENSION MEASUREMENTS OF
HYDROPHILIC IONIC LIQUIDS AQUEOUS SOLUTIONS

Mara G. Freire
a
, Joo A. P. Coutinho
b
, Jos N. Canongia Lopes
a
,
Lus P. N. Rebelo
a
, Isabel M. Marrucho
b
*
a
Instituto de Tecnologia Qumica e Biolgica, ITQB2, Universidade Nova de Lisboa, Av.
Repblica, Apartado 127, 2780-901 Oeiras, Portugal
b
CICECO, Departamento de Qumica, Universidade de Aveiro, 3810-193 Aveiro,
Portugal
*imarrucho@ua.pt

Over the last few years, ionic liquids (ILs) have attracted worldwide
scientific attention and interest in both academic and industry fields. Unlike
molecular liquids, an IL is an organic salt and its microscopic structure is usually
composed of a large cation with low order of molecular symmetry. Their large
ions tend to reduce the lattice energy of the structure as well as to augment the
importance of entropic factors, and hence, to lower their melting point and
remaining liquid at or near room temperature.
Some of the ions composing ILs present an amphiphilic character allowing
them to be used as a new class of surfactants capable of promoting or stabilizing
common dispersions or emulsions. This possibility prospects an application, that
of replacing some toxic surfactants used nowadays. Recently, ILs composed of
1-alkyl-3-methylimidazolium cation with long alkyl side chain lengths,
[C
n
mim]
+
, have been extensively studied through their self-aggregation and
micelle formation [1]. Nevertheless, a different approach in the field of colloid
and interface science was already reported with the surface tensions of pure
hydrophobic imidazolium-based ILs showing that ILs present remarkably low
surface entropies compared to other organic compounds [2]. Apart from these
studies, the surface activity of short alkyl chain length imidazolium-based ILs in
aqueous solutions is a poorly studied field.
In this work, we report the surface adsorption and the water surface tension
reduction by short side chain length imidazolium-based ILs. The selected ILs
allowed the study of the alkyl chain length and number of alkyl substitutions
impact. In addition, the application of the Gibbs adsorption isotherm, maximum
surface excess concentration and minimum surface area/molecule at the air-water
interface were estimated and discussed. The surface activity of each IL and their
derived properties were obtained through experimental measurements of surface
tensions carried out with the Pt/Ir Whilhelmy plate method at 298.15 K and
atmospheric pressure.

[1] M. Blesic, M.H. Marques, N.V. Pechkova, K.R. Seddon, L.P.N. Rebelo, A. Lopes.
Green Chem. 9 (2007) 481.
[2] M.G. Freire, P.J. Carvalho, A.M. Fernandes, I.M. Marrucho, A.J. Queimada, J.A.P.
Coutinho. J. Colloid Interface Sci. 314 (2007) 621.
252


THEORETICAL STUDY OF THE HOOH (X,
1
A)
POTENTIAL ENERGY SURFACE

Daniela V. Coelho*, Joo Brando
Departamento de Qumica, Bioqumica e Farmcia, Universidade do Algarve, 8005-139
Faro, Portugal
*dcoelho@ualg.pl

From the incidence of solar radiation on stratospheric ozone (Hartley band),
the outcoming excited oxygen atom is a very reactive chemical species. Its
reactions with water molecule and molecular hydrogen are two of the main
reactions whose uncertainties on the kinetic coefficients highly contribute to the
error propagation on the modelling of atmospheric chemistry and ozone
depletion cycle.
Most of the theoretical studies of atmospheric dynamics have been carried
out using potential energy surfaces (PESs) focused on the region close to the
transition state. On the other hand, it has been noted that features of the PES in
the shallow van der Waals regions of reactants and products can play a decisive
role in the outcome of encounters between reactive species [1-3]. Chemical
accurate studies are nowadays feasible for small systems using high quality basis
and extrapolation techniques to complete basis set limit [4].
To study the dynamics of the O(
1
D)+H
2
O reaction we need a complete PES
for the singlet ground state of the hydrogen peroxide, H
2
O
2
. Due to its
overwhelming importance in chemistry, there is a lot of spectroscopic data and
ab initio calculations on this system. However, in spite of it, the published
surfaces (see 5, and references therein) reproduce the region near the equilibrium
geometry, but they dont represent well the different dissociation channels in
accordance to the Wigner-Witmer rules. Using computed ab initio energies the
potential energy surface should be fitted to a 3x3 matrix in order to represent all
the different dissociation fragments [6].
In this communication we present a chemical accurate ab initio study of the
ground singlet state of this system covering all the dissociation channels. We
also characterize all the relevant minima and saddle points connecting them with
reagents and products.

[1] D. Skouteris, D.E. Manolopoulos, W. Bian, H.-J. Werner, L.-H. Lai, K. Liu, Science
286 (1999) 1637.
[2] D.T. Andersen and M I. Lester, J. Phys. Chem. A 107 (2003) 2606.
[3] P.F. Weck and N. Balakrishnan, International Reviews in Physical Chemistry 25
(2006) 283.
[4] A.J.C. Varandas P., Chem. Phys. Lett. 443 (2007) 398.
[5] R. Says, C. Oliva, M. Gonzlez, J. Chem. Phys. 115 (2001) 8828.
[6] See, e.g., J.N. Murrell, S. Carter, J. Phys. Chem. 88 (1984) 4887.
253


HO
2
POTENTIAL ENERGY SURFACE WITH
SPECTROSCOPIC ACCURACY: DMBE IV-M

Joo Brando
a
*, Jonathan Tennyson
b
, Carolina M. A. Rio
a

a
Departamento de Qumica, Bioqumica e Farmcia, Universidade do Algarve, 8005-139
Faro, Portugal
b
Department of Physics and Astronomy, University College London, London WC1E 6BT,
UK.
*jbrandao@ualg.pl

Seven potential energy surfaces [1-9] for the hydroperoxyl radical are com-
pared. The potentials were determined from either high quality ab initio
calculations, fits to spectroscopic data, or a combination of the two approaches.
Vibration-rotation calculations are performed on each potential and the results
compared with experiment. Using the DVR3D program suite [10] we compare
the spectroscopic predictions of these potentials and conclude that none of the
potentials are entirely satisfactory for spectroscopic studies.
Due to the high quality of the dynamical results from the DMBE IV potential
we propose to improve their spectroscopic properties adding a small term to
slightly modify the bottom well, while keeping the overall behavior of the PES
in those regions that should play an important role in controlling the reaction
dynamics in this system.
The functional form used is a polynomial times a quadratic term in the
displacement coordinates from the equilibrium geometry. To ensure the permute-
tion symmetry of this system we follow the ideas of Schmelzer and Murrell [11]
to define the coordinates for this additional term.
The modified DMBE IV: DMBE IV-M accurately reproduces the vibrational
levels (errors < 0.005 cm
-1
) and rotational constants, while keeping constant the
remaining features of this PES.

[1] S.Farantos, E.C. Leisegang, J.N. Murrell, K.Sorbie, J.J.C. Teixeira-Dias, and A.J.C.
Varandas, Molec. Phys. 34 (1977) 947.
[2] M.R. Pastrana, L.A.M. Quintales, J.Brando, and A.J.C. Varandas, J. Phys. Chem. 94
(1990) 8073.
[3] P.R. Bunker, I.P. Hamilton, and P.Jensen, J. Molec. Spectrosc. 155 (1992) 44.
[4] C.E. Dateo (1994), non published work, see V.J. Barclay, C.E. Dateo, and I.P.
Hamilton, J. Chem. Phys. 101 (1994) 6766.
[5] B.Kendrick and R.T. Pack, J. Chem. Phys. 102 (1995) 1994.
[6] A.J.C. Varandas, J.M. Bowman, and B.Gazdy, Chem. Phys. Lett. 233 (1995) 405.
[7] C.Xu, D.Xie, S.Zhang, D. H.Lin, and H.Guo, J. Chem. Phys. 122 (2005) 244305.
[8] S.Lin, H.Guo, P.Honvault, and D.Xie, J. Phys.Chem. B 110 (2006) 23641.
[9] D.Xie, C.Xu, H.T-S, H.Rabitz, G.Lendvay, S.Lin, and H.Guo, J. Chem. Phys. 126
(2007) 074315.
[10] J.Tennyson, J.R. Henderson, and N.G. Fulton, Computer Phys. Comms. 86 (1995)
175.
[11] A.Schmelzer and J.N. Murrell, Int. J. Quant. Chem. (1985) 287.
254


STRUCTURE EFFECTS ON THE INTERACTION OF
PHENOLIC ACIDS WITH DNA

Joana Vitorino, M. J. Sottomayor
Centro de Investigao em Qumica CIQ(UP), Departamento de Qumica, Faculdade
de Cincias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007, Porto,
Portugal
*joana.martavitorino@gmail.com, mjsotto@fc.up.pt

Recent interest in flavonoids and phenolic acids has been stimulated due to
their antioxidative and possible anticarcinogenic activities. Although many
anticancer drugs exert their primary biological effects by reversibly binding to
nucleic acids, very few studies on the possible interaction of phenolic
compounds with the DNA molecule exist in the literature.
The aim of the present work is to study the interaction of 3,4-
dihydroxybenzoic acid, 3,4-dihydroxyphenylacetic acid, hydrocaffeic acid and
caffeic acid with DNA, as part of a project devoted to the study of the interaction
between DNA and phenolic compounds.
A combination of micro-DSC and UV spectroscopy has been used to
evaluate the effect of these compounds on the thermal stability of double
stranded DNA, in aqueous solution. The characteristics of DNA thermal
denaturation have been used as a measure of the effect of the compounds on the
stability of the double helix.
Micro-DSC has been used to study the process of thermal denaturation of
DNA in solutions containing each of the acids. The observed enthalpy of
transition, the transition temperature and the heat capacity increment of DNA
thermal denaturation were determined for each compound. The dependence of
the melting temperature, enthalpy and heat capacity increment on acid
concentration was established for each acid.
UV thermal denaturation curves were also recorded under the same
experimental conditions as the DSC measurements. The transition temperature
values and the thermodynamic parameters of thermal denaturation were
determined and compared with the values obtained by micro-DSC.
The results indicate that the acids interact with the DNA molecule and
suggest an effect of the size and the degree of saturation of the lateral chain of
the acids on the extent of the interaction.

Thanks are due to Fundao para a Cincia e Tecnologia (FCT) for financial support to
Centro de Investigao em Qumica da Universidade do Porto (CIQ/UP).
255


ESTUDO TERMOQUMICO, EXPERIMENTAL E
TERICO, DE ALGUMAS HIDROXI-TETRALONAS

Clara C. S. Sousa
a
*, M. Agostinha R. Matos
a
, Victor M. F. Morais
a,b

a
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias
da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal
b
Instituto de Cincias Biomdicas Abel Salazar, Universidade do Porto, P-4099-003
Porto, Portugal
*clara.sousa@fc.up.pt

As tetralonas correspondem a uma classe de compostos orgnicos com um
papel bastante importante em sntese orgnica devido sua elevada reactividade.
So, por isso, bastante utilizadas como ponto de partida para a sntese de um
vasto conjunto de compostos heterocclicos com actividade biolgica [1] e
farmacolgica [2].
Determinaram-se os valores das entalpias de formao padro, em fase
condensada da 5-hidroxi-1-tetralona e da 6-hidroxi-1-tetralona utilizando a
tcnica de calorimetria de combusto em bomba esttica em seio de oxignio.
Combinando estes valores com os das entalpias de sublimao obtidas por
microcalorimetria Calvet obtiveram-se as entalpias de formao padro dos
compostos em fase gasosa, a T= 298.15K.
A geometria mais estvel dos compostos foi obtida usando a teoria dos
funcionais de densidade com o funcional B3LYP e dois conjuntos de funes de
base: 6-31G* e 6-311G**. Efectuou-se ainda um clculo do tipo scf com o
conjunto de funes de base cc-pVTZ. Os valores das entalpias de formao
padro, em fase gasosa, foram estimados utilizando um conjunto de reaces
isodsmicas e/ou homodsmicas adequadas.
Verificou-se que os resultados experimentais e os obtidos pelo mtodo de
clculo referido se encontram de acordo o que nos permitiu estimar as entalpias
de formao padro, em fase gasosa, para outros derivados cujo estudo
experimental no se realizou, 7-hidroxi-1-tetralona e 8-hidroxi-1-tetralona.

[1] A. Herrera, R. Martnez-Alvarez, M. Chioua, R. Chatt, R. Chioua, A. Snchez, J.
Almy. Tetrahedron, 62 (2006) 2799.
[2] M. J. Fisher, R. T. Backer, S. Husain, H. M. Hsiung, J. T. Mullaney, T. P. OBrian, P.
L. Ornstein, R. R. Rothhaar, J. M. Zgombick, K. Briner. Bioorg. Med. Chem. Lett., 15
(2005) 4459.
256


IMPORTANCE OF GLUCOSE FOR HUMAN
NEUTROPHILS OXIDATIVE BURST IN VITRO

Marisa Freitas
a
*, Graa Porto
b
, Jos L. F. C. Lima
a
, Eduarda
Fernandes
a
a
REQUIMTE, Departamento de Qumica-Fsica, Faculdade de Farmcia, Universidade
do Porto, Rua Anbal Cunha 164, 4099-030 Porto, Portugal
b
Servio de Hematologia Clnica, HGSA, Hospital Geral de Santo Antnio
*marisafreitas@ff.up.pt

One of the most important defense systems of neutrophils corresponds to
their ability to mediate a strong oxidative burst through the formation of reactive
oxygen species (ROS) and reactive nitrogen species (RNS). The evaluation of
ROS and RNS production by neutrophils, as well as the factors that can interfere
with that production, is currently a matter of extensive research. The contribution
of glucose for neutrophils oxidative burst has been controversial, since some
authors reported that a glucose challenge induces a consistent increase in ROS,
while others reported that high glucose concentrations impairs O
2
.- production.
Thus, the main objective of the present study was to attest the effect of different
concentrations of glucose on oxidative burst of neutrophils induced by PMA.
Once confirmed, the pathways leading to a better response of neutrophils were
evaluated measuring the influence of glucose in the energetic levels and
biochemical pathways involved in the production of NADPH.
The results demonstrated that glucose potentiates PMA-induced neutrophil
burst in a concentration dependent manner. Glucose-mediated potentiation of
PMA-induced neutrophil burst was not related to a putative increase of ATP
levels, but rather on the activation the pentose phosphate pathway (PPP), which
constitutes an essential pathway for NADPH supply, required for reactive
species production through NADPH oxidase.
We concluded that the presence of glucose is important as a source of
NADPH through PPP. The concentration 0.55 mM of glucose, 10 times lower
than the usually refered on literature, provided the best response of neutrophils to
PMA.

