Chem.

Listy, 99, s49s652 (2005) Physical &Applied Chemistry

s621
REFERENCES
1. Fonseca F. C., Muccillo R.: Solid State Ionics 166, 157
(2004).
2. Dokiya M.: Solid State Ionics 152, 383 (2002).
3. Pena M. A., Fierro J. L. G.: Chem. Rev. 101, 1981
(2001).
4. Bhalla A. S., Guo R., Roy R.: Mat Res Innovat 4, 326
(2000).
5. Kurzweil P., Fischle H. J.: Journal of Power Sources
127, 331 (2004).
6. Hsieh G., Mason T. O., Pederson L. R.: Solid State Ionic
91, 203 (1996).
7. Balazs G. B., Glass R. S.: Solid State Ionics 76, 155
(1995).
8. Godickemeir M., Gauckler L. J.: J. Elctrochem. Soc
145, 414 (1998).
9. Mogensen M., Sammes N. M., Tompsett G. A.: Solid
State Ionics 129, 63 (2002).
10. MacDonald J. R.: Impedance Spectroscopy. John Wiley
& Sons Inc., USA 1987.
P39 POLYMERIZATION OF DISSOLVED HUMIC
SUBSTANCES CATALYZED BY IRON
AND MANGANESE PORPHYRIN
DANIELA MEJKALOV
a
, PELLEGRINO CONTE
b
,
RICCARDO SPACCINI
b
, MILOSLAV PEKA
a
and ALESSANDRO PICCOLO
b
a
Institute of Physical and Applied Chemistry, Faculty of
Chemistry, Brno University of Technology, Purky ova 118,
612 00 Brno, Czech Republic, smejkalova@fch.vutbr.cz,
b
Dipartimento di Scienze del Suolo, della Pianta e dellAm-
biente, Universit di Napoli Federico II, via Universit 100,
800 55 Portici (Na), Italy, alpiccol@unina.it
Introduction
Even though formation of humic substances (HS) is one
of the least understood aspects of humus chemistry, it is re-
cognized that oxidoreductive enzymes, such as polyphenolo-
xidases produced by microorganisms and plants are directly
involved in these processes. The active site of these enzymes
is formed by metal porphyrins that are able to catalyze the
oxidation of humic constituents phenolic moieties into
free radicals that in turn can be stabilized by spontaneous
coupling to each other without additional involvement of the
catalyst
1
.
Since HS are important contributors to C cycle as major
source of CO
2
and C reservoir, it is of paramount importance
to increase the stability of these compounds against further
biotic and abiotic degradation
2
. Recent insights into humic
substances indicated that rather than being high molecular
weight polymers, they are associations of heterogeneous
molecules stabilized by hydrophobic interactions into only
apparently high molecular weights
3
. With this understanding,
it could be reasoned to mimic the catalytic coupling of HS
phenolic constituents and in this way stabilize humic com-
pounds by increasing the number of intermolecular covalent
bonds.
Previous work
4
has shown that synthetic iron porphyrin
successfully catalyzed the oxidative polymerization of HS
when H
2
O
2
was used as singlet oxygen donor. The aim of
this work was to verify whether photo-oxidation could sub-
stitute the presence of singlet oxygen donor in the biomimetic
polymerization of humic material.
Materials and methods
Detailed description of humic material extraction, bi-
omimetic catalysis and High Performance Size Exclusion
Chromatography (HPSEC) system used in this work is given
elsewhere
4
.
Results and discussion
Biomimetic polymerization of lignite humic material,
induced by UV light exposure, was followed by HPSEC
system coupled with UV and refractive index (RI) detectors.
The efciency of biomimetic catalysts, namely manganese
(Mn-pha) and iron porphyrin (Fe-pha) was evaluated by de-
termination of the average molecular weight (Mwa) values of
control and catalyzed samples.
The addition of metal porphyrin catalyst to the non-
-exposed humic solutions did not vary the Mwa values
previously obtained for control humic solution. However,
signicant changes of molecular weight were detected in the
UV light exposed samples. Percentage increase of Mwa is
shown in Fig. 1. and 2.
According to the UV-detected (280 nm) chromato-
grams, the irradiated humic material increased Mwa by 4 and
11 % after 5.5 h and 14 and 12 % after 13 h of exposure to
UV light, in the presence of Mn- and Fe-pha, respectively
(Fig. 1.). The time course progression of the UV light indu-
ced photo-oxidation was observed when already irradiated
samples for 13 h were further collected after 8 and 11 d from
the exposition. This time the Mwa values reached an increase
of 27 and 23 % after 8 d and of 34 % after 11 d since UV
exposure (Fig. 1.).
Since UV detector reveals only the molecular absorpti-
vity of chromophore groups at chosen wavelength, the Mwa
was determined also from chromatograms collected by RI
detector that is able to follow the overall mass distribution
of humic matter. Evaluation of RI-detected size exclu-
sion chromatograms veried the general increase of Mwa
values obtained during photo-induced oxidative polyme-
rization of dissolved humic material. In fact, polymerized
humic materials increased the Mwa values by 9 and 6 %
after 5.5 h and 6 % after 13 h of exposure to UV light, in
the presence of Mn- and Fe-Pha, respectively, compared to
the control HA solution (Fig. 2.). Then a signicant increase
in molecular dimension was observed for samples analyzed
after 8 and 11 d following 13 h irradiation with UV light.
In this case, Mwa was increased by 24 and 32 % after 8 and
11 d from the UV irradiation in the presence of Mn-pha,
Chem. Listy, 99, s49s652 (2005) Physical &Applied Chemistry
s622
respectively, whereas the increase of Mwa values obtained
with the Fe-Pha catalyst was 13 and 50 % after the same time
courses (Fig. 2.).
REFERENCES
1. Dec J., Haider K., Bollag, JM.: Soil Sci. 166, 660671
(2001)
2. Clapp C. E., Hayes M. H. B.: Soil Sci. 164, 777789
(1999)
3. Piccolo A., Cozzolino A., Conte P., Spaccini R.: Natu-
rwissenschaften, 87, 391394 (2000)
4. Piccolo A., Conte P., Tagliatesta P.: Biomacromolecules
6, 351358 (2005)
P40 DETERMINATION OF ROTATIONAL
MOLECULAR CONSTANTS
HANA SORMOVA
a,b
and JEAN DEMAISON
b
a
Institute of Physical and Applied Chemistry, Faculty of
Chemistry, Brno University of Technology, Purkynova 118,
612 00 Brno, Czech Republic, hanka@milansorm.cz
b
Laboratoire de Physique des Lasers, Atomes et Molecules,
UMR CNRS 8523, Universite de Lille I, 596 55 Villenevue
dAscq Cedex, France, Jean.Demaison@univ-lille1.fr
Introduction
The accuracy of the molecular constants determina-
tion is important for prediction of the transition frequency
of the observed molecules. If we know the exact molecular
constants then it will be easier to measure the spectra of the
molecules and also to economize with the time of measure-
ment and the sample.
This article, therefore, describes the methods of deter-
mining the rotational molecular constants from the experi-
mental data and of computing their accuracy. This method is
part of the program RotSimul
1
which helps to calculate these
constants automatically.
The principle of the rotational molecular constants
determination
The determination of rotational molecular constants is
based on the theoretical calculations of the transition fre-
quencies between the higher and lower energetic states. For
example, the formula
2
for the symmetric prolate rotor is as
follows:
2 1 4 1 2 1
3 2
B J D J D J K ( ) ( ) ( )
J JK

