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Review article
Abstract
The porphyrins, naturally occurring macrocyclic compounds, have, in the last 10 years, gained increasing interest
in analytical chemistry. This review based on 123 original literature references, mostly published in the 1990s, presents
catalytic applications of metalloporphyrins in electroanalysis as electroactive agents in ion selective membranes, as
unique reagents in spectrophotometry and as new stationary phases offering unusual resolution in HPLC. The
collected data are also presented in four tables. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Porphyrins; Metalloporphyrins; Preconcentration; HPLC stationary phases
1. Introduction
The porphyrins are a class of naturally occurring macrocyclic compounds, which play a very
important role in the metabolism of living organisms. The porphyrin molecule contains four
pyrrole rings linked via methine bridges (Fig. 1).
The porphyrin nucleus is a tetradentate ligand in
which the space available for a coordinated metal
has a maximum diameter of approximately 3.7 A,
[1]. When coordination occurs, two protons are
removed from the pyrrole nitrogen atoms, leaving
two negative charges. The porphyrin ring system
is very stable and exhibits aromatic character. The
* Corresponding author. Tel.: +48-22-8223532; fax: + 4822-8223532.
E-mail address: trojan@chem.uw.edu.pl (M. Trojanowicz)
0039-9140/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 2 9 1 - X
210
Name
ATPPS
CoTRBP
CPI
m-BrTPPS4
OBTPPS
OEP
p-NO2Bz-TPPS
(p-OH)TPP
ProP
TAPP
TCPP
TMAP
TMHPP
T(1-MPy)P
TMPyP
T(3-MPy)P
T(4-MOP)PS4
TMOPP
TPP
TPPS3
TPPS4
TPyP
Table 2
Spectrophotometric determination of metal ions with porphyrin reagents
Metal ion
Reagent
T(1-MPy)P
Cu(II)
TPPS3
Cu(II)
TPP
Cu(II)
T(3-MPy)P
Cu(II)
TMAP
Cu(II)
Cu(II)
p-NO2Bz-TPPS
CPI
Co(II)
Cd(II)
Zn(II)
T(1-MPy)P
TPPS4
Zn(II)
TPPS4
Zn(II)
TPP
Zn(II)
TPPS4
Zn(II)
Pd(II)
TPPS4
TPPS4
Mg(II)
T(4-MPy)P
Bi(III)
p-NO2B2TAPS
Ag(I)
TPyP
Ni(II)
TPPS4
Li(I)
OBTPPS
Complexation at pH 9, L-cysteine
(room temp., 5 min) then acidify
with H2SO4
pH 4 (100, 1 min) then pH 2.5
with chloroacetic acid
Solubilised by Na-laurylsulfate at
pH 4.7+NH2OH (100, 3 min)
then pH 0.61.2 with H2SO4
pH 6+NH2OH (100, 7 min) then
acidify with H2SO4
Complexation at pH 4.15.9+Lascorbic acid
pH 5 (90, 7 min)
Complexation at pH 8 (90, 10
min)
+Imidazole or pyridine
pH 9.8+Pb(II)+L-tryptophan
pH 7.1+imidazole+Cd(II) (room
temp., 30 min)
pH 6+imidazole+Pb(II) (room
temp., 30 min) then EDTA
Glacial acetic acid (room temp.,
6070 min)
pH 4.8+imidazole (stop-flow for 1
min)
pH 88.7+Mn(II)+NH2OH
pH 4+ascorbic acid (100, 7 min)
then pH 2.5
pH 9.110.6+8-quinolinol (100,
60 min)
pH 5.9+Cd(II) (35, 2 min) then
SDS
(100, 10 min)+ethanol, acidified
with H2SO4
Complexation at pH 89+Cd(II)+
imidazole (100)
pH 11+EDTA+Mg(II)
Absorption spectra
Range of
determination
Interference
Ref.