Acknowledgements: Marisa Freitas acknowledges Fundao para a Cincia e Tecnologia
(FCT) and Fundo Social Europeu (FSE) her PhD grant (SFRH/BD/28502/2006).
257


REDUCTASES DE LEVEDURAS - BIOMARCADORES DE
STRESS PELO VANDIO E ISOPROTURO

Sara Gonalves
a
, Marta Candeias
a
, Ana Conim
a
, Tnia Rosado
a
,
Isabel Alves-Pereira
a,b
Rui Ferreira
a,b
*
a
Departamento de Qumica, Universidade de vora, Ap 94, 7002-554 vora, Portugal
b
Instituto de Cincias Agrrias Mediterrnicas (ICAM), Ap94, 7002-554 vora, Portugal
*raf@uevora.pt

O pentxido de vandio, V
2
O
5
, forma pentavalente utilizada na industria do
cido sulfrico e dos fitofrmacos descrito como o composto de vandio mais
txico para os eucariotas com circulao ambiental. O isoproturo um
herbicida da famlia das fenilureias, (3-(4-isopropilfenil)-1,1-dimetilureia, com
permanncia elevada em solos e guas superficiais. A toxicidade por metais e
poluentes orgnicos resulta da formao de espcies reactivas de oxignio (ERO)
geradas pelo transporte de electres mitocondrial e/ou microssomal que causam
danos em biomolculas, via peroxidao lipdica. As leveduras possuem
enzimas envolvidos na remoo de EROs, como o glutationo reductase (GR, EC
1.6.4.2) que integra o ciclo redox do glutationo e gera potencial redutor, GSH,
necessrio a outros enzimas antioxidativos, glutationo S-transferase (GST, EC
2.5.1.18) e catalase T (CAT T, EC 1.11.1.6). Alteraes nas actividades
enzimticas GR e NADPH (P450) reductase (NADPHred, EC 1.6.2.4) induzidas
por nveis baixos de agentes de stress em meios aquosos, podem ser indicadores
da presena de metais e fitofrmacos.
Consequentemente, o objectivo deste trabalho foi quantificar nveis
intracelulares de reductases (GR e NADPHred) de leveduras vnicas
Saccharomices cerevisiae UE-M
3
,

nativas do Alentejo, expostas 3 e 72 h a
|V
2
O
5
| (0,5-2 mM) ou de |isoproturo| (5-100 M), tendo em vista aplicar o
perfil de resposta enzimtica a estes poluentes na deteco integrada de vandio
e de isoproturo em meios aquosos. As actividades GR e NADPHred foram
quantificadas na fraco ps-peroxissomal e microssomal, respectivamente [1,2].
Os resultados obtidos mostram que o V
2
O
5
e o isoproturo, provocaram
alteraes significativas nas actividades GR e NADPHred nos nveis e tempos de
exposio testados. No que diz respeito actividade GR, a resposta foi mais
uniforme para os dois compostos em estudo, nos ensaios de 72 h de exposio
com induo da actividade especfica altamente significativa (72-186 % V
2
O
5
e
34-119 % isoproturo). Nos ensaios com tempo de exposio de apenas 3 h
ocorreu uma resposta bimodal dos enzima GR e NADPHred ao vandio, com
activao significativa para 2,0 mM de V
2
O
5
no meio de cultura.
GR e NADPHred de levedura podem ser utilizados para detectar a presena
de vandio ou isoproturo em meios aquosos.
[1] D.M. Goldberg e R.J. Spooner. Clinical Enzymology Symposia, Piccin Medical
Books, London, 1977.
[2] D.M. Ziegler e L.L. Poulsen. Methods in Enzymology, Academic Press, NY, 1978.
258


ANTIOXIDANT ACTIVITY OF PORTUGUESE
HONEY SAMPLES

Edmur Aires, Isabel C. F. R. Ferreira*, Letcia M. Estevinho

CIMO, Escola Superior Agrria, Instituto Politcnico de Bragana, Campus de Santa
Apolnia, Apartado 1172, 5301-855 Bragana, Portugal.
*iferreira@ipb.pt

Reactive oxygen species are known to be implicated in many cell disorders
and in the development of many diseases including cardiovascular diseases,
atherosclerosis, cataracts, chronic inflammation, or neurodegenerative diseases
such as Alzheimers or Parkinsons disease. Thus, synthetic antioxidants are
widely used in food industry, but because of their toxic and carcinogenic effects,
their use is being restricted. The pursuit for novel natural sources of bioactive
compounds, namely those who present antioxidant activity, has been acquiring
higher significance, since these compounds may contribute for the prevention of
diseases in which free radicals are implicated. Honey is a natural food, rich in
essential nutrients, produced by different species of bees. The use of honey in
medicine is an old tradition being its medicinal properties known since ancient
times. Its high content in phenolic compounds might contribute to important
antioxidant properties.
In this study, the antioxidant activity of two honey samples from Trs-os-
Montes region (light and dark) were evaluated through chemical and biochemical
assays: DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging activity,
reducing power, inhibition of |-carotene bleaching, and inhibition of lipid
peroxidation in pig brain tissue through formation of thiobarbituric acid reactive
substances (TBARS). For all the methods EC
50
values were calculated in order to
evaluate the antioxidant efficiency of each sample. The total phenols and
flavonoid contents were also obtained and correlated with antioxidant activity.
The dark sample revealed better antioxidant properties, presenting lower EC
50

values than the light sample. The highest antioxidant contents (phenols and
flavonoids) were also found for the first sample.
259


ANTIOXIDANT ACTIVITY OF NON STEROIDAL ANTI-
INFLAMATORY DRUGS ANTIPIRYNE AND DERIVATIVES

Abel Vieira
a
*, Pedro Santos
a
, Alexandra Antunes
a
, Joo Noronha
a
,
Eduarda Fernandes
b
a
REQUIMTE/CQFB, Departamento de Qumica, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal
b
REQUIMTE/CEQUP, Departamento de Qumica-Fsica, Faculdade de Farmcia,
Universidade do Porto, Portugal
*ajvieira@dq.fct.unl.pt

Antipyrine (I) and 4-Dimethylaminoantipyrine (II) are pyrazolone
derivatives with therapeutical effects, which have been attributed to their
analgesic, antipyretic and anti-inflammatory properties. These compounds have
also been appointed as potential antioxidants. Previous results show a much
higher antioxidant activity of II as compared to I, which was attributed to
capacity of the former to undergo oxidation followed by demethylation in the
reaction with free radicals,

giving rise to 4-methyl-aminoantipyrine (III), which
can be further demethylated to 4-aminoantipyrine (IV).
To evaluate the antioxidant capacity of antipiryne and its derivatives, these
compounds have been reacted with oxidising radicals. Upon reaction with
sulphate radical anion, generated by chemical methods, the one electron oxidised
form of II, a radical cation, was obtained and its structure characterised by ESR
spectroscopy (the same spectrum is also obtained by oxidation with OH). The
radical cations of III and IV were not stable enough to be measured. Compounds
I-IV were also reacted with hydroxyl radical, generated either by radiomimetic
methods (e.g. Fenton reaction) or by radiolysis of aqueous solutions (with -
irradiation from a
60
Co source). The final stable products were analysed and
identified by HPLC-MS and
1
H-NMR techniques.
In conclusion, the results show that the antioxidising effect of these pyrazolones
results from their capacity to react with highly oxidising species. The
methylamino-derivatives undergo successive demethylation. In addition, in all
cases, hydroxylation on both aromatic and heterocyclic rings occurs.

N
N
O
C
6
H
5
N
N
N
O
C
6
H
5
NH
N
N
O
C
6
H
5
NH
2
[O] [O]
Final Oxidation Products
II
III
IV
N
N
O
C
6
H
5
I
;

N
N
O
N
OH N
N
O
N
HO
Final hydroxylation products

ESR spectrum of the radical cation of II
260


HETEROGENEIZAO DE COMPLEXOS DE
COORDENAO DE ALPHA DIIMINAS DE NIQUEL
PARA A POLIMERIZAO DE ETILENO

Ins Matos
a,b
*, Isabel Fonseca
c
, Ana M. Botelho do Rego
a
, M. A. N.
D. A. Lemos
b
, Auguste Fernandes
b
, Rita Catalo
b
, Francisco Lemos
b
,
Maria M. Marques
a

a
Centro de Qumica Estrutural, Instituto Superior Tcnico, Departamento de Engenharia
Qumica, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
b
IBB, Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical
Engineering, Instituto Superior Tcnico
c
REQUIMTE, Faculdade de Cincia e Tecnologia, Universidade Nova de Lisboa, 2829-
516 Caparica, Portugal
*inesmatosa@gmail.com

Introduo
Um dos objectivos deste trabalho consistiu no desenvolvimento de novos
catalisadores heterogneos partindo de precursores catalticos estudados em fase
homognea. O interesse deste estudo reside na possibilidade de se obter
catalisadores heterogneos que confiram ao polmero caractersticas semelhantes
[1] s que possvel obter quando se aplica um precursor cataltico de centro
activo uniforme em fase homognea [2].

Resultados e concluso
Apresenta-se o estudo da preparao e
caracterizao de catalisadores heterogneos
com centro activo uniforme.
Foram aplicados dois mtodos de preparao: 1) a impregnao directa do
complexo de alfa diimina de Nquel (fig1) - um catalisador do tipo Brookhart -
no material de suporte; 2) a alterao da superfcie do suporte por introduo do
metal e posterior insero/coordenao do ligando orgnico. Os suportes
estudados foram o NaY e o MCM41.
O primeiro mtodo demonstrou ser bastante eficiente, uma vez que o
catalisador heterogneo resultante permanece com elevada actividade cataltica,
e o polmero obtido na reaco de polimerizao apresenta as mesmas
caractersticas estruturais do polmero obtido com o sistema homogneo. No
entanto tem a desvantagem de ficar muito pouco complexo impregnado no
suporte dificultando a sua caracterizao. Este trabalho mostrou que possvel
preparar catalisadores com actividade razovel seguindo o segundo mtodo.
Conclui-se que necessrio uma ligao forte do metal ao suporte para que seja
possvel que ocorra heterogeneizao com sucesso.
[1] S.D. Ittel, L.K. Jonhson, M. Brookhart, Chem. Rev. 100 (2000) 1169.
[2] J.R. Svern, J.C. Chadwick, R. Duchateau, N. Friederichs, Chem. Rev. 105 (2005) 4073.
N N
Ni
Si
Si
Br Br

Figure 1
261


OXIDAO SELECTIVA DE GLICEROL CATALISADA
POR METAIS NOBRES EM CARVO ACTIVADO

E. G. Rodrigues, O. S. G. P. Soares, S. A. C. Carabineiro, F.
Gonalves, M. F. R. Pereira, J. L. Figueiredo, J. J. M. rfo*
Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM,
Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*jjmo@fe.up.pt

Os incentivos recentes produo de biodiesel, tanto nos Estados Unidos
como na Europa, conduziram inundao do mercado com glicerol, que um
sub-produto do respectivo processo de fabrico. Atendendo a que por cada
tonelada de biodiesel produzido se obtm cerca de 100 kg de glicerol,
importante encontrar formas de valorizar aquele composto. A oxidao cataltica
do glicerol uma opo prometedora, desde que o catalisador utilizado seja
suficientemente activo e, sobretudo, selectivo para a formao de compostos tais
como o cido glicrico e/ou a dihidroxiacetona, potenciais intermedirios nas
indstrias de qumica fina, nomeadamente na farmacutica. O processo tem
vindo a ser investigado, sendo os catalisadores base de platina, de paldio ou
de ouro, suportados em carvo activado, os mais estudados [1-3].
Neste trabalho, estudou-se a influncia da natureza do metal (Pd, Pt, Ir, Rh ou
Au) e da qumica superficial do carvo activado na oxidao selectiva do
glicerol. Esta foi realizada num reactor semi-fechado presso de 3 bar e na
gama de temperaturas entre 30 C e 60 C, usando uma concentrao inicial de
glicerol de 0,3 mol/L. Para produzir suportes com propriedades qumicas
superficiais diferentes, partiu-se do carvo activado NORIT ROX 0.8 (ACo),
tendo-se efectuado os seguintes tratamentos: oxidao em fase lquida com
HNO
3
6M (AC
1
) (suporte cido) e tratamento trmico em azoto a 900C (AC
2
)
(suporte bsico). Foram seleccionadas as fraces com um dimetro de partculas
entre 0,1 e 0,3 mm. Os catalisadores (1%wt de metal) foram preparados pela
tcnica de impregnao incipiente utilizando solues apropriadas de cada um
dos metais (PdCl
2
, H
2
PtCl
6
, RhCl
3
, (NH
4
)
3
IrCl
6
ou HAuCl
4
) e, no caso do ouro,
tambm por imobilizao a partir de uma soluo coloidal. Aps secagem numa
estufa a 100 C durante 24 h, as amostras preparadas por impregnao incipiente
foram submetidas a tratamento trmico em azoto e posteriormente reduzidas com
hidrognio, usando diferentes protocolos. Os catalisadores preparados foram
caracterizados por quimissoro de hidrognio, adsoro de azoto a 77 K, DSC,
TPR, XPS e TEM. Para efeitos comparativos, foi igualmente considerado neste
trabalho o catalisador de referncia Au/C do World Gold Council.
Agradecimentos: Fundao para a Cincia e a Tecnologia (FCT) e FEDER (POCTI/1181) pelo
financiamento e World Gold Council pela amostra de referncia.
[1] R. Garcia, M. Besson, P Gallezot, Appl. Catal. A: Gen. 127 (1995) 165.
[2] S. Demirel-Glen, M. Lucas, P. Claus, Catal. Today 102-103 (2005) 166.

[3] W.C. Ketchie, M. Murayama, R.J. Davis, Top. Catal. 44 (2007) 307.
262


DEGRADAO FOTO-OXIDATIVA DO TERPOLMERO
ACRILONITRILO-BUTADIENO-ESTIRENO

Raquel M. Santos
a,b
*, Gabriela L. Botelho
a
, Ana V. Machado
b
, Jorge
S. Conduto
c
a
Departamento de Qumica, Universidade do Minho, Campus de Gualtar, 4710-057
Braga, Portugal.
b
Departamento de Engenharia de Polmeros, Universidade do Minho, Campus de
Azurm, 4800-058 Guimares, Portugal
c
COLORGAL-Cores de Portugal Lda, Zona Industrial das Corredouras 2630-355 Arruda
dos Vinhos, Portugal
*raquel_miriam_santos@hotmail.com

Os artigos fabricados com materiais polimricos esto sujeitos a degradao,
devido ocorrncia de reaces qumicas, de que resultam alteraes das
propriedades qumicas, fsicas e mecnicas. Estas so essenciais do ponto de
vista da utilizao dos materiais, pois condicionam o seu tempo de vida til. So
diversos os factores que podem conduzir degradao dos materiais polimricos,
nomeadamente, factores externos relacionados com as condies atmosfricas e
factores inerentes ao prprio material [1].
O acrilonitrilo-butadieno-estireno (ABS) um termopolmero com grande
aplicao na indstria transformadora de plsticos devido excelente
combinao entre boas propriedades e custo compatvel para um polmero de
engenharia. Todavia, este material apresenta tendncia para amarelecer durante o
processamento e conhecido por apresentar uma resistncia inaceitvel aos UV
[2] contrariamente a outros materiais polimricos [3].
Actualmente a seleco do tipo/quantidade de aditivos utilizados para
minimizar a degradao feita com base empirica, uma vez que os mecanismos
de degradao e estabilizao no se encontram devidamente investigados.
Assim, o presente projecto tem como principal objectivo a compreenso do
mecanismo de degradao foto-oxidativa de ABS de forma a desenvolver novos
produtos com desempenho optimizado radiao ultravioleta.
Neste trabalho sero apresentados os resultados obtidos da degradao foto-
oxidativa realizada numa cmara xenoteste que simula as condies climatricas
exteriores segundo a norma ISO 4892-2. A caracterizao fsico-qumica e
mecnica foi efectuada de modo a ser possvel avaliar os efeitos da radiao
ultravioleta sobre o polmero e, posteriormente propor um mecanismo de
degradao.

[1] J.F. Rabek, Polymer Photodegradation- Mechanisms and Experimental Methods,
Chapman & Hall (1995).
[2] M.M. Motyakin, S. Schlick, Polymer Degradation & Stability 76 (2002) 25.
[3] G. Botelho, M. Silva, A. Gonalves, V. Sencadas, J. Nunes, S. Lanceros Mendez,
Polymer Degradation & Stability (2008) in press.
263



300 400 500 600
0,0
0,8
1,6
2,4


A
b
s
(nm)
Leuco
Keto
SPECTRAL AND PHOTOPHYSICAL STUDIES OF
SUBSTITUTED INDIGO DER. IN THEIR LEUCO FORMS

Raquel Rondo
a
*, J. Seixas de Melo
a
, M. J. Melo
b
, G. Voss
c

a
Departamento de Qumica, Universidade de Coimbra, P3004-535 Coimbra, Portugal
b
Dep. de Conservao e Restauro and ReQuimte, FCT, Univ. Nova de Lisboa, Portugal
c
Department of Bioorganic Chemistry, Univ. of Bayreuth, D-95440 Bayreuth, Germany
*raquel.rondao@sapo.pt

The natural Indigo plant, Isatis tinctoria, is a talismanic molecule who has
linked civilizations.

Several illustrative examples of Indigos impact to mankind
history are the sacred blue of the Jewishs, the tecklet, the blue of Napoleons
Bonaparte army uniforms and the still famous blue jeans [1]. Part of this
longevity is related with its stability. The electronic spectra and photophysics of
indigo and related molecules has been recently investigated [2-4].


In this work, the spectral and photophysical properties of some di-, tetra- and
hexa-substituted indigo derivatives in their leuco form were investigated in
solution. The study comprises absorption and emission spectra, together with
quantitative measurements of quantum yields of fluorescence (|
F
) and singlet
oxygen formation (|
A
) and fluorescence lifetimes (t
F
). Transient triplet-triplet
spectra and yields were also obtained.
In the case of keto forms (weakly fluorescent) (Scheme 1) intramolecular H-
bonds are suggested to provide a channel for the rapid radiationless deactivation
from the lowest singlet excited state to the ground state whereas with the leuco
forms there is competition between internal conversion, triplet formation, and
fluorescence deactivation processes. The leuco forms, however, presents a much
higher Stokes shifts when compared with the keto form, suggesting an excited-
state geometry different from the ground-state geometry, possibly involving
rotational photoisomerization where hydrogen proton transfer between N-H and
C=O groups is not likely to occur [2-4].
Acknowledgments: Financial support from FEDER and FCT (project POCI/QUI/
55672/2004 The Molecules of Color in Art: a Photochemical Study). R. Rondo
acknowledges FCT for a PhD grant (SFRH/BD/38882/2007)
[1] Balfour-Paul, J. Indigo; British Museum Press, 2000.
[2] J. Seixas de Melo, A. P. Moura, M. J. Melo, J. Phys. Chem. A 108 (2004) 6975.
[3] J. Seixas de Melo, R. Rondo, H. D. Burrows, M.J. Melo, S. Navaratnam, R. Edge, G.
Voss, J.Phys.Chem.A 110 (2006) 13653.
[4] J. Seixas de Melo, R. Rondo, H.D. Burrows, M.J. Melo, S. Navaratnam, R. Edge, G.
Voss, ChemPhysChem 7 (2006) 2303.