(1)
where is the transition frequency, B represents the rota-
tional constant, J and K are the rotational quantum numbers
(where |K| = 0, 1 J), D
J
and D
JK
are centrifugal distortion
constants they depend on the bond strength.
The equation (1) is applicable to most measurements,
but sometimes it is necessary to use a different higher order
correction for centrifugal stretching where H
J
, H
JK
, H
KJ
are
the centrifugal sextic
3


h B J D J D J K
H J J J H
( ) ( ) ( )
( ) |( ) |
2 1 4 1 2 1
1 2 4
3 2
3 2 3
J JK
J JKK
KJ
( )
( ) }
J K
H J K


1
2 1
3 2
4
(2)
If we measure the dependence of the transition frequency
on the rotational quantum number J, then it is possible to
use the multi-linear regression (3) and through this procedure
determine the values of rotational molecular constants
4,5
.
y b b x b x b x
0 1 1 2 2 3 3
(3)
where y represents the transition frequency, x
1
, x
2
, x
3
, pre-
sent the terms (J+1, (J+1)
3
, and parameters b
1
, b
2
, b
3
,
are the tting molecular constants. Using the knowledge of
0
10
20
30
40
50
UV 5.5h, 0d UV 13h, 0d UV 13h, 8d UV 13h, 11d
l
n
c
r
e
a
s
e

o
f

M
w
a

(
%
)
Mn-pha
Fe-pha
0
10
20
30
40
UV 5.5h, 0d UV 13h, 0d UV 13h, 8d UV 13h, 11d
l
n
c
r
e
a
s
e

o
f

M
w
a

(
%
)
Mn-pha
Fe-pha
Fig. 1. Percentage increase of apparent weight-average mo-
lecular weight (Mwa) of lignite humic solutions added with
Mn-pha or Fe-pha catalyst and exposed to UV light for 5.5 or
13 h, right after exposure (0 d), after 8 and 11 d after irradiation
end. HPSEC chromatograms were revealed by UV detector
Fig. 2. Percentage increase of apparent weight-average mo-
lecular weight (Mwa) of lignite humic solutions added with
Mn-pha or Fe-pha catalyst and exposed to UV light for 5.5 or
13 h, right after exposure (0 d), after 8 and 11 d after irradiation
end. HPSEC chromatograms were revealed by RI detector