lmax (nm)
o (105)
423
3. 9
660 mgl1
[3]
434
4.8
660 ng l1
Zn
[4]
414
4.7
140 ng l1
[5]
434
3.5
113 ng l1
Fe(III) and Pd
[6]
411
5.1
Sn(II), I, ClO
4
[7]
413
414
4.2
Up to 100 ng
l1
130 mgl1
35128 mgl1
[8]
[9]
380
448
425
1.7
4.5
0.323 mgl1
10150 ng l1
[10]
[11]
421
4.7
Zn, Hg(II)
Mn(II), Co(II)\40 mg l1
Fe(III)\70 mgl1
Cu, Co(II), Mn(II)
[12]
551
0.14
424
Up to 100
mgl1
Up to 200
Cu
mgl1
Up to 2.5 mgl1
413
411
2.8
2.2
[15]
[16]
[17]
466
[18]
425
1.8
[19]
418
2.3
[20]
490
2.0
Up to 1.1 mg
l1
Up to 0.36 mg
l1
Up to 150 ng
l1
7700 mgl1
Hg(II)
[21,22]
[13]
[14]
Cu(II)
Condition
211
212
Table 3
Potentiometric methods based on the use of porphyrin
Analyte
Electroactive component
Range of response,
pX
Electrode
matrix
Inorganic anions
Inorganic anions
Chloride
NO
2 , F
Iodide
Iodide
Iodide
SCN
Salicylate
Ni2+
Co2+
15
25
PVC
PVC
SRa
Polysiloxane
Carbon
Ag
Pt
PVC
PVC
PVC
PVC
Water
15
16
14
16
35
16
16
Human serum
Edible seaweed
Urine
Serum, urine
Chocolate
[51]
[53]
[54]
[55]
[56]
[57]
[58]
[52]
[59]
[60]
[61]
2. Spectrophotometric methods
Several porphyrins become useful as the spectrophotometric reagents for the determination of
metal ions (Table 2). Their certain disadvantage is
that the incorporation reaction of the metal ion in
the porphyrin ring is very slow and the rate of
metalloporphyrin formation is several orders of
magnitude lower than with the common ligands.
The slow reaction rate is the result of difficulty in
deforming of porphyrin ring. The porphyrins with
substituents at the pyrrole nitrogen, such as Nalkyl or N-benzyl, are more reactive than their
non-substituted analogues. Alkylation of any of
the pyrrole nitrogen will lead to an increase in the
distortion of the macrocycle and this in turn leads
to an increase in the basicity of a particular
pyrrole nitrogen. To enhance the reaction rate
several procedures, except heating, have been
employed.
The complexation of metal ion by porphyrin
can be enhanced substantially by the use of an
auxiliary complexing agent. For example, the rate
of complexation of TMPyP with Cu(II) and
Mg(II) was accelerated by L-cysteine [3] and 8quinolinol [7], respectively. The mechanisms for
this process have not been clearly elucidated and
the auxiliary complexing agents are very specific
for each system.
The organic ligands with an extended p-electron
structure, such as imidazole or bipyridine [912]
213
Table 4
Voltammetric determination involving the use of porphyrinsa
Analyte
Electrode
material
Modifier
Measuring
technique
Analysed sample
Ref.
Organohalides
Sugars
Oxygen
Oxygen
Graphite
Graphite paste
Pt
Au
Aqueous sample
[62]
[63]
[64]
[65]
Oxygen
Hydrazine
Phenols
NO
NO
NO
Ag/colloid/PVA
Carbon paste
Glassy carbon
Glassy carbon
Glassy carbon
Carbon fibre
CoTMPyP
CuTPP
poly[MProP], M =Ni2+, Co2+, Cu2+
NiTMHPP
NiTMHPP
NiTMHPP
NO
NO
Carbon fibre
Carbon fibre
[NiTMHPP]poly
[NiTMHPP]poly
SWV, CV
CV
Amperometry
CV, RRDE,
RDE
CV
CV
CV
CV
CV, DVP
Chronoamperometry
CV
CV, DVP
NO
NO
NO
NO, NO
2
Carbon fibre
Carbon fibre
Glassy carbon
Vitreous carbon
disk
Glassy carbon
Vitreous carbon
Carbon or Pt
Carbon fibre
Carbon fibre
Glassy carbon
NiTMHPP
NiTMHPP
Haemoglobin
Poly [FeProP], poly [FeTPPS4], poly
[FeTMPyP]
CoTRBP/ZnTPPS4
CoTPyP
TMHP
[NiTMHPP]poly
[NiTMHPP]poly
TPP
CV
CV
CV
DVP
DVP
ASV
[78]
[79]
Water
[80]
Single biological cells [81]
Single biological cells [82]
Tap water
[83]
Glassy carbon
NiTAPP
CV
Paracetamol
[84]
Glassy carbon
Hg
Hg
Hg
NiTMHPP
TMAP
CuTMAP
NiTMPyP
CV
CV
CV
CV, chronocoulometry
SWV, CV
Methanol solutions
Calf thymus DNA
Calf thymus DNA
Calf thymus DNA
[85]
[86]
[87]
[88]
NO2 SO2
3
2
NO
2 SO3
Ni2+
Ni2+
Ni2+
Heavy metals,
Cu2+
Acetoaminophen
Alcohols
DNA
DNA
DNA
ZnProP
CoTRBP
DVP
DVP
Amperometry
CV
Amperometry,
CV
Solutions saturated
with NO
Blood
Blood, single endothelial cells
Rat brain, blood
Rat brain, blood
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[89]
[90]
a
CV, cyclic voltammetry; DVP, differential pulse voltammetry; SWV, square wave voltammetry; ASV, anodic stripping
voltammetry; RRDE, rotating ring disk electrode voltammetry; RDE, rotating disk electrode voltammetry.