N
N
O
O
H
H
N
N
H
H
-
O
O
-
KETO LEUCO
Scheme 1
264


APPLICATION OF BIOPOLYMER AGAR TO GREEN
PACKAGING AND COATING

Ana M. M.Sousa*, Ronald D. Villanueva, Loic Hilliou, Maria P.
Gonalves
REQUIMTE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-
465 Porto, Portugal
*ana.sousa@fe.up.pt

The objectives of this work include the optimization of the agar extraction
from Gracilaria vermiculophylla, the production of gels and biodegradable films
and the application of the agar extract as an edible coating in fruits. The effect of
alkali pre-treatment (duration and NaOH concentration) and extraction time were
separately investigated and optimized in terms of agar yield, gel strength and
Youngs modulus. Alkali pre-treatment (PT) was carried out at 0.5, 1.5, 2.5 and
3.5 h and at NaOH concentrations of 0, 2, 4, 6 and 8%, in a full factorial design.
The highest yield and gel strength were obtained at 3.5 h duration and 6%
NaOH, thus the succeeding extraction optimization was done employing these
PT conditions. Extractions were carried out at 1.5, 2, 2.5 and 3 h and best agar
quality was obtained for a 2-hour extraction time. Therefore, the optimum
conditions for agar extraction from the alga are 3 h PT duration, 6% NaOH
concentration and 2 h extraction time. Films from agar extracted using the
optimum conditions were made using the knife coating technique. The physical
properties of films such as hygroscopicity, mechanical resistance, thermal
stability, solubility and permeability to water vapour were characterized. The
agar films were transparent, optically clear and possess good mechanical and
barrier properties, which make them interesting materials for edible coating.
Therefore, the potential application to fresh fruit preservation was investigated.

265


GOLD ON MAGNETITE NANOPARTICLES: GROWTH TO
A CORE-SHELL SYSTEM

Pedro Quaresma
a,e
*, Peter Eaton
a
, Ricardo Franco
b
, Patrcia Carvalho
c
,
Joo Pedro Araujo
d
, Pedro Baptista
e
, Eullia Pereira
a

a
REQUIMTE, Faculdade de Cincias, Universidade do Porto, R. Campo Alegre 687,
4169-007 Porto, Portugal
b
REQUIMTE, Departamento de Qumica, CQFB, FCT-UNL, 2829-516 Caparica, Portugal
c
Departamento de Engenharia de Materiais, IST, Av. Rovisco Pais 1049-100 Lisboa, Portugal
d
IFIMUP, R. Campo Alegre, 678, 4169-007 Porto, Portugal
e
CIGMH, Departamento de Cincias da Vida, FCT-UNL, 2829-516 Caparica, Portugal
*pedro.quaresma@fc.up.pt

Magnetic nanoparticles for selective capture of biomolecules in complex
mixtures is gaining momentum in bionanotechnology by providing significant
advantages over traditional methods of separation [1]. A magnetite-gold core-
shell structure would grant researchers with an integrated detection and gene
fishing platform by means of the detection properties of gold nanoparticle
systems combined with a magnetic component [2, 3]. Magnetic nanoparticles of
Fe
3
O
4
were produced using a acetylacetonate metal precursor resulting in
enhanced control over size and monodispersity, as confirmed by transmission
electron microscopy (TEM) [4]. An ultrasound mediated procedure was
employed for in-situ formation of gold nuclei on the surface of magnetite
nanoparticles. The growth of the gold nuclei on the magnetite to a gold shell
layer was achieved by an iterative addition of gold precursor and reducing agent.
The growth of the gold layer was followed by TEM, UV-Vis and EDS. Magnetic
measurements were performed by SQUID and show the superparamagnetic
character of the formed particles. MFM studies were also performed. Several
parameters, such as gold precursor concentration, reductant concentration, rate of
reagents addition and initial nanoparticle concentration were analysed. Also,
different chemical reductants were evaluated for their ability to produce a
complete gold shell.

[1] A. Ito, M. Shinkai, H. Honda, T. Kobayashi, J. Biosci. Bioeng. 100 (2005) 1.
[2] L.Y. Wang, J. Luo, Q. Fan, M. Suzuki, I.S. Suzuki, M.H. Engelhard, Y.H. Lin, N.
Kim, J.Q. Wang, C.J. Zhong, J. Phys. Chem. B 109 (2005) 21593.
[3] C. Xu, J. Xie, D. Ho, C. Wang, N. Kohler, E.G. Walsh, J.R. Morgan, Y.E. Chin, S.
Sun, Angew. Chem.-Int. Ed. 47 (2008) 173.
[4] S.H. Sun, H. Zeng, D.B. Robinson, S. Raoux, P.M. Rice, S.X. Wang, G.X. Li, J. Am.
Chem. Soc. 126 (2004) 273.
266


MORDANT ION INFLUENCE IN COLOUR HUE AND
PHOTODEGRADATION OF WOOL DYED FIBERS

Vanessa Pimenta
a
, Ana Manhita
a
, Helena Vargas
b
, Isabel Ribeiro
b
,
Teresa Pacheco
c
, Jos Miro
a,d
, Cristina T. da Costa
a
, Antnio
Candeias
a
, Teresa Ferreira
a,e
*
a
University of vora, Chemistry Department and CQE, R. Romo Ramalho, 59, 7000
vora, Portugal
b
Museums and Conservation Institute, Materials Studies Department, Portugal
c
National Museum of Ancient Art (MNAA), Lisboa, Portugal
d
University of vora, Geosciences Department & Geophysics Center of vora, Portugal
e
CCMM, Faculty of Sciences, University of Lisbon, Portugal
*tasf@uevora.pt

Materials studies is a very important issue for providing the knowledge
required for an appropriate conservation of a textile object. Moreover, it supplies
information that combined with cultural and social data allows a better
description of certain historical periods and their ways of living. Arraiolos
tapestries are clearly one of the most important cultural expressions of Alentejo
region, being a significant part of its cultural heritage. In this context, it is of
main interest the materials investigation to identify the mordant and natural dyes
employed in their manufacture, since the hues and colours in the textiles depend
on the nature and concentration of the mordant and dyestuff employed.
The analysis of historical textiles should be preceded by the preparation of
dyed wool references. Wool samples were mordanted with aluminium, copper
and iron salts, in different concentrations. Although copper and iron were never
referred by Rivara [1] in his dye recipe book, iron has already been found in
some historical wool fibers of the Arraiolos rugs analyzed, belonging to the
Portuguese Ancient Art National Museum collection (MNAA). Weld (Reseda
luteola L.) and onions skins (Allium cepa L.), commonly used yellow dye
sources, were used as sources of yellow hues. The dyed samples were also
prepared by two distinct methodologies. In general, brownish and greenish
colour patterns were obtained for samples in which iron or copper were used
while yellow/orange colours were shown with aluminium salt. Accelerated light
ageing studies produced differentiate colour alterations (measured by
colorimetry) in samples dyed with the same dye source but different mordant.
Degradation products identification was done by LC-DAD-MS analysis of the
artificially aged wool extracts. SEM/EDS characterization confirmed the
different concentrations of mordant in the samples and in some cases loss of the
wool scaled structure due to the acidic character of the mordanting solution.

This work is integrated in the project REMATAR- Rediscovering the Materials of
Arraiolos Tapestries (PTDC/HAH/64045/2006).

[1] J.H.C. Rivara, Memorias da Vila de Arrayolos, C. M. Arraiolos, Arraiolos, 1985.
267


TEORES DE VITAMINA E EM DIFERENTES
VARIEDADES DE CASTANEA SATI VA

Joo C. M. Barreira
a,b
, Rita C. Alves
b
, Susana Casal
b
, Isabel C. F. R.
Ferreira
a
, Jos Alberto Pereira
a
* M. Beatriz P. P. Oliveira
b
*

a
CIMO, Escola Superior Agrria, Instituto Politcnico de Bragana, Campus de Santa
Apolnia, Apartado 1172, 5301-855 Bragana, Portugal
b
REQUIMTE, Servio de Bromatologia, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*beatoliv@ff.up.pt, jpereira@ipb.pt

Vitamina E a designao comum de uma famlia de compostos
relacionados, nomeadamente os tocoferis e os tocotrienis, caracterizada por
conter uma cadeia lateral isoprnica ligada ao cromanol [1]. A caracterizao
qualitativa e quantitativa dos diferentes vitmeros, apesar de estruturalmente
similares, fundamentada pelas diferenas nas respectivas actividades
biolgicas.
Apesar do estudo deste grupo de substncias ter merecido a ateno de
diversos grupos de investigao, no temos conhecimento da sua aplicao
fraco lipdica da castanha.
Neste sentido, o objectivo deste trabalho consistiu em desenvolver uma
metodologia para caracterizar os ismeros da vitamina E presentes em diferentes
variedades de castanha (Castanea sativa). Para tal foram seleccionadas quatro
variedades regionais: Avelaneira, Boaventura, Judia e Longal.
A extraco da fraco lipdica utilizou ter de petrleo como solvente
extractor em Soxhlet, em presena de BHT para preservar a integridade dos
vitmeros presentes. Usou-se como padro interno tocol e a anlise
cromatogrfica decorreu em fase normal/HPLC/DAD/FL (
ex
= 290 nm;
em
=
330nm) com uma coluna Inertsil 5 SI (250 e mm) da Varian (Middelburg,
Holanda) temperatura ambiente. A fase mvel utilizada foi a mistura de hexano
e dioxano (97:3, v/v) com um fluxo de 0,7 ml/min e um volume de injeco de
20 l.
Dos vitmeros da vitamina E, o -tocoferol o maioritrio para todas as
variedades avaliadas, revelando quantidades superiores a 400 g/g leo. Foram
identificados e quantificados 5 vitmeros (-tocoferol, -tocoferol, -tocotrienol,
o-tocoferol e o-tocotrienol).

[1] J.S. Amaral, S. Casal, D. Torres, R.M. Seabra, B.P.P. Oliveira. Anal. Sci. 21 (2005)
1545.
268


IMPROVED CHROMATOGRAPHIC METHODOLOGIES
FOR FOOD CONTROL MARKERS OF QUALITY

Elvira M. Gaspar*, Joo F. Lopes, Ana F. Lucena
Departamento de Qumica, CQFB-Requimte, Faculdade de Cincias e Tecnologia,
Universidade Nova de Lisboa. Quinta da Torre, 2829-516 Caparica, Portugal
*emg@dq.fct.unl.pt

There is a recognized need to develop simple and reliable methods for the
analysis of markers of quality of food products. During processing and storage of
carbohydrate containing foods, chemical modifications can take place. 5-
Hydroxymethylfurfural (5-HMF), 5-methylfurfural (5-MF) and 2-furfural (F) are
recognized parameters related to the freshness and quality of some foods. They
have been used to evaluate both the quality of the processing method and the
organoleptic characteristics of the final products. The Codex Alimentarius of the
WHO and the European Union (EU Directive 110/2001 [1]) have established a
maximum HMF quality level in honey (40 mgKg
-1
) and in apple juice (50 mgKg
-
1
) as deterioration and heat-treatment indicator. The Federation of Fruit Juice
Processors (IFFJP) recommends a maximum concentration of 5-10 mgL
-1
of
HMF in fruit juices and 25 mgL
-1
in fruit concentrates [2].
Patulin is a mycotoxin produced by several fungal species of Penicillium,
Aspergillus and Byssochlamys which grow on fruit especially apples, pears and
grapes [3]. The occurrence of patulin as a natural contaminant of fruit juices,
indicative of the quality of the fruit used in production, is a worldwide problem
and international recommendations and regulations have been made for
maximum levels permitted in consumer products. Joint FAO/WHO Expert
Committee on Food Additives (JECFA) established the provisional maximum
torelable daily intake (PMTDI) for patulin from 1 to 0.4 gKg
-1
body mass/day.
This work describes improved, simple, economical methodologies for the
simultaneous determination of furanic Maillard derivatives (furfurals) and
patulin in food products. The compounds were determined by reversed-phase
HPLC-DAD and/or DI-SPME-GC-(FID/TOF-MS). The methods, simple and
accurate, showed good recoveries of furfurals (ranged from 50 to 100 %, with an
overall mean of 93%) and patulin (ranged from 55 to 100%, with an overall
mean of 92%); they were applied to different commercial food matrices. The
one-step, sensitive (the limits of detection for patulin and HMF were 0.007 ppm
and 0.7 ppm respectively, using HPLC methodology), no time consuming
methodologies will contribute to characterize and quantify the presence of these
compounds in human diet, will make possible to determine the toxicological
relevance of human exposure to furfurals and patulin, their biological role and
long-term implications of their consumption for human health.

[1] Directive 2001/110/EC of 20 December 2001. Off. J. Eur. Commun.
[2] H.K. FranK, Alimenta 3 (1974) 98.
[3] M.H. Iha and M. Sabino, J. Assoc. Off. Anal. Chem. (AOAC) Intern.89 (2006) 139.
269


MDULO DE EXTRACO SEM MEMBRANA:
APLICAO ANLISE DE SO
2
EM VINHO

M. F. Anunciao, J. P. Pacheco, J. A. Rodrigues*, A. A. Barros

Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre, 687, 4169-007,
Porto, Portugal
*jarodrig@fc.up.pt

A maioria das metodologias analticas requer pelo menos um passo de
separao na preparao de amostras. A separao em linha e subsequente
deteco de compostos volteis ou semi-volteis normalmente realizada atravs
de dois tipos de sistemas baseados em membranas: difuso gasosa e
pervaporao analtica Apesar destes sistemas serem muito teis na separao
selectiva de compostos volteis, tm como principal desvantagem a colmatao
da membrana e consequente necessidade de substituio [1].
Neste trabalho, desenvolveu-se um novo mdulo para extraco de
compostos volteis por difuso gasosa, sem necessidade de uso de membrana.
Este mdulo possui um funcionamento similar a um mdulo de extraco por
difuso gasosa convencional. constitudo por uma cmara inferior, na qual a
amostra passa. Os compostos volteis difundem-se para o interior do mdulo
onde se encontra uma pequena cpsula em suspenso. Estes compostos circulam
livremente no interior do mdulo e so recolhidos numa soluo de recolha
existente na cpsula suspensa. Consegue-se, desta forma, a extraco de
compostos volteis sem recorrer ao uso de uma membrana, ultrapassando-se,
assim, os problemas relacionados com o seu uso.
O mdulo sem membrana foi utilizado para a determinao de SO
2
no vinho.
A tcnica analtica utilizada para a medio analtica foi a voltametria. O SO
2

um aditivo alimentar muito importante devido, essencialmente ao seu poder
antioxidante e por apresentar propriedades anti-spticas, pelo que a sua
determinao de grande importncia para a indstria vitivincola [2].
A metodologia desenvolvida consiste na acidulao em linha e introduo
contnua da amostra na cmara inferior do mdulo de extraco sem membrana.
Na cpsula suspensa colocada uma soluo tampo acetato. Ao fim de um certo
perodo de tempo esta soluo recolhida e analisada voltametricamente. Os
resultados obtidos foram comparados com o mtodo de Ripper, actualmente
usado como norma portuguesa [3].

[1] N. Choengchan, T. Mantim, P. Wilairat, P.K. Dasgupta, S. Motomizu, D. Nacapricha.
Anal. Chim. Acta 579 (2006) 33.
[2] D. Bird, Understanding wine technology: The science of wine explained, The Wine
Appreciation Guild, 4 ed., E.U.A., 2005.
[3] Annimo, Norma Portuguesa: Bebidas e Alcolicas e Espirituosas Determinao
dos Teores de Anidrido Sulfuroso (Dixido de Enxofre) livre, combinado e total,
Instituto Portugus da Qualidade, NP 2220.
270


DETERMINATION OF H
2
O
2
BY FLOW INJECTION
ANALYSIS BASED ON TITANIUMPEROXIDE COMPLEX

Joana Ribeiro*, Marcela A. Segundo, Salette Reis, Jos L. F. C. Lima
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia, Universidade do
Porto, Rua Anbal Cunha, 164, 4099-030 Porto, Portugal
*joananiz@hotmail.com

Hydrogen peroxide (H
2
O
2
) presents a wide range of applications, including
bleaching of pulp and paper, manufacturing of fine chemicals and
pharmaceuticals, effluent treatment, and it is also used in the cosmetic and food
industry [1]. In addition, H
2
O
2
plays an important role in biological systems,
belonging to the reactive oxygen species group. Nowadays, research about
antioxidants and oxidative stress has focused attention upon this species [2]. In
this context, fast and reliable methods for determination of H
2
O
2
are necessary.
With this purpose, various analytical procedures have been suggested for the
automatic H
2
O
2
measurement, including those based on flow injection analysis
(FIA) [3].
In this work, the automatic determination of H
2
O
2
was based on the titanium-
peroxide [TiO
2
]
2+
complex. Using a three channel FIA manifold, H
2
O
2
was
injected into a carrier stream (H
2
O), which was further merged with Ti(IV)OSO
4
and H
2
SO
4
streams. In the reaction coil, complexation between H
2
O
2
and Ti(IV)
took place, originating [TiO
2
]
2+
complex, which was detected
spectrophotometrically at 405 nm [4]. The mixing order of reagents, the length
of reaction coil and the concentration of reagents were studied in order to
improve the sensitivity of the method. The results showed no statistical
difference between the two distinct manifold configurations applied, indicating
that the mixing order of reagents did not influence the analytical performance.
The best results were obtained for a reaction coil of 50 cm. Concerning the
concentration of reagents tested, Ti(IV)OSO
4
2.5 x 10
-2
M and H
2
SO
4
1.0 M
were chosen. The figures of merit and application to real samples are currently
under investigation.

Acknowledgements: Joana Ribeiro thanks Fundao para a Cincia e Tecnologia (FCT)
for the grant SFRH/BD/29857/2006.

[1] I.L. Mattos, K. A. Shiraishi, A. D. Braz, J. R. Fernandes. Quim. Nova 26 (2003) 373.
[2] G.P. Bienert, J.K. Schjoerring, T.P. Jahn. Biochim. Biophys. Acta 1758 (2006) 994.
[3] M.S. Bloomfield. Talanta 64 (2004) 1175.
[4] D.W. OSullivan, M. Tyree. Int. J. Chem. Kinetics 39 (2007) 457.
271


SINGLE-STANDARD CALIBRATION IN SIA
ANALYTICAL SYSTEMS

Leonel G. C. Soares*, Rui A. S. Lapa
REQUIMTE, Faculdade de Farmcia da Universidade do Porto, Rua Anbal Cunha, 164,
4099-030 Porto
*leonelgasparsoares@gmail.com

The flow techniques provide a wide range of possibilities being calibration
and dilution schemes applicable to a variety of analytical methodologies [l, 2].
Among the flow techniques, the Sequential Injection Analysis (SIA) analytical
systems have been applied in the refinement of calibration techniques to
accompany the wide range of analytical applications.
The preparation of accurate calibration standards is critical in chemical
analysis been time consuming and requires the presence of a technician. The
classification of empirical calibration methods points four distinct classes
according to both preparative and interpretative manners in the procedure: the
conventional method (CM), the indirect method (IM), the internal standard
method (ISM) and the dilution method (DM) [3].
In the dilution method a sample and a single standard solution, either
prepared separately or added to the sample, are progressively diluted and they
are exposed to measurements at every dilution stage [3]. Each pair of signals
obtained allows the analyte to be determined either in interpolative or
extrapolative way, respectively with the aid of two-point calibration graph. If the
interferents are present in the sample assayed it is believed that the interference
effect has a chance to be successively diluted and, consequently, the analyte
concentration found in the sample of possibly great dilution is assumed to be the
final analytical result.
In this work, a simple extrapolative process applied to a SIA technique was
developed to generate a set of precisely diluted aliquots from a single standard.
The evaluation of the process was done in the the determination of nitrite in
water samples.

[1] J. Ruzicka, E.H. Hansen. Flow Injection Analysis, Wiley, New York, 2
nd
ed., 1988.
[2] J. Ruzicka. Anal. Chem. 55 (1983) 1986.
[3] Pawe Koscielniak, Marcin Wieczorek, Joanna Kozak, Magorzata Herman, Analytica
Chimica Acta 600 (2007) 6.
272


TECNOLOGIA CAD/CAM APLICADA AO
DESENVOLVIMENTO DE SISTEMAS DE FLUXO

Eunice R. G. O. Rodrigues
a
*, M. Gabriela T. C. Ribeiro
b
, Rui A. S. Lapa
a

a
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha 164, 4099-030 Porto, Portugal
b
REQUIMTE, Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre
687, 4169-007 Porto, Portugal
*eunice@ff.up.pt

A integrao e a miniaturizao de sistemas de fluxo e dos seus componentes
tm sido alvo de interesse crescente, o que tem promovido o desenvolvimento de
sistemas de fluxo em que todos os componentes necessrios esto integrados
numa mesma estrutura. Deste modo, tem sido possvel o desenvolvimento de
sistemas analticos compactos, robustos e de elevada portabilidade.
Adicionalmente, a miniaturizao dos sistemas de fluxo possibilita uma
diminuio do consumo de amostras e reagentes e um aumento do ritmo de
amostragem. Contudo, algumas tcnicas de construo requerem equipamento de
elevado custo e de operao especializada, o que tem dificultado a sua
implementao na maioria dos laboratrios [1].
O trabalho em curso tem como objectivo o desenvolvimento de estratgias e
processos simples e de baixo custo para o desenvolvimento de sistemas de fluxo
integrados. Diversos suportes foram avaliados, tendo o polimetilmetacrilato
(PMMA) apresentado as caractersticas fsicas e qumicas adequadas para a
implementao dos dispositivos com recurso a uma estratgia CAD/CAM.
Para a selagem dos dispositivos, diferentes estratgias foram desenvolvidas e
testadas, tendo sido seleccionada a fotopolimerizao de cido acrlico por UV,
devido simplicidade e rapidez do processo, aliado a uma selagem perfeita dos
sistemas. A integrao de detectores pticos na mesma estrutura rgida tambm
foi testada, tendo a sua integrao sido alcanada com sucesso.
A avaliao dos sistemas desenvolvidos foi realizada atravs do estudo
comparativo das caractersticas de funcionamento dos sistemas propostos com as
dos sistemas de fluxo clssicos (reactores de Teflon). Posteriormente, os
sistemas desenvolvidos foram aplicados na determinao de diversas espcies,
nomeadamente clcio e magnsio em guas naturais e cloro-hexidina em
formulaes farmacuticas.

Agradecimentos: E.R.G.O. Rodrigues agradece FCT a bolsa de doutoramento
(SFRH/BD/23417/2005).

[1] K. W. Oh, R. Rong, C. H. Ahn, J. Micromech. Microeng. 15 (2005) 2449.
273


BENZOYLDIAZENIDO-Re(III) AND OXO-Re(V)
COMPLEXES BEARING N,N- AND N,O-TYPE LIGANDS

Arlinda Furtado
a
*, Catarina Travassos
a
, Alexander M. Kirillov
b
, M.
Ftima C. Guedes da Silva
b,c
, Lusa M. D. R. S. Martins
a,b
, Elisabete
C. B. A. Alegria
a,b
, Armando J. L. Pombeiro
b

a
Departamento de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa, R.
Conselheiro Emdio Navarro 1, 1950-062, Lisboa, Portugal;
b
Centro de Qumica Estrutural, Complexo I, Instituto Superior Tcnico, TU Lisbon, Av.
Rovisco Pais, 1049-001, Lisboa, Portugal;
c
Universidade Lusfona de Humanidades e Tecnologias, ULHT Lisbon, Av. do Campo
Grande, 376, 1749-024, Lisboa, Portugal.
*
arlinda_furtado@hotmail.com

Recently, we have synthesized a series of Re(V), Re(III) and Re(I)
complexes with various N-donor ligands (including scorpionates [1],
aminopolyalcohols, aminoacids and N-heterocycle species [2]), which have
shown some interesting structural, catalytic and electrochemical features [1,2].
Extending these studies to other N-donor ligands such as 2-aminopyrimidine
(2-NH
2
-pyrm), 2,2-bipyridine (2,2-bpy) and pyrazinecarboxylic acid (Hpca),
we now report the new benzoyldiazenido-Re(III) compounds [ReCl{
1
-
NNC(O)Ph}(2-NH-pyrm)(PPh
3
)
2
] (1) and [ReCl
2
{
1
-NNC(O)Ph}(2,2-
bpy)(PPh
3
)] (2), as well as oxo-Re(V) complex [ReOCl
2
(pca)(PPh
3
)] (3). They
have been prepared by reacting the corresponding N-species with either
benzoylhydrazido- [ReCl
2
{
2
-NNC(O)Ph}(PPh
3
)
2
] or oxo-rhenium
[ReOCl
3
(PPh
3
)
2
] precursors, and characterized by IR,
1
H,
13
C{
1
H} and
31
P{
1
H}
NMR spectroscopies, FAB
+
-MS, elemental and single-crystal X-ray diffraction
(for 1 and 2) analyses.
Re
PPh
3
O
Cl
O
Cl
O
N
N
1 2 3
Re
PPh
3
PPh
3
HN
Cl
N
N C Ph
O
N
N Re
PPh
3
Cl
Cl
N
N C Ph
O
N
N

Acknowledgements: This work has been partially supported by the Foundation for Science
and Technology (FCT), Portugal, and its POCI 2010 (FEDER funded) program.

[1] E.C.B. Alegria, M.V. Kirillova, L.M.D.R.S. Martins, A.J.L. Pombeiro. Appl. Cat. A.
317 (2007) 43; E.C.B. Alegria, L.M.D.R.S. Martins, M. Haukka, A.J.L. Pombeiro.
Dalton Trans. (2006) 4954; E.C.B. Alegria, L.M.D.R.S. Martins, M.F.C.G. Silva,
A.J.L. Pombeiro, J. Organomet. Chem. 690 (2005) 1947.
[2] A.M. Kirillov, M. Haukka, M.F.C. Guedes da Silva, A.J.L. Pombeiro. Eur. J. Inorg.
Chem. (2007) 1556; A.M. Kirillov, M. Haukka, M.F.C. Guedes da Silva, A.J.L.
Pombeiro. Eur. J. Inorg. Chem. (2005) 2071; A.M. Kirillov, M. Haukka, M.V.
Kirillova, A.J.L. Pombeiro. Adv. Synth. Cat. 347 (2005) 1435.
274


SILVER NANOWIRES: PHOTOCATALYTIC SYNTHESIS
AND CHARACTERIZATION

Ins V. Osrio
a
, Adelaide Miranda
a
, Patrcia A. Carvalho
b
, Eullia
Pereira
a
*

a
REQUIMTE - Departamento de Qumica, Faculdade de Cincias, Universidade do
Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
b
Departamento de Engenharia de Materiais, Instituto Superior Tcnico, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
*efpereir@fc.up.pt

One of the greatest challenges of nanotechnology is the preparation of
anisotropic nanoparticles with controlled size and shape. In order to get a better
insight onto the factors governing anistropic growth of Ag nanoparticles, we
have studied the formation of Ag nanowires using a novel photocatalytic
reducing method and citrate as the capping agent. Citrate is known to promote
the formation of anisotropic Ag nanoparticles [1], but the results reported so far
show that the morphology and size of the nanoparticles obtained are strongly
dependent not only on the capping effect, but also on the kinetics of the reducing
reaction [2].
Ag nanowires were obtained by photocatalytic reduction of AgNO
3
in the
presence of sodium citrate (NaCit), by a method adapted from the literature [3].
Formation of Ag nanowires was detected after only 2 min. of reaction by the
typical plasmon band at 600 nm, and was confirmed by TEM. The nanowires
obtained are not stable in solution, and undergo a morphological transition to
spherical nanoparticles. The results are indicative that the morphological
transition probably involves oxidative etching and agglomeration/aggregation of
nanoparticles.

[1] S.H. Zhang, Z.Y. Jiang, Z.X. Xie, X. Xu, R.B. Huang, L.S. Zheng, J. Phys. Chem. B
109 (2005) 9416.
[2] Z.S. Pillai, P.V. Kamat, J. Phys. Chem. B, 108 (2004) 945; Henglein, A.; Giersig, M.
J. Phys. Chem. B 103 (1999) 9533.
[3] Y.J. Song, Y. Yang, C.J. Medforth, E. Pereira, A.K. Singh, H.F. Xu, Y.B. Jiang, C.J.
Brinker, F. van Swol, J.A. Shelnutt, J. Am. Chem. Soc. 126 (2004) 635.
275


CHIRAL JACOBSEN COMPLEXES IMMOBILISED IN
PILLARED CLAYS

Helena Alves
a
* Joo Pires
b
, Marta Andrade
b
, Ana P. Carvalho
b
,
Clara Pereira
a
, Susana L. H. Rebelo
a
, Cristina Freire
a
a
REQUIMTE, Dep. Qumica, FCUP, 4169-007 Porto, Portugal
b
Dep. Qumica e Bioqumica and CQB, FCUL, 1749-016 Lisboa, Portugal
*hmbalves@gmail.com

The immobilisation of homogeneous catalysts in porous solids is well known
and has been extensively reviewed in the literature [1]. From the immobilisation
methodologies, the less studied is the one where the inorganic complex is
immobilised during the preparation of the solid support itself. The main reason is
that few materials can be prepared in a way that preserves the integrity of the
complex during that procedure. Although this method was used before with
pillared clays [2], this is, for the best of our knowledge, the first communication
of a chiral complex immobilised in a pillared clay (PILC) by this type of
procedure. Chiral Jacobsen complexes are important catalysts for the asymmetric
epoxidation of olefins, which is a powerful strategy for the synthesis of chiral
intermediates in pharmaceutical and agrochemical industries [3].
In this work, chiral Jacobsen complex was immobilised in a pillared clay by a
simultaneous encapsulation/pillaring methodology and characterised by N
2

adsorption, Mn bulk analysis and FTIR. Textural parameters of the samples are
given in Table 1. The catalytic activity of the new materials was evaluated in the
epoxidation of several olefins, at 0C, using m-CPBA/NMO as oxidant, in
dichloromethane.

Table 1. Textural characteristics of pillared clays with a chiral Jacobsen complex
PILC A
BET

(m
2
/g)
Microporous Volume
(cm
3
/g)
Basal spacing
(nm)
Mn content
(mol)
method 1 194 0.060 1.84 45
method 2 213 0.081 1.86 47

Acknowledgments: This work was funded by FCT through Projects Ref.
POCI/CTM/56192/2004 and PTDC/CTM/65718/2006. CP and SR thank FCT for grants.

[1] D.Vos et al., Chem. Rev., 102 (2002) 3615.
[2] B. Cardoso et al., Micropor. Mesopor. Mater. 86 (2005) 295.
[3] P. Das et al., J. Mol. Catal. A: Chem. 248 (2006) 135.
276


NO
2
Cl
Figura 1. Frmula de
estrutura dos ismeros de
monocloronitrobenzeno.
ESTUDO TERMOQUMICO DOS TRS ISMEROS DO
MONOCLORONITROBENZENO

Ana I. M. C. Lobo Ferreira*, Ana R. G. Moreno, Manuel A. V. Ribeiro
da Silva
Centro de Investigao em Qumica, Departamento de Qumica, Faculdade de Cincias,
Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007, Porto, Portugal
*ana.ferreira@fc.up.pt

Os derivados clorados do nitrobenzeno merecem
especial ateno, no s devido sua produo em
grande escala, sendo utilizados como intermedirios
qumicos em diversos processos industriais, como na
produo de pesticidas, herbicidas, pigmentos,
frmacos, etc., mas tambm pela elevada toxicidade
exibida, sendo substncias suspeitas de provocar
vrios tipos de toxicidades, como: hematoxicidade,
nefrotoxicidade, esplenotoxicidade e hepatoxicidade
[1], estando includos na lista de compostos orgnicos
poluentes da Unio Europeia [2].
O presente trabalho engloba-se num estudo mais vasto, que tem vindo a ser
desenvolvido neste Centro de Investigao, sobre o efeito energtico da
introduo de tomos de halogneo no anel aromtico de derivados do benzeno
[3], tal como do fenol, do anisol e da anilina. Assim, neste trabalho, efectuou-se
o estudo termoqumico de derivados monoclorados do nitrobenzeno. Os valores
das entalpias molares de formao padro em fase gasosa, a T=298.15 K, dos
trs ismeros de cloronitrobenzeno, foram obtidos a partir das energias molares
de combusto padro, em seio de oxignio, a T=298.15 K, medidas por
calorimetria de combusto em bomba rotativa, e das entalpias molares de
sublimao padro, a T=298.15 K, determinadas por microcalorimetria Calvet de
altas temperaturas. Os valores das entalpias molares de formao padro em fase
gasosa, a T=298.15 K, obtidos experimentalmente foram comparados com os
valores estimados pelo mtodo de Cox [4], e interpretados em termos de
contribuies estruturais.