214
metal chelates. One way to avoid such interferences is to utilise the spectral shift of free reagent
upon acidification [4]. The stable metalloporphyrins (e.g. with Cu(II) or Pd(II) ions) once
formed, do not dissociate readily in acid medium
and show a strong absorption band in the region
where the protonated reagent does not absorb.
The second approach utilises the spectral shift of
the excess of free reagent by chelation with Pb(II)
[29]. This can be applied to metalloporphyrins
which tend to dissociate upon acidification, such
as Cd(II), Mn(II) or Zn(II). Another way to avoid
spectral interferences is the introduction of a suitable N-substituted porphyrin, whose absorption
band does not overlap with the spectra of the
complex [17].
Due to large stability and catalytic behaviour
several metalloporphyrins have found various applications in chemical analysis. Indirect spectrophotometric determination of trace cyanide in
waste waters was based on inhibition of reaction
of tetrakis(1-methyl-2-pyridinio)porphyrin with
silver ions [30]. On the basis of the diazotization
reaction of tetrakis(4-aminophenyl)porphyrin [31]
and
[5-(4-aminophenyl)
tetrakis(4-pyridyl)porphyrin [32] with nitrite ion, a sensitive spectrophotometric determination for nitrite was developed. The complex of Fe(III) with
tetrakis(1-methyl-4-pyridyl)porphyrin was applied
as a catalyst for indamine dye formation, which
can be used for spectrophotometric determination
of hydrogen peroxide [33]. The oxo[tetra(4pyridyl) porphyrinato]titanium(IV) complex could
be used to detect trace amounts of hydrogen
peroxide [34] and oxalate ions [35]. The flow
procedure for determination of hydrogen peroxide
was based on the catalytic effect of immobilised
Mn(III) complex with TPPS4 [36].
In recent studies, immobilised porphyrins were
also employed in the design of optochemical sensors for pH [37,38], thiocyanate [39], oxygen [40
42], metal ions [43] and for analysis of a mixture
of gases [44]. The optical pH sensor obtained by
electrostatic immobilisation of TMAP on a sulfonated surface of transparent polystyrene resin
can be used in the pH 1.54.5 region [38]. The
fibre optic sensor developed by electropolymerization of Co(p-OH)TPP on the surface of indi-
215
Table 5
Application of porphyrins in metal analysis by HPLCa
Analyte
Sample
Porphyrin
Column
Eluent
Ref.
Bovine liver
TPP
Acetone/ACN
[103]
Electroplating waste
liquor, tin alloy
Aqueous sample
TPP
Methanol/H2O/
chloroform
Methanol/H2O/
acetyloaceton/
amine
[96]
TPP
Lichrosorb RP18
Micropak
MCH-5
TSK Gel ODS80TH
[97]
Tap water
Peach leaves
THPP
m-BrTPPS4
Ethanol/H2O
ACN/H2O/TBABr
[104]
[105]
River water
m-BrTPPS4
ACN/H2O/TEAI
[98]
m-BrTPPS4
ACN/H2O/TEAI
[99]
TCPP
Tap water
TCPP
Peach leaves
TPPS4
Cu(II), Zn(II)
Peanuts
TPPS4
Tea
TPPS4
Cu(II), Zn(II)
Peanuts
TPPS4
TPPS4
T(4-MOP)PS4
[112]
[100]
Acetone/H2O/
BTEACl
Acetone/H2O/
BTEACl
ACN/H2O/
BTEACl
NaCl/tartaric acid
[108]
ACN/H2O/TEAI
[111]
[109]
[101]
[110]
a
ACN, acetonitrile; TBABr, tetrabutylammonium bromide; TEAI, tetraethylammonium iodide; BTEACl, benzyltriethylammonium chloride; TBP, tributylphosphate.