[1] S.K. Hong, D.K. Anestis, J.G. Ball, M.A. Valentovic, G.O. Rankin Toxicol. Letters
129 (2002) 133.
[2] S. Lacorte, P. Viana, M. Guillamon, R. Tauler, T. Vinhas, D. Barcelo J. Environ.
Monit 3 (2001) 475.
[3] M.A.V. Ribeiro da Silva, M.L.C.C.H. Ferro, F. Jiye J. Chem. Thermodyn. 26 (1994)
839; M.A.V. Ribeiro da Silva, A.I.M.C.L. Ferreira J. Chem. Thermodyn. 40 (2008)
362; M.A.V. Ribeiro da Silva, J.R.B. Gomes, A.I.M.C.L. Ferreira J. Phys. Chem. B
109 (2005) 13356.
[4] J.D. Cox, A Method for Estimating the Enthalpies of Formation of Benzene
Derivatives in the Gas State, NPL (National Physical Laboratory) Report Chem 83
June, 1978.
277


INVESTIGAO NOS ENSINOS SUPERIOR-
SECUNDRIO: UMA EXPERINCIA
EM QUMICA INORGNICA

A. Pontinha*, V. Pacheco, L. Martins
Departamento de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa, Rua
Conselheiro Emdio Navarro,1 1959-007 Lisboa
*apontinha@deq.isel.ipl.pt

Com o propsito de contribuir para o desenvolvimento e divulgao, no
ensino secundrio, das actividades de I&D realizadas no Laboratrio de Qumica
Inorgnica do Departamento de Engenharia Qumica do Instituto Superior de
Engenharia de Lisboa, e motivar os alunos
para a investigao e tecnologias associadas,
realizaram-se vrios estgios no mbito da
Ocupao Cientifica de Jovens nas Frias
promovidos pela Agncia Nacional para a
Cultura Cientifica e Tecnolgica - Cincia
Viva.
Os trabalhos efectuados tiveram como
objectivo preparar os alunos para a utilizao
de tcnicas e equipamentos mais usados no
Laboratrio de Qumica Inorgnica, bem como
promover o contacto entre os alunos do ensino
secundrio e os investigadores e professores da
instituio.
Nesta comunicao so divulgados os
referidos estgios, bem como o contributo deste tipo de aces para a formao e
experincia pessoal dos intervenientes.

[1] L. R. Summerlin, J. L. Ealy, Jr.. Demonstraes Qumicas, Sociedade Portuguesa de
Qumica, Vol. 1, 2 ed., Lisboa, 1995.
[2] L. R. Summerlin, C. L. Borgford, J. B. Ealy. Demonstraes Qumicas, Sociedade
Portuguesa de Qumica, Vol. 2, Lisboa, 1996.
[3] D. F. Shriver, P.W. Atkins. Inorganic Chemistry, Oxford University Press, 3 ed.,
UK,1999.
[4] R. Chang. Qumica, McGraw-Hill, 5 ed., Lisboa, 1994.

278


ESTRELA VERDE: UMA MTRICA DE VERDURA
PARA AVALIO DE EXPERINCIAS LABORATORIAIS

M. G. T. C. Ribeiro*, D. A. Costa, B. Faria, A. Neves, A. A. S. C.
Machado
Dep. de Qumica, Fac. de Cincias do Porto, R. Campo Alegre, 687, Porto 4169-007
*gribeiro@fc.up.pt

Quando se consideram os objectivos societrios gerais do tema aglutinador
deste encontro, Qumica e Inovao, surge inevitavelmente como primeiro
objectivo o Desenvolvimento Sustentvel. A perseguio da Sustentabilidade
pela qumica realizada proactivamente pela Qumica Verde (QV, em sentido
lato, incluindo a Engenharia Verde) e impe que aquela cincia seja ensinada
segundo esta nova postura. Neste contexto, iniciou-se neste Departamento uma
linha de actividade dirigida implementao do ensino da QV no ensino
secundrio. Para instilar nos estudantes a nova mentalidade de praticar a
qumica, o ensino experimental desta deve adoptar experincias que envolvam
intencionalmente como objectivo o aumento da verdura e que evidenciem como
possvel concretiz-lo por meio da realizao paralela de verses tradicionais e
com verdura acrescida.
Para implementao da QV necessrio realizar a aferio da verdura, uma
grandeza muito complexa, cuja avaliao passa pela utilizao de ferramentas e
mtricas apropriadas (p.ex. [1]). Para utilizao simples a nvel elementar, para
avaliao da verdura das experincias de qumica, nomeadamente de reaces
qumicas, tem-se em construo uma nova mtrica semiquantitativa, grfica, a
chamada Estrela Verde (GreenStar), na qual se consideram globalmente os
Doze Princpios da QV [2]. A mtrica consiste em avaliar a verdura referente a
cada um destes, numa escala de 1 a 3, por meio de critrios pr-definidos e
representar os resultados num grfico de estrela (quanto mais cheia for a estrela,
maior a verdura).
A Estrela Verde ser exemplificada pela anlise da verdura da sntese
laboratorial do sulfato de tetraminocobre(II), que faz parte do programa actual da
disciplina de Fsica e Qumica do 11 ano do Ensino Secundrio ( a nica
experincia de qumica preparativa realizada no 10 e 11 anos) em funo do
modo como realizada (macro/microescala) e tendo em vista a sua optimizao
verde. Os resultados sero comparados com os obtidos pela EcoScale, uma
outra mtrica recentemente introduzida com o mesmo fim de avaliar as
experincias de sntese no laboratrio [3].

[1] A.A.S.C. Machado. QUIMICA 107 (2007) 47.
[2] P.T. Anastas, J. C. Warner. Green Chemistry, Oxford UP, 1998, p. 30.
[3] K. van Aken, L. Strekowski, L. Patiny. Beilstein J. Org. Chem. 2 (2006) 1.
279


TEATRO CIENTFICO: ALGUNS DADOS SOBRE O
IMPACTO DA PEA OXIGNIO NOS ALUNOS

Cludia C. Saraiva
a
*, M. Joo Monte
b
, J. C. Paiva
b

a
Escola E.B. 2,3/S de Penalva do Castelo, R. Escola, 3550-140 P. Castelo
b
Departamento de Qumica da Faculdade de Cincias da Universidade do Porto, R.
Campo Alegre, 687, 4169-007 Porto
*claudiacsaraiva@gmail.com

Numa era em que se recorre, cada vez mais, a estratgias diversificadas no
ensino da Qumica, com o intuito de motivar os alunos para o seu processo de
ensino/aprendizagem, torna-se oportuno pedagogicamente recorrer tambm
expresso dramtica.
possvel aprender cincia (e Qumica, em particular) para alm dos livros,
assistindo a uma pea de teatro? Esta estratgia j utilizada noutras reas do
saber, como a Histria e a Literatura. Mas ser possvel utilizar a linguagem
dramtica e teatral como uma aliada do processo de ensino/aprendizagem da
Qumica? Far sentido realizar, nas escolas, peas de teatro de ndole cientfica?
Estaro os alunos interessados em actividades deste gnero?
Oxignio, de Carl Djerassi e Roald Hoffmann, foi levada cena, durante os
meses de Janeiro e Fevereiro de 2006, pela Companhia Seiva Trupe, no Teatro
do Campo Alegre, no Porto, tendo sido criadas sesses especiais para as escolas.
Foi levada a cabo uma investigao quantitativa que envolveu 738 alunos e
cujo objectivo foi a verificao da influncia do Teatro Cientfico na motivao
dos alunos, do ensino secundrio e do 3 ciclo do ensino bsico, para o estudo da
Qumica. Em particular, pretendeu conhecer-se o impacto que a pea Oxignio
provocou nos alunos que a ela assistiram, nas questes relacionadas com a
histria da Qumica, os conceitos e a motivao para a disciplina.
Aps terem assistido referida pea, foi solicitado aos alunos que
respondessem a um questionrio elaborado para o efeito, no sentido de averiguar
alguns dados de chegada ao visionamento da pea, algumas expectativas, o
impacto da pea e prospectivas no que concerne sensibilidade face Qumica.
Os resultados obtidos revelaram que os alunos que assistiram pea esto
interessados, na sua maioria, em repetir a experincia, referindo que o facto de
terem sido espectadores de uma pea cientfica foi um aspecto motivador para a
aprendizagem da Qumica. Manifestaram, tambm, interesse pela existncia de
peas que abordassem esta temtica, nas escolas que frequentam. de salientar
que os alunos, na sua maioria, responderam correctamente s questes que
abordam factos cientficos, o que sugere que os contedos transmitidos foram
assimilados. O estudo revelou tambm alguns constrangimentos associados
estratgia pedaggica de usar o teatro como ponte para o ensino da Qumica.
Esta investigao deve ser encarada, porm, como um estudo-piloto, um
ponto de partida para eventuais estudos mais aprofundados e abrangentes sobre
esta temtica.
280


A AVENTURA, O MISTRIO E A QUMICA

Marta Pinheiro
a
, Joo P. Leal
b,c
*
a
Escola Bsica dos 2. e 3. Ciclos Jos Tagarro, Rua Dr. Marcelino Mesquita, 2070-102
Cartaxo, Portugal
b
Departamento de Qumica, Instituto Tecnolgico e Nuclear, Estrada Nacional 10, 2686-
953 Sacavm, Portugal
c
Centro de Qumica e Bioqumica, Faculdade de Cincias da Universidade de Lisboa,
Campo Grande, 1149-016 Lisboa, Portugal
*jpleal@itn.pt, jpleal@fc.ul.pt

Contar histrias (ou a Histria) um dos mais antigos meios utilizados pela
Humanidade para transmitir conhecimentos. Esta tradio, oral ou escrita, foi
durante algum tempo menorizada no processo de divulgao das Cincias. No
entanto, nas ltimas dcadas, tem-se verificado um aumento muito significativo
dos chamados textos de divulgao cientfica.
Tambm, uma literatura com uma vertente
mais policial, mas dando a conhecer os
aspectos cientficos envolvidos tem
despontado em anos mais recentes, quer no
aspecto mais clssico (livros) quer
transvasando mais recentemente para o
panorama do audiovisual (sries televisivas e
filmes). importante que tambm na Qumica
essa divulgao seja feita.
Nesta comunicao d-se a conhecer o
trabalho originado numa Tese de Mestrado e
que gerou uma srie de histrias de cariz policial, sobre um grupo de jovens
investigadores que usam os seus conhecimentos de Qumica para a resoluo dos
vrios mistrios com que so confrontados.
As vrias histrias tm abordagens distintas e pressupem um nvel de
conhecimento diverso conforme as idades do pblico alvo, que se pretende v
desde os alunos do 1 ciclo at aos do 9 ano de escolaridade. Tambm a prpria
formatao, o tipo e dimenso da letra, vai sendo alterada conforme o pblico a
quem a histria se destina.
As histrias escritas com base em diferentes contedos da Qumica podero
ser utilizadas para o ensino de alguns temas, para os alunos adquirirem e
testarem os seus conhecimentos numa espcie de clube ou aula de investigao,
ou como pura diverso enquanto aprofundam os seus conhecimentos.
Est neste momento em equao qual a melhor forma de divulgar as vrias
histrias.
281


TCNICAS ANALITICAS APLICADAS AO
ESTUDO DE PIGMENTOS DO SCULO XIX E SUA
CONTRIBUIO PARA O ENSINO

Maria F. Antnio
a
*, F. M. Costa
b
a
Escola Secundria Jos Saramago - Mafra
b
Faculdade de Cincias da Universidade de Lisboa,

Centro de Cincias Moleculares e
Materiais
*Prof.fernandaantonio@gmail.com

No fim do sculo XVIII, a qumica surgiu como cincia experimental, devido
aos trabalhos desenvolvidos pelos qumicos da poca. A partir da, passou a
responder s necessidades do homem, nas mais diversas vertentes,
nomeadamente na descoberta de novos materiais e o aperfeioamento de
mtodos de anlise que conduziram a um progresso cada vez mais acentuado. A
qumica, como cincia, tem uma vasta aplicao, nomeadamente na arte, e de
uma forma concreta, na pintura. Os materiais utilizados numa pintura so
variadssimos e a sua origem pode ser orgnica ou inorgnica consoante o fim a
que se destinam. Destes materiais, destacam-se por exemplo os pigmentos
utilizados no sculo XIX |1, 2|, devido ao seu aumento significativo. Pigmentos
que em pocas anteriores gozaram de grande importncia e preferncia, foram
preteridos em relao a outros, nomeadamente, a substituio de pigmentos
minerais de origem natural por pigmentos sintticos com idntica composio
qumica.
Para realizar o estudo de pigmentos necessrio recorrer rea da qumica
analtica instrumental. As tcnicas analticas usadas so variadas |3|, entre elas a
espectroscopia de infravermelho, a espectroscopia de emisso no ultravioleta, a
espectroscopia de fluorescncia de raios X, a espectrometria de massa, a datao
com base no decaimento radioactivo do carbono, tcnicas de cromatografia |4| e
mtodos microqumicos, entre outros. Contudo, para caracterizar o tipo de
material, quase sempre necessrio recorrer a mais do que uma tcnica de
anlise. Para efectuar essa escolha, fundamental o conhecimento e estudo
qumico dos processos analticos envolvidos, para eventuais aplicaes no
mbito do ensino |5|.

|1| I.S. Butler, J.Chem. Educ. 62 (1985) 334.
|2| R.L. Feller, (ed.), Artists' Pigments. A handbook of their history and characteristics,
Volume 1, Washington, National Gallery of Art, 1986.
|3| Raymond J. Merlunas, Studies in Conservation 33 (1988) 107.
|4| Liliane Maschhlein Kleinr, Studies in Conservation 19 (1974) 107.
|5| Maria F. Antnio, Qumica e Arte e Sua componente Pedaggica, tese de Mestrado
em Qumica para o Ensino, 2006.
282


Figura 1. Apontadores da Tabela
Peridica do portal Mocho
9)Apontadores
CONTEXTUALIZAO CURRICULAR
EM TABELAS PERIDICAS DIGITAIS

Flora M. B. Ferreira
a
*, Joo C. Paiva
b

a
EB 2,3 Dr. Manuel de Brito Camacho, Estrada Municipal n.539, 7600-032 Aljustrel
b
Departamento de Qumica da Universidade do Porto, Rua do Campo Alegre n.687,
4169-007 Porto
*flora.ferreira@iol.pt

A Tabela Peridica (TP) considerada
uma das mais importantes referncias na
Qumica. Em contexto educativo, tambm
um suporte dirio para os alunos, em
particular nos 9, 10 e 12 anos, visto ser
dado especial destaque ao contedo
Tabela Peridica nesses momentos de
aprendizagem. O aparecimento das novas
tecnologias permitiu a elaborao de TP
digitais, as quais permitem aceder a uma
grande quantidade de informao de um
modo mais rpido e cmodo. Por outro lado, agora possvel associar TP
interactividade, com vrios elementos multimdia, o que, muitas vezes, contitui
um factor de motivao para os alunos.
No portal Mocho [1] j se encontram alguns apontadores de TP disponveis
on-line. No entanto, de acordo com as competncias que se pretendem
desenvolver, deve-se ser crtico na seleco das ferramentas multimdia. H que
ter em conta diversos factores, tais como a ausncia de incorreces cientficas, a
possvel envolvncia de concepes alternativas, a interactividade
proporcionada, a existncia de uma vertente ldica, entre outros. ainda
importante, conduzir a explorao da TP por parte dos alunos, no sentido de no
gerar disperso. Para tal, pode-se recorrer a Roteiros de Explorao, a
Webquests, entre outros materiais. No entanto, no se deve descurar da utilizao
de outras estratgias no mediadas digitalmente, como, por exemplo, o trabalho
de grupo e a discusso.
A investigao-aco [2] levada a cabo com base numa TP digital permitiu,
entre outros aspectos, concluir que os exploradores construram uma perspectiva
diferente acerca da utilidade do computador e da Internet na escola e na
construo de conhecimento. Das principais concluses deste estudo se d conta
neste trabalho.