216
3.1. Potentiometry
With potentiometric sensors, the recognition
process is a selective binding event which transduces analyte ionic activity into a potential readout. Efforts during recent years have focused
primarily on the development of membrane ion
selective electrodes (ISE) for various analytes, the
synthesis of new (more selective) ionophores and
microfabrication and integration of miniaturised
potentiometric probes.
Several metalloporphyrins were used as electroactive components in the membrane of ion
selective electrodes, and their potentiometric response to anions has been interpreted by a dissociation ion-exchange mechanism or metalligand
interaction mechanism [4561].
ical sensors was also presented [44]. The rhodiumand cobalt-based sensors demonstrated a preference for thiophene and amines, while the sensors
with manganese preferred methanol. The results
obtained led to the overall conclusion that such a
sensor array could be used for analysis of complex
gas mixtures.
217
Table 6
Retention factors of selected amino acids on different protoporphyrin (ProP) and tetraphenylporphyrin (TPP) silica columnsa
H2TPP
H2ProP
ZnTPP
ZnProP
CuTPP
CuProP
a
Gly
His
Lys
Cys
Ser
Phe
Trp
Glu
0.1
0.1
0.1
0.1
0.8
0.1
0.3
1.0
1.5
2.1
6.0
4.1
0.1
1.2
0.2
1.7
0.7
2.2
0.1
0.2
0.1
0.2
3.4
0.3
0.1
0.1
0.1
0.1
1.4
0.1
0.5
1.5
0.5
2.1
6.0
8.7
2.4
10.5
1.2
13.9
6.0
109.0
0
0
0
0
0
0
Mobile phase 50 mM phosphate buffer at pH 7.0; flow rate 1 ml min1; detection UV 214 nm [115,121].
(i.e. ClO
4 \SCN \I \salicylate \Br \ Cl ).
Schulthess et al. [45] reported chloride and nitrite
selective electrodes based on lipophilic vitamin B12
derivatives as ionophores. These electrodes were
the first anion selective electrodes for which selectivity sequence was different from the Hofmeister
series.
Fig. 6. The comparison of the retention factors for di and tripeptides obtained with 25 cm H2TPP, 25 cm ZnTPP and 5 cm CuTPP
columns using 50 mM phosphate pH = 7+ 10% ACN as eluent at a flow rate of 1 ml min 1; injection volume 20 ml, UV detection
210 nm [123].
218
3.2. Voltammetry
decay products in biological systems are important in understanding their physiological role.
Malinski and coworkers [71 73] described the
applications of carbon fibre microelectrodes
coated with a film of NiTMHPP for this purpose.
Carbon fibre ultramicroelectrodes modified
with a conductive polymer film of Ni(II)TMHPP
have been used for voltammetric determination of
nitric oxide in biological samples [72 75], as well
as for measurements of nickel in water samples
[80] and in single cells [81,82].
Different iron porphyrins have been used in the
design of sensors for nitric oxide and nitrite determination. Fig. 2 shows the proposed mechanism
of interaction between NO and NO
2 and iron
porphyrins. The authors confirmed the formation
of
iron
nitrosyl
porphyrin
complex
[Fe(III)(NO)]+ by absorption spectral changes
observed at coated electrodes. The changes of the
Soret band were observed, when the Fe(III) from
complex with porphyrin had been reduced to
Fe(II) porphyrin complex [77].
A TPP-coated glassy carbon electrode was used
for anodic stripping voltammetry of heavy metals
[83]. Such an electrode showed an increase in
sensitivity for the detection of copper compared
to an uncoated one. The influence of TPP layer
thickness, pH, and accumulation time on copper
detection and interferences with other cations was
investigated. The detection limit of copper was
found to be 12 mg l 1 for an accumulation time of
30 s.
Graphite electrodes coated with thin films of
electropolymerized protoporphyrin can suppress
the interfering oxidation of ascorbic acid without
a significant decrease of response to dopamine
[89]. The metalloprotoporphyrin films prepared
by electropolymerization of NiProP, CoProP or
CuProP on glassy carbon electrode have been
used as sensors