[1] Centro de Fsica Computacional. Mocho Portal de ensino das cincias e de cultura
cientfica (1998). Consultado em 31-02-2008, disponvel em http://www.mocho.pt.
[2] F. M. B. Ferreira. Tabela Peridica Interactiva on-line: uma experincia com alunos
do 10 ano e reformulao do recurso digital. Tese de Mestrado em Educao
Multimdia. Faculdade de Cincias da Universidade do Porto, Porto (2005). 202.
283


CONTRIBUIES DA FILOSOFIA DA QUMICA PARA
UMA DIDTICA DA QUMICA

Marcos Antonio Pinto Ribeiro
a
*, Tatiana Gonalves Sardinha
b
, Hyrlam
Souza Ferreira
b

a
UESB Universidade Estadual do Sudoeste da Bahia
b
UESB Universidade Estadual do Sudoeste da Bahia
*marcolimite@yahoo.com.br,

Qumica uma cincia central, mas insular e negligenciada pelas
consideraes filosficas[1], discusses conceituais so poucas e superficiais[2].
Ontologicamente dependente da Fsica alimenta possvel reduo epistemolgica
destituindo-a de problemas Filosficos[1]. Antirrealismo, positivismo lgico e
realismo tcito da produo Qumica dificultam uma epistemologia regional[1]
implicando em: Discurso implcito dos objetivos cientficos; imunidade perante
problematizaes da Filosofia da Cincia; Teoria e experimento como
instrumentos. interferindo na autonomia e na compreensibilidade, afetando
critrios de seletividade e organizao, problema central de uma didtica
Qumica[1]. Educao Qumica necessita de uma Filosofia da Qumica[4].
Concernente s questes internas de mtodos, conceitos e ontologia,
institucionaliza-se em 1994 discutindo: autonomia e sua reduo a Fsica;
natureza e a especificidade da Qumica terica; lgica e uma epistemologia semi-
emprica/semi-teorica; Lies trazidas da Histria da Qumica; Princpios que
guiam e tem guiado a produo cientficas; realidade das leis e das entidades;
Qumica e prticaem particular o entendimento filosfico da qumica sinttica;
Papel da instrumentao. No ensino persistem: o uso da linguagem cotidiana
dentro de um contexto cientfico; simplificaes de conceitos; uso de definies
e de modelos mltiplos; memorizao simples de conceitos e algoritmos;
sobreposio de conceitos similares; dotar os objetos de caractersticas humanas;
conhecimento inadequado de pr-requisitos; circularidade de conceitos;
Dificuldades de interpretaes macro/micro; pouca compreenso de modelos,
leis, teorias; variedades de conceitos fundamentais e pouca aprendizagem
integrativa. Aqui a Filosofia da Qumica deve desempenhar papel decisivo ao:
definir claramente nveis de linguagem e discurso, uma metaqumica; natureza
da explicao e a importncia dos modelos; clarificao de conceitos nucleares;
especificao de uma didtica[4].

[1] SCERRI, Eric R (2005). Some Aspects of the Metaphysics of Chemistry and the
Nature of the Elements", HYLE 11-2, (pp. 127-145).
[2] CALDIN, Edward F (2002).: "The Structure of Chemistry in Relation to the
Philosophy of Science", HYLE 8-2, pp. 103-121.
[3] SCHUMMER, Joachim (1998): "The Chemical Core of Chemistry I: A Conceptual
Approach", HYLE 4-1, pp. 129-162.
[4] ERDURAN, S. (2001). Philosophy of chemistry: An emerging field with implications
for chemistry education. Science & Education, 10, 581-593.
284


Figure 1. EquilibrAction logotype
PORTUGUESE PARTICIPATION IN CROSSNET:
EQUILIBRACTION THE NATIONAL PROJECT

Susana Fonseca
a
*, Joo Paiva
b
, Antnio Ferreira
c
, Joo Vale
d

a
Escola Secundria Pluricurricular de Santa Maria Maior, Rua Manuel Fiza Jnior,
4901-872 Viana do Castelo, Portugal
b
Departamento de Qumica da Faculdade de Cincias da Universidade do Porto, Rua do
Campo Alegre 687, 4169-007 Porto, Portugal
c
Escola Secundria de Avelar Brotero, Rua General Humberto Delgado, 3030-327
Coimbra, Portugal
d
Escola EB 2/3 Prof. Carlos Teixeira, 4820-405 Fafe, Portugal
*susanafonsec@clix.pt

The European Project CROSSNET is coordinated by Kiel Universitys IPN
in Germany and focuses in crossing boundaries in Education. The Portuguese
Project, named EquilibrAction, relies on the use of computational resources
potential to transpose barriers in the teaching of Chemical Equilibrium. These
barriers correspond to limitations that block a fully integrated teaching of this
thematic. By integrated teaching we mean a classroom practice effectively
associated to methods and theories that are valued in our days.
Taking into account the difficulties reported in the teaching / learning of
Chemical Equilibrium and the recognized computational resources capabilities in
this field [1-4], we defined specific barriers to cross / result of the transposition:
- Learning the concepts / Learning in context;
- Passive learning / Active learning;
- Formal Abstraction / Facilitated Abstraction.
Considering these barriers, three teachers are developing case studies to
conclude about the utility of different approaches based on multimedia resources.
For each case study, different instruments are used, like questionnaires and video
record. Nevertheless, transversal instruments are also applied, like logbooks and
interviews. The interviews are made by one teacher to the class of another
teacher in order to encourage students sincerity.
The conduction of the case studies implies the use of the EquilibrAction
WebSite: http://nautilus.fis.uc.pt/cec/ea/. In this platform there are available
resources associated to a specific approach,
which includes guides for application,
information about common difficulties and
consolidation materials. In the
EquilibrAction WebSite communities can
also interact and exchange materials.
[1] M. Sandberg, M.K. Bellamy. J. Chem. 80 (2003) 456.
[2] J.C. Paiva, V.M.S. Gil, A.F. Correia. J. Chem. Ed. 79 (2002) 640.
[3] J. Russell, R. Kosma, T. Jones, J. Wykoff, N. Marx, J. Davis. J. Chem. Ed. 74 (1997)
330.
[4] H. Hameed, M. Hackling, & P. Garnett. J. Sci. Ed. 15 (1993) 221.
285


BIOCOMBUSTVEIS

Snia J. Rocha*, Diogo A. M. M. G. Rocha, Frederico A. R. B.
Junqueira, Joo A. S. Saraiva, Mafalda P. S. Ramos, Ricardo S.
Bessa, Rui P. C. Carvalho
a
Escola Secundria c/ 3 ciclo Augusto Gomes, Rua de Damo, Matosinhos, 4450-107
Matosinhos
*s_j_rocha@hotmail.com

Os biocombustveis, nomeadamente bioetanol e biodiesel, so considerados
combustveis alternativos que visam essencialmente reduzir a dependncia
energtica do petrleo. Estes tm sido implementados no sector dos transportes,
o biodiesel para substituir parcial ou totalmente o gasleo e o bioetanol para
substituir parcial ou totalmente a gasolina. Em Portugal, apenas o biodiesel est a
ser produzido e usado no sector dos transportes. Convm salientar que, os
biocombustveis continuam a ser uma alternativa energtica no ciclo do carbono,
pelo que no considerada uma alternativa ambientalmente sustentvel.
O projecto denominado Biocombustveis est a ser desenvolvido por um
grupo de discentes do 3 Ciclo do Ensino Bsico e Ensino Secundrio e tem
como objectivo consciencializar os mesmos e a comunidade, de um modo geral,
para as vantagens e as desvantagens da produo e uso de biocombustveis.
Ao longo do projecto, pretende-se focar as questes energticas e ambientais
relativas s matrias-primas seleccionadas e aos mtodos usados na produo de
biocombustveis. Simultaneamente, pretende-se envolver toda a comunidade na
recolha de leos alimentares usados (OAU). Os OAU esto a ser colocados num
oleo e posteriormente sero reencaminhados para o local apropriado. Deste
modo, pretende-se que toda a comunidade participe na recolha de OAU e
compreenda a necessidade de os reciclar. Os discentes esto envolvidos na
campanha de sensibilizao e na produo de materiais de divulgao.
A componente laboratorial compreende a produo do bioetanol e do
biodiesel. A produo do bioetanol implica trs etapas: (a) hidrlise da sacarose
e do amido, (b) fermentao alcolica e (c) destilao. A produo de biodiesel
baseia-se numa reaco de transesterificao, recorrendo a leos alimentares
usados e leos alimentares virgens como matrias-primas. Posteriormente,
realiza-se a saponificao com o intuito de reutilizar a glicerina obtida para
produzir sabo.
Esta comunicao pretende divulgar o projecto que est a ser desenvolvido e
simultaneamente salientar as diferentes etapas da concretizao do mesmo.
O Projecto Biocombustveis encontra-se online e pode ser consultado no
seguinte endereo: http://biocombustiveis-esag.blogspot.com.

Agradecimentos: Agradece-se Fundao Ildio Pinho, Banco Esprito Santo e Ministrio
da Educao pelo Prmio Cincia na Escola.
286


PROTOCOLOS EXPERIMENTAIS YOUTUBE

Manuel Matos
a
*, Margarida Portugal
b
, Srgio P. Costa
a
, Hugo F.A.
Siva
a
, Nelson A.F. Silva
a
, Pedro L. Galego
a
, Alda M. Carmo
a
, Alice R.
Catarino
a
, Isabel B. Godinho
a
, Nair N. Alua
a
, Celeste M. Serra
a

a
ISEL-DEQ, R. Cons. Emido Navarro, 1, 1959-007 Lisboa
b
ESELx, Campus de Benfica do IPL, 1549 - 003 Lisboa
*mmatos@deq.isel.ipl.pt

So cada vez mais complexos e sofisticados os procedimentos e
equipamentos usados no ensino das tcnicas experimentais em qumica . O
nmero de alunos em cada aula tem vindo tambm a aumentar. Os professores
so ainda confrontados com o desafio de ensinar diferentes tcnicas mesma
turma em escassas horas. Quanto aos alunos, tm no s de aprender a tcnica
proposta, bem como o funcionamento dos equipamentos envolvidos num tempo
reduzido.
A subjugao do processo de aprendizagem de uma nova tcnica s
dificuldades de operao do equipamento afasta os alunos do essencial: a
compreenso cientfica do mtodo que esto a aprender [1].
De modo a ultrapassar as
dificuldades enunciadas criou-se um
ambiente virtual que simula a
experincia que os alunos vo encontrar
no laboratrio [2]. So disponibilizadas
via www folhas de hipertexto
desenvolvidas contendo elementos
multimdia como filmes e fotos, blocos
interactivos baseados em flash ou javascript. Os alunos podem assim ensaiar o
protocolo experimental antes de o realizar, focando a sua ateno nos aspectos
conceptuais. Os alunos encontram um laboratrio virtual idntico ao que iro
encontrar na realidade [3]. Cada equipamento apresentado atravs de um filme
em que se explica o seu funcionamento. Quando os alunos chegam ao laboratrio
para realizar os ensaios j se encontram familiarizados com as funes e
comandos mais importantes do equipamento e tambm com os principais passos
da experimentao.
Esta abordagem envolvendo tecnologias de informao baseadas na internet
tem-se revelado bastante positiva. Os alunos mostram-se mais confiantes e
autnomos nos procedimentos operacionais e centrados no problema cientfico
em estudo. Utilizam-se tcnicas de comunicao permitidas pelos actuais meios
informticos e que nos permitem inovar para alm dos protocolos em papel.

[1] D. Hodson, Teaching Science, Open University Press, Londres, 1994.
[2] M.D. Koretsky, D. Amatore, C. Barnes, S. Kimura, IEEE Transactions on Education,
51 (2008) 76.
[3] J. Cuadros, X. Tomas, J.J. Molins, L.G. Sabate, A. Balfagon, Afinidad 64 (2007) 450.
287


MICROSCOPIA QUMICA E CRISTAIS: UMA
REVOLUO CULTURAL EM CURSO

Clementina Teixeira*
Centro de Qumica Estrutural, Instituto Superior Tcnico, Universidade Tcnica de
Lisboa, Av. Rovisco Pais 1049-001 Lisboa
*clementina@ist.utl.pt

Micrositeseeing: palavra sugerida para a pesquisa de sites de microscopia na
Web. A par de estudos em reas especializadas, como so a Qumica Forense, a
caracterizao de materiais (polmeros, compsitos, surfactantes) a Petrologia
(estudo de minerais, rochas, meteoritos), a microbiologia, a medicina, a
engenharia de cristais, cada vez aumenta mais a associao das tcnicas
microscpicas ao ensino ldico em clubes de cincia e s artes, podendo j
afirmar-se que existe uma revoluo cultural em curso. Novas palavras surgem
tais como micscapes, microscapes, bioscapes, expressions e impressions,
associadas, principalmente, fotomicrografia de luz polarizada. Pretende-se
nesta comunicao apresentar as potencialidades da microscopia qumica de
Chamot e Mason no campo do crescimento de cristais e estudo de reaces
qumicas, salientando o seu papel de relevncia no ensino da Qumica e a sua
possvel ligao a indstrias que possam explorar a sua componente esttica.






















Figura 1. Microscopia Qumica: estudo de reaces e formao de cristais.

Financiamento FCT e Projecto Cincia Viva, CV/VI/ID976.

Formao de cristais com ocluso molecular , associada limpeza da prata.



Alterao do hbito cristalino do NaCl. Diluio de cido sulfrico
288


Figura 1. Geometria de
repulso mnima para AB
9
.
O MODELO DA ESFERA RGIDA EM FOLHA DE
CLCULO: DA TETRA NONACOORDENAO

Mrio Valente*, Helena Moreira
Colgio D.Duarte (Porto), Rua de Visconde de Setbal, 82/100, 4200-497 Porto
*madmage1@yahoo.com

Numa poca em que a modelao computacional assume uma
preponderncia crescente, constituiu para ns um desafio pedaggico
interessante a criao de uma aplicao numa folha de clculo que permitisse a
determinao de geometrias de repulso mnima e
que envolvesse noes de matemtica, fsica e
qumica acessveis a alunos do ensino secundrio.
O modelo escolhido Modelo da Esfera
Rgida - assume que a geometria de uma espcie
molecular (constituda por um tomo ou io
central e dois ou mais tomos perifricos)
devida repulso entre os tomos perifricos,
tomados como cargas pontuais assentes sobre uma
esfera centrada no tomo central [1]. A
considervel simplicidade deste modelo revelou-se ideal para o fim proposto.
As repulses entre cada par de cargas pontuais, R
a,b
, foram calculadas por:
6
)
2
)
1
z
2
(z
2
)
1
y
2
(y
2
)
1
x
2
((x
1,2
R

+ + =

em que as coordenadas (x
1
, y
1
, z
1
) e (x
2
, y
2
, z
2
) so as coordenadas cartesianas das
cargas pontuais 1 e 2, respectivamente, e a repulso total foi calculada por:

= + =
=
1 n
1 i
n
1 i j
j i, T
R R

Por comodidade de visualizao usaram-se coordenadas esfricas que depois
foram convertidas em coordenadas cartesianas para a execuo dos clculos. As
posies iniciais das cargas pontuais foram variadas individualmente ou em
grupos, at que se chegou a mnimos de R
T
. A visualizao das estruturas
resultantes foi feita usando um programa freeware encontrado na internet [2].
So apresentados os resultados chegados para espcies moleculares do tipo
AB
n
(n = 4 a 9), por exemplo, Figura 1, que, tendo sido conseguidos de uma
forma muito simples, so idnticos aos encontrados na literatura [3].

[1] M.C. Favas e D.L. Kepert, Prog. Inorg. Chem. 28 (1981) 309; D.L. Kepert,
Prog.Inorg.Chem. 25 (1979) 41; D.L. Kepert, Prog. Inorg. Chem. 24 (1978) 179;
M.G.B. Drew, Prog. Inorg. Chem., 23 (1977) 67.
[2] http://www.chemcraftprog.com.
[3] D.L. Kepert, Coordination Numbers and Geometries, em Comprehensive
Coordination Chemistry, Vol.1, Eds. G. Wilkinson, R.D. Gilland e J.A. McCleverty,
Pergamon, Oxnia, 1987.
289


DA FLORESTA FOLHA DE PAPEL EXPLORANDO O
PROCESSO DO PONTO DE VISTA PEDAGGICO

Patrcia Fial
a
, Jorge Pinheiro
b
, Arlindo Gomes
a
, Lcia Silva
a
*,
a
Departamento de Qumica, Universidade da Beira Interior, Rua Marqus dvila e
Bolama, 6200 Covilh
b
Instituto Politcnico da Guarda, Escola Superior de Educao, Av. Dr. S Carneiro
n50, 6301-559 Guarda
*luciasilva@ubi.pt

No ensino bsico e secundrio qualquer currculo e correspondentes
programas devem ser adequados ao nosso pas, tendo em conta a realidade das
escolas e da sociedade portuguesa (especialmente alunos e professores)
fundamental que a reviso curricular assuma frontalmente o dever que lhe assiste
de recuperar atrasos e de contribuir para um nvel de literacia e cultural mais
elevados que frequentam a escola aproximando-os dos seus colegas de pases
mais desenvolvidos, tendo o carcter prtico-laboratorial uma grande
importncia.
O ensino da Cincia est estruturado em torno de duas ideias principais:
- A compreenso do mundo na sua globalidade e complexidade, requer
o recurso de interdisciplinaridade com vista a conciliar as anlises fragmentadas
que as vises analticas dos saberes disciplinares fomentam e fundamentam. As
vises disciplinares sero sempre complementares.
- Escolhem-se situaes-problema do quotidiano, familiares aos alunos
a partir dos quais se organizam estratgias de ensino e de aprendizagem que iro
reflectir a necessidade de esclarecer contedos e processos da cincia e da
tecnologia, bem como das suas inter-relaes com a sociedade, proporcionando o
desenvolvimento de atitudes e valores.
No meu trabalho Da floresta folha de papel, exploro o processo do ponto
de vista pedaggico. Incluindo contedos cientficos permeados de valores e
princpios, e relaes entre experincias educacionais e experincias de vida.
importante transmitir aos alunos como uma simples folha de papel que
utiliza no seu dia-a-dia passa por vrios processos, como de uma simples rvore
passa folha do papel! Esta transformao passa por vrias etapas e cada etapa
possui um contedo cientfico (fsico-qumico) para explorar e aprender.
Neste trabalho o que se pretende a partir das vrias etapas de fabricao do
papel analisar contedos e inserir experincias no mbito do ensino bsico e
secundrio relacionadas com situaes do dia-a-dia de modo a transmitir
contedos da disciplina de fsica e qumica. Para alm de transmitir e sensibilizar
os alunos para os problemas ambientais envolvidos.

290


A FILOSOFIA DA QUMICA, O DISCURSO QUMICO E A
EDUCAO QUMICA

Duarte Costa Pereira*
Departamento de Qumica da Faculdade de Cincias da Universidade do Porto, R. do
Campo Alegre, 687, 4150-007 Porto
*dcpereir@fc.up.pt

A Qumica nunca fora objecto da ateno sria dos filsofos antes da ltima dcada
do sculo passado. Tratada no meio do conjunto das Cincias ela era ontolgica e
epistemologicamente reduzida Fsica, at porque no se lhe atribuia um fundamento
prprio, como acontecia s outras cincias: a matematizao no caso da Fsica e os
fundamentos diacrnicos da evoluo para a Biologia, da tectnica para a Geologia e da
cosmognese para a Astronomia. Efectivamente a histria da Qumica no parecia
inspirar uma grande narrativa fundacional e as redues, quer newtonianas (o prprio
Newton dedicou muito do seu tempo Qumica) quer qunticas, Fsica deixavam (e
deixam) muito a desejar Este estado de coisas foi interrompido em 1994 por uma srie
de filsofos que entenderam que a Qumica tinha necessidade de uma filosofia prpria,
reunindo-se pela primeira vez um congresso de Filosofia da Qumica, tendo esta
disciplina passado a contar, com rgos de comunicao prprios (Hyle e Foundations of
Chemistry) e dedicando-lhe, a partir da, a prestigiada ACS espao nos seus congressos.
Perante tal panorama, o autor que tinha tratado a partir da dcada de 70, algumas das
principais questes da Filosofia da Qumica, como a Estrutura, a Epistemologia, o Discurso
e o papel dos Modelos, defende nesta comunicao, em face dos desenvolvimentos
recentes, uma caracterizao desta disciplina ideal para a educao:
ONTOLOGIA- reduo Fsica mas no s Mecnica Quntica, que vrios autores
contemporneos denunciam mas tambm Mecnica Estatstica [1].
EPISTEMOLOGIA- fundada, no na matematizao nem em perspectivas diacrnicas mas
numa rede reaccional atemporal [2], que valoriza as relaes sistmicas [3].
METODOLOGIA- predomina a experimentao, negligenciada na filosofia da Cincia
mas que na Qumica desempenha um papel fundamental na construo e refinao de
conceitos e na relao com a Tecnologia [4].
DISCURSO-A existncia da base epistemolgica reaccional em rede permite um discurso
de acordo com os preceitos contemporneos da Cincia [5] e uma insero rigorosa no
paradigma construcionista emergente da Educao Cientfica [6], adaptado ao e-learning.
[1] D. Costa Pereira, (1995) A Epistemologia da Qumica e a estrutura e lgica dos seus
Discursos, Qumica - Boletim da SPQ.
[2] J. Schummer, HYLE - An International Journal for the Philosophy of Chemistry, 4 (1998) 129.
[3] P. Senge, The Fifth Discipline, Senge, The Art and Practice of the Learning Organization,
New York, Doubleday (1990).
[4] J. Schummer, Die Rolle des Experiments in der Chemie, in: P. Janich (ed.), Philosophische
Perspektiven der Chemie, Bibliographisches Institut, Mannheim, (1994) pp. 27.
[5] D. Costa Pereira, Nova Educao na Nova Cincia para a Nova Sociedade,Vol I- Fundamentos
de uma Pedagogia Cientfica Contempornea, Editora da Universidade do Porto (2007).
[6] D. Costa Pereira, (2008) From conceptual change to discourse analysis. The paradigm shift
induced in Science Education by e-Learning, Educao Formao & Tecnologias, vol. I (1).
291


TEORIA CONSTRUCTAL PARA O ENSINO DA QUMICA
E DA ENGENHARIA QUMICA

Lus M. P. Horta*
Escola EB 2,3/S Professor Mendes dos Remdios, Rua Professor Joo Porto, 6050 Nisa
*lmph2k@iol.pt

A Teoria Constructal aborda a formao fsica da configurao de fluxos na
Natureza e na Engenharia [1-2-3]; est em diversas reas como por exemplo a
optimizao de uma pilha de combustvel PEM [11]; a previso da morfologia
slida dendrtica [4]; sistemas de fluxos naturais [1-2-9]; energia verde [6], o
envelhecimento fisiolgico [10]; as Pirmides Egpcias e o fluxo dos
combustveis fsseis [2]; a circulao atmosfrica global e o clima [3]; reactores
qumicos dendritos slidos - gs [3]; a forma da Torre Eiffel [8]. A Teoria
Constructal torna-se assim incontornvel para os Engenheiros, Qumicos e
Bioqumicos, que ao conhece-la aprofundadamente podem criar oportunidades
para novas conexes e interaces, podendo conduzir criatividade e inovao.
Para a Formao Contnua de Professores, e de acordo com a perspectiva
CTSA, para os grupos de Fsica e Qumica; Biologia e Geologia; Matemtica e
Cincias da Natureza; Educao Fsica, devidos aos avanos j publicados
revela-se de extraordinria relevncia [1-2-3-5-6-7-8-10].

[1] Bejan, Adrian (2000). Shape and Structure, from Engineering to Nature, 1st Edition,
Cambridge: Cambridge University Press.
[2] Bejan, Adrian (2006). Advanced Engineering Thermodynamics, 3
rd
Edition, NJ:
Wiley, Hoboken.
[3] Bejan, A., Lorente, S. Constructal theory of generation of Configuration in nature and
engineering, Journal of Applied Physics 100 (2006) 041301.
[4] Ciobanas, A., Bejan, A., Fautrelle, Y. Dendritic solidification morphology viewed
from the perspective of constructal theory, J. Phys. D: Appl. Phys. 39 (2006) 5252.
[5] Horta, Lus Miguel (2006) Sustainable Development Tables for Science Teachers
Training within the Information Society. In 2
nd
International Green Energy
Conference, Oshawa, Ontario, Canada.
[6] Horta, Lus Miguel (2006) Gold in the information Era. In the XX National Meeting
of the Portuguese Chemical Society, Monte da Caparica, Lisboa, Portugal.
[7] Horta, Lus Miguel (2007) Introduo Teoria Constructal no Espao Web 2.0. In
the XII ENEC, UTAD, Vila Real, Portugal.
[8] La Tour Eiffel a livr son equation, Interview with A. Bejan, Science & Vie, No.
1050, March 2005, pp. 18-19.
[9] Reis, H., Miguel, A., Constructal Theory and Flow Architectures in Living Systems,
Thermal Science 10 (2006) 57.
[10] Andresen et all, Allometric scaling and maximum efficiency in physiological eigen
time, 99 (2002) 5822.
[11] Vargas et al Constructal flow structure for a PEM fuel cell, International Journal of
Heat and Mass Transfer 47 (2004) 4177.
292


NOMENCLATURA DOS ELEMENTOS QUMICOS

M. Clara F. Magalhes
a
*, Jos A. L. Costa
b
, Roberto B. Faria
c
, M.
Helena Garcia
d
, Rui T. Henriques
e
, Bernardo J. Herold
e
, Adlio A. S.
C. Machado
f
, Joaquim Maralo
g
, Osvaldo A. Serra
h

a
Departamento de Qumica e CICECO, Universidade de Aveiro, 3810-193 Aveiro
b
Escola Secundria de Jos Estvo, Av. 25 de Abril, 3811-901 Aveiro
c
Dep. Qumica Inorgnica, Univ. Federal do Rio de Janeiro, 21941-972 Rio de Janeiro
d
Dep. de Qumica e Bioqumica, Fac. de Cincias, Univ. de Lisboa, 1749-016 Lisboa
e
Dep. de Qumica, Instituto Superior Tcnico, Av. Rovisco Pais, 1049-001 Lisboa
f
Dep. de Qumica, Faculdade de Cincias da Universidade do Porto, 4169-007 Porto
g
Departamento de Qumica, ITN, Estrada Nacional 10, 2686-953 Sacavm
h
Dep. Qumica/FFCLRP, Universidade de So Paulo, 14040-901 Ribeiro Preto SP
*mclara@ua.pt

Um problema fundamental com que se defronta a comisso luso-brasileira [1]
que est a traduzir a Nomenclature of Inorganic Chemistry, Recomendaes da
IUPAC de 2005, o de harmonizar a nomenclatura em portugus nas variantes
de Portugal e do Brasil, na sequncia de decises da IUPAC de haver uma nica
proposta de nomenclatura por lngua.
Esta comunicao visa divulgar as alteraes propostas aos nomes utilizados
actualmente para designar os elementos qumicos.
Na tabela seguinte apresentam-se os nomes recomendados dos elementos que
apresentavam mais do que uma verso na variante do portugus de Portugal ou
que ainda no tinham nome atribudo:

Tabela 1. Nomes recomendados.
N Atmico Nomes antigos Nome recomendado
7 Azoto e nitrognio Nitrognio
24 Crmio e cromo Cromo
85 Astatnio e stato stato
96 Einstnio e einstinio Einstnio
109 Meitenrio e meitnrio Meitenrio
110 - Darmstcio
111 - Roentgnio

A fonte principal dos nomes recomendados para os elementos novos foi o
Dicionrio da Lngua Portuguesa Contempornea da Academia das Cincias.
Nesta comunicao ser apresentada a escrita dos nomes dos elementos
qumicos em portugus nas variantes de Portugal e do Brasil, acompanhada das
explicaes que justificam as escolhas apresentadas, j que a referida
harmonizao obrigou a algumas adaptaes como se v na tabela apresentada.

[1] A comisso constituda por membros propostos pela Sociedade Portuguesa de
Qumica e pelas Sociedade Brasileira de Qumica (SBQ) e Comit Brasileiro para
Assuntos de Qumica junto IUPAC (CBAQ).
293


CRIAO DE AULAS MULTIMDIA: O DOCENTE
SOZINHO OU COM A AJUDA DE UM INFORMTICO

Maria F. Simes
a
, Maria Isabel Ismael
b
, Joo L. Belo
c
*
a
Professora. Associada do Departamento de Psicologia da UBI, Rua Marqus d'vila e
Bolama, 6201-001 Covilh
b
Professora Auxiliar do Departamento de Qumica da UBI
c
Prof. Adjunto da Escola Superior de Sade Dr. Lopes Dias IPCB, Largo Dr. Lopes
Dias - Apartado 59, 6001-909 Castelo Branco
*jbelo@esald.ipcb.pt

Alguns eventos recentes, modificaram radicalmente a docncia e a
aprendizagem da Qumica acarretando um acrscimo de trabalho aos docentes,
de forma a alterarem a sua leccionao. necessrio garantir que os alunos
tenham bases slidas de onde possam consolidar os novos conhecimentos que se
lhes pretende transmitir bem como permitir ao aluno que seja ela prprio a
estabelecer o seu ritmo de aprendizagem. Foi no contexto anteriormente descrito
que se comearam a ponderar solues que ajustassem o processo de ensino e
aprendizagem s novas condicionantes. Foi neste sentido que o uso das novas
tecnologias emergiu como um dos possveis caminhos para colmatar estas
alteraes [1-2]. Numa rea como a Qumica, onde a visualizao dos processos
e reaces de extrema importncia [3] as TIC (Tecnologias da Informao e
Comunicao) no s permitiram uma adequao s novas exigncias bem como
permitem encarar a docncia de uma forma distinta, onde se interliga o ensino
presencial com o ensino via processos electrnicos, o denominado blended
learning.
Quase todas as Instituies de Ensino Superior possuem LMS (Learning
Management System) ou ditas Plataformas de Ensino Electrnico, incentivados
os docentes e alunos a fazerem uso delas. Contudo algo muito importante est a
faltar, necessrio ensinar as usar essa ferramenta ou caso seja necessrio
fornecer ajuda especializada. Neste trabalho iremos apresentar alguns exemplos
desenvolvidos pelos nosso grupo [4] evidenciado os diferentes resultados que se
podem atingir sendo apenas o docente a criar os seus contedos multimdia, at
ao caso de criao de contedos envolvendo uma equipa em que se conjugaram
os conhecimentos cientficos, pedaggicos e informticos.
[1] Paulsen, M.F., The Online Report on Pedagogical Techniques for Computer-Mediated
Communication. 1995, NKI Oslo, Norway.
[2] Simes, J.A.M., De regresso aos Gregos? A crise das cincias tradicionais, in Boletim
da Sociedade Portuguesa de Qumica. 2005. p. 12-13.
[3] Gillett, J.E., Chemical Engineering Education in the Next Century. Chemical
Engenniering Technology, 2001. 24(6): p. 561-570.
[4] Belo, J.L. and L. Opitz. A multimedia chemistry lesson, for an e-learning platform. in
INTED2007. International Technology, Education and Development Conference.
2007. Valencia - Spain: International Association of Technology, Education and
Development (IATED), C/ Dr. Vicente Zaragoz 70-9, 46020 Valencia SPAIN.
294


A CONSTRUO DO CUBO

Jaime F. B. Puna*, Brulio S. Baptista
ISEL, Dept. Eng. Qumica, R. Cons. Emdio Navarro, 1, 1959-007 Lisboa
*jpuna@deq.isel.ipl.pt

Esta comunicao insere-se no painel Inovao no Ensino da Qumica e da
Engenharia Qumica e pretende focar a experincia que foi conseguida com
alunos do Ensino Secundrio, no Ensino da Tecnologia Qumica. Para tal, foram
utilizadas duas metodologias: as visitas que vrios alunos efectuaram ao Lab. de
Tecnologia Qumica (LTQ) do ISEL e o contacto que mantiveram com os
diversos equipamentos ali instalados e, por outro lado, a realizao de
determinados trabalhos experimentais que alguns desses alunos tiveram
oportunidade de desenvolver no LTQ, utilizando tecnologias de processo
qumico e de operaes unitrias escala piloto
[1]
. Assim, de acordo com as
metodologias referidas, tentou-se a construo do cubo, da seguinte forma
[2]
:
1) Desenhar na folha A4 a planificao do cubo: apresentao da instituio
(ISEL) ao mundo do ensino secundrio, suas potencialidades, nomeadamente, no
Laboratrio de Tecnologia Qumica.
2) Recortar a planificao do cubo:
visitas dos alunos do ensino secundrio ao
ISEL.
3) Dobragem da planificao do cubo
pelas arestas: realizao de trabalhos
experimentais dos alunos do ensino
secundrio no Laboratrio de Tecnologia
Qumica do DEQ/ISEL.
4) Colagem das faces: Evoluo
cognitiva e psicomotora dos intervenientes
no processo (alunos, docentes, escolas).
De referir que os trabalhos experimentais realizaram-se ao abrigo do
programa Cincia Viva Ocupao Cientfica de Jovens nas Frias.

Tabela 1. Trabalhos experimentais desenvolvidos pelos alunos do Ens. Sec. no LTQ.
Ano Lectivo Trabalho experimental N. alunos
2005/2006
Produo de Etanol por Destilao
Produo de Acar
2
2
2006/2007
Permutador de Calor
Clula de Combustvel
Cintica de reaco em reactor Batch e CSTR
2
2
2

[1] H. S. Fogler. Elements of Chemical Reaction Engineering, 3
rd
Edition, Prentice-Hall,
1998.
[2] L. W. Andersen. Objectives, evaluation, and the improvement of education, Elsevier
B.V., Vol. 31, 2005.
Figura 1: Reactor Batch e CSTR.
295


CONSTRUO E EXPLORAO DIDCTICA DE
CALORMETROS

Jos A. L. Costa
a
*, Guida M. M. Bastos
a
, M. Clara F. Magalhes
b

a
Escola Secundria Jos Estvo, Av. 25 de Abril, Ap. 3, 3811-901 Aveiro
b
Departamento de Qumica e CICECO, Universidade de Aveiro, 3810 Aveiro
*jos.costa@esje.edu.pt

No novo programa de Qumica do 12 Ano [1], uma das actividades
laboratoriais obrigatrias a determinao da entalpia de neutralizao da
reaco NaOH(aq) + HCl(aq). Para a realizao desta actividade so necessrios
calormetros que nem sempre as Escolas possuem, no entanto possvel realiz-
la, com bons resultados, recorrendo utilizao de calormetros econmicos
construdos por reutilizao de materiais do quotidiano (garrafas de plstico,
copos e isoladores diferentes). Neste poster sero apresentados modelos de
calormetros construdos pelos autores do projecto e a sua explorao didctica
na sala de aula.
Para a utilizao destes calormetros em sala de aula, necessrio determinar
a constante dos calormetros, pelo qual se apresentar um processo simples para
a sua determinao.
Os calormetros construdos podem ser utilizados na sala de aula para
diversas actividades laboratoriais. Sero apresentados resultados experimentais
obtidos na utilizao dos calormetros na determinao de entalpias de
dissoluo, de fuso e na determinao da concentrao de um cido por
titulao calorimtrica.
A construo dos calormetros pode constituir per si um momento de
aprendizagem, envolvendo alunos da rea de projecto ou de Clubes de Cincia,
pois tero de pesquisar, seleccionar e testar materiais, optimizando o calormetro.

















296


OPTIMIZAO DE UM MTODO DE HPLC PARA
DETERMINAO DE ADITIVOS ALIMENTARES

Elsa Pereira
a
*, Celeste Serra
a
, Lusa Oliveira
b
, Elsa Vasco
b

a
Departamento de Engenharia Qumica, Instituto Superior de Engenharia de Lisboa, R.
Conselheiro Emdio Navarro n1, 1959-007 Lisboa, Portugal
b
Departamento de Alimentao e Nutrio, Instituto Nacional de Sade Dr. Ricardo
Jorge, Av. Padre Cruz 1649-016 Lisboa, Portugal
*elsambp@gmail.com

Os aditivos alimentares desempenham um papel vital na indstria alimentar
moderna, sendo geralmente utilizados com o objectivo de manter a qualidade e
as caractersticas dos gneros alimentcios. Para garantir o consumo seguro de
alimentos com aditivos, a Unio Europeia legisla a sua utilizao, limitando o
seu uso, estabelecendo doses dirias admissveis e obrigando os Estados
Membros a estabelecer um sistema regular de vigilncia para monitorizao do
consumo [1- 4]. Para obter essa informao, para alm de dados de consumo so
tambm necessrios mtodos de anlise robustos de modo a quantificar os nveis
dessas substncias numa larga variedade de matrizes alimentares.
Este estudo descreve o desenvolvimento da optimizao de um mtodo de
HPLC de fase reversa, baseado na norma EN 12856 [5], para a determinao de
aditivos alimentares.
A optimizao envolveu essencialmente a escolha da fase estacionria, a
composio e o fluxo da fase mvel de modo a permitir uma boa resoluo
cromatogrfica dos aditivos alimentares em estudo e simultaneamente diminuir o
tempo de anlise. Para alm, dos aditivos sacarina, acessulfame K e aspartame ,
usados como adoantes, do cido srbico e do cido benzico, utilizados como
conservantes, foram tambm estudados a cafena e a teobromina. Estabelecidas
as condies analticas foram validadas curvas de calibrao para as substncias
mencionadas. Foi verificada a existncia de linearidade e homogeneidade para a
gama de trabalho e foram calculados os limites de quantificao e deteco para
cada um dos compostos estudados.

[1] Q. Chen, J. Wan, J. Chromatogr. A, 937 (2001) 57.
[2] Directiva 94/35/EC Parlamento Europeu e Conselho de 30 de Junho 1994 relativa aos
edulcorantes para utilizao nos gneros alimentares.
[3] Directiva 94/36/EC do Parlamento Europeu e do Conselho de 30 de Junho de 1994
relativa ao corantes para utilizao nos gneros alimentcios.
[4] Directiva 95/2/CE Parlamento Europeu e do Conselho de 20 de Fevereiro de 1995
relativa aos aditivos alimentares com excepo dos corantes e dos edulcorantes.
[5] EN 12856, 1999, Foodstuffs Determination of acesulfame-K, aspartame and
saccharin - High performance liquid chromatographic method.
297


A QUMICA ANALTICA, NAS PGINAS DE O
I NSTI TUTO, NA SEGUNDA METADE DO SCULO XIX

Antnio J. F. Leonardo*, Dcio R. Martins, Carlos Fiolhais
Departamento de Fsica da FCTUC e Centro de Fsica Computacional, Rua Larga,
Universidade de Coimbra 3004-516 Coimbra
*ajleonardo@iol.pt

O Instituto de Coimbra (IC) foi uma academia cientfica e literria que existiu
em Coimbra de 1852 at dcada de 80 do sculo passado. A ela pertenceram
personalidades proeminentes do panorama cientfico portugus, em particular
professores da Universidade de Coimbra (UC). A actividade destes acadmicos
vem exposta nas pginas da revista, publicada por essa sociedade, com o nome
de O Instituto. Por exemplo, a evoluo da Qumica no nosso pas pode ser
estudada com base no conjunto de artigos que foram publicados neste peridico.
Divulgamos aqui parte do estudo que efectumos da evoluo da anlise qumica
ao longo da segunda metade do sculo XIX.
A Qumica Forense ou Toxicologia foi uma rea tratada com particular
relevo nO Instituto. Em vrios artigos publicados a partir de 1855, Antnio
Augusto da Costa Simes, professor da Faculdade de Medicina descreveu os
processos experimentais realizados no Laboratorio Chimico da UC para a
deteco do arsnico e de alcalides [1]. Comparativamente, apresentavam-se os
mtodos experimentais utilizados no Laboratrio Qumico Municipal do Porto
por Ferreira da Silva no mbito de um processo de medicina legal realizado em
1893.
Mas a actividade de Costa Simes tambm incluiu a anlise qumica,
nomeadamente das guas termais do Luso, e das guas de abastecimento pblico.
Com efeito, a anlise qumica de guas termais suscitou um grande nmero de
artigos de professores da Faculdade de Medicina da UC e, posteriormente, dos
qumicos mais notveis do pas, como Ferreira da Silva e Santos Silva. Pela
comparao dos mtodos utilizados ao longo deste perodo, relatados nos artigos
dO Instituto, pode-se verificar como a qumica analtica se desenvolveu em
Portugal na segunda metade do sculo XIX.
Apresentamos tambm algumas concluses retiradas do relatrio de Charles
Lepierre relativo ao Segundo Congresso Internacional de Chymica Applicada,
realizado em 1896 em Paris, onde participou um comit portugus.

[1] SIMES, A. A. Costa (1855). CHIMICA LEGAL. O Instituto. Vol. 4., pp. 10, 55, 69,
81, 120, 188, 258, 267.
[2] SILVA, A. J. Ferreira e SOUTO, Agostinho A. (1894). O caso medico-legal Silva
Pereira. O Instituto. Vol. 41., pp. 619, 672.
[3] LEPIERRE, Charles (1895). Relatrio sobre 2. Congresso Internacional de Chymica
Applicada. O Instituto. Vol. 43., pp. 762, 877. Vol. 44., p. 16, 153, 222, 358, 467,
665, 661.
298


INNOVATION IN COOKING
CHEMISTRY HAS A DECISIVE ROLE

Paulina Mata
a,b
*, Joana Moura
a
, Margarida Guerreiro
a
, Catarina
Prista
a,c
, Maria Loureiro Dias
a,c

a
Cooking.Lab, INOVISA, Tapada da Ajuda,1349-017 Lisboa
b
Dep Qumica, Fac Cincias e Tecnologia, Univ. Nova de Lisboa, 2829-516 Caparica
c
Instituto Superior de Agronomia, Univ. Tcnica de Lisboa, 1349-017 Lisboa
*paulina.mata@dq.fct.unl.pt

In the last decade a profound change is occurring in the way of cooking and
eating. However there is a gap at the technical level between the traditional
restaurants and the food industry sector. In recent years the most innovative
chefs became aware of this and of the fact that technological evolution in
cooking is slow and access to science and technology can bring new tools for an
increased creativity potential.
Molecular Gastronomy [1, 2] is the scientific discipline devoted to the study
of culinary transformations and gastronomical phenomena in general. It is a
multidisciplinary science in which the chemical component is of decisive
importance. Introduced in 1988 by Nicholas Kurti and Herv This, Molecular
Gastronomy can have important technological and educational applications.
In the last years in Europe, pioneer in Molecular Gastronomy research, the
collaboration between scientists, universities and research institutes, and chefs
and restaurants is increasing in number and scope. Collaborations started in an
informal way, but are now becoming more institutional. Gastronomy has an
important role in the tourism industry, and the transfer of knowledge and know-
how from science is seen as particularly interesting and considered crucial from
an economic point of view.
In the last four years, we have been doing research and working on the
technological applications of molecular gastronomy. We have mainly focused on
the study of hydrocolloids and emulsifiers, analyzing their properties and
devising innovative ways of using them in a gastronomical context. Another area
is the development of new and innovative applications of microbiology in
gastronomy.
We have been working with professional cooks that want to enlarge their
knowledge, and benefit from scientific developments to improve traditional
cooking techniques and introduce new ones. The necessity to keep up with the
most recent developments in this area is widely recognized.
Although research at an academic level is always a main concern, in order to
be able to answer to specific solicitations from chefs and also the industry a
small enterprise was created - Cooking.Lab [3].

[1] H. This, Angew. Chem. Int. Ed. Engl. 41 (2002) 83.
[2] H. This, EMBO Rep. 2006, 7 (2006) 1062.
[3] http://cookinglab.net/
299


DESENVOLVIMENTO DE UM LABORATRIO REMOTO
COM APLICAO NO ENSINO DA QUMICA

M. Gabriela T. C. Ribeiro
a
, Eunice R. G. O Rodrigues
b
, Rui A. S. Lapa
b
*
a
REQUIMTE, Faculdade de Cincias da Universidade do Porto, Rua do Campo Alegre
687, 4169-007 Porto, Portugal
b
REQUIMTE, Servio de Qumica-Fsica, Faculdade de Farmcia da Universidade do
Porto, Rua Anbal Cunha 164, 4099-030 Porto, Portugal
*ruilapa@ff.up.pt

A evoluo das redes de comunicao tm vindo a permitir e simplificar
muitos processos em que a comunicao em tempo real essencial. A
experimentao remota uma das reas que tem sido beneficiada, permitindo
disponibilizar recursos formativos sem
necessidade de grande investimento em
materiais e equipamentos e, simultaneamente,
constituir uma ferramenta pedaggica
cativante e facilmente adaptvel a diversas
situaes [1].
No sentido de disponibilizar uma
ferramenta que cumprisse objectivos
pedaggicos e em simultneo aumentasse o
envolvimento dos formadores, desenvolveu-se
um laboratrio remoto destinado execuo
remota de determinaes analticas, e que
simultaneamente permitisse integrar conceitos qumicos e instrumentais
associados anlise qumica.
O laboratrio desenvolvido foi organizado em cinco nveis, partindo da
interligao de dispositivos de laboratrio at gesto de acesso. A estrutura
lgica em que se baseou o sistema analtico remotamente opervel tem como
base uma estratgia de automatizao laboratorial robusta, baseada no conceito
de Anlise por Injeco Sequencial (SIA) e concebida para a realizao de um
conjunto determinaes analticas que podem ser seleccionadas, de acordo com a
oportunidade e o interesse pedaggico.
A gesto de acessos foi implementada de forma que o utilizador remoto
calendarize as operaes a realizar, permitindo-lhe controlar o sistema analtico,
podendo todos os demais utilizadores acompanhar a evoluo do processo
analtico tanto em termos da evoluo das variveis do sistema como aceder
imagem em tempo real.

Agradecimentos: E.R.G.O. Rodrigues agradece FCT a bolsa de doutoramento
(SFRH/BD/23417/2005). Os autores agradecem ao projecto Cincia Viva PVI-0216.

[1] J. V. Nickerson, J. E. Corter, S. K. Esche, C. Chassapis. Computers & Education, 49
(2007) 708.

Figura 1. Esquema genrico
do laboratrio remoto.
300


MEDIO DA DENSIDADE DE LQUIDOS UTILIZANDO
O MTODO DO PICNMETRO

Elsa Batista*, Nelson Almeida, Eduarda Filipe
Instituto Portugus da Qualidade, Rua Antnio Gio, 2 Caparica
*ebatista@mail.ipq.pt

A densidade uma propriedade dos lquidos essencial para a sua
caracterizao qumica. Existem vrios mtodos distintos para a determinao da
densidade e a sua escolha depende da exactido com que se pretende efectuar a
medio. O mtodo do picnmetro um mtodo bastante expedido, econmico,
que no necessita de instrumentao especfica e com incertezas inferiores a
0,001 g/ml [1].
Existem vrios tipos de picnmetros de
vidro ou metal, utilizados para a
determinao da densidade de diferentes
tipos de lquidos, desde gua, tintas e
diluentes. O picnmetro constitudo por
um recipiente e uma tampa que possui um
orifcio.
Neste trabalho foi utilizado um
picnmetro de vidro Gay-Lussac.
O princpio do mtodo consiste em
encher o picnmetro com o lquido a ser testado at que haja transvasamento. O
excesso de lquido removido e a densidade calculada atravs determinao da
massa do lquido contida no picnmetro e do volume do picnmetro
(previamente conhecido atravs da sua calibrao) para uma temperatura de
referncia de 20C [2].
Os resultados da determinao da densidade da gua ultra-pura, n-nonano,
gasolina e gasleo so apresentados e discutidos neste trabalho, juntamente com
a metodologia aplicada na avaliao das componentes de incerteza, sendo
descrito o modelo matemtico respectivo

[3].

[1] ISO 2811(1997) - Paints and varnishes-Determination of density-Annex B.
[2] ISO 4787 (1984) - Laboratory glassware - Volumetric glassware: Methods for use and
testing of capacity.
[3] GUM - Guia para a expresso da incerteza de medio nos Laboratrios de
Calibrao, IPQ, 2005.
Figura 1. Picnmetro Gay-Lussac.
301


FERRAMENTA WEB PARA O CLCULO DE ESTADOS
VIBRACIONAIS EM TEMPO REAL

Joo P. M. Poiares*, Srgio P. J. Rodrigues, Jorge M. C. Marques

Departamento de Qumica, Universidade de Coimbra, 3004-535 Coimbra, Portugal
*jepetto@sapo.pt

No ensino da Qumica Quntica os modelos mais realistas so quase sempre
remetidos para cursos avanados [1, 2]. O argumento mais utilizado para
justificar esta opo est associado complexidade das ferramentas matemticas
necessrias resoluo da equao de Schrdinger para esses modelos.
Actualmente, o uso massivo de computadores e o acesso generalizado
Internet perspectivam novos mtodos e ferramentas de ensino. Com estes
pressupostos, desenvolvemos uma ferramenta web [3] que permite calcular (e
representar graficamente), em tempo real, os estados vibracionais para vrios
potenciais modelo unidimensionais. A ferramenta disponibiliza vrios
potenciais: caixa de potencial (incluindo duplo poo) [1], oscilador harmnico
[2] e potenciais de Morse [4], Lennard-Jones [5], e Rydberg-extendido [6].
O utilizador pode escolher entre efectuar os clculos com os parmetros
predefinidos em cada potencial ou inserir os seus prprios parmetros. Todos os
estados vibracionais calculados (energias e funes de onda) so armazenados
em ficheiros que podem ser acedidos pelo utilizador, o que lhe permite usar essa
informao no seu prprio computador, por exemplo, para fazer representaes
grficas em folha de clculo ou Gnuplot [7]. Alm disso, a ferramenta web
permite tambm, de uma forma simples, alterar os grficos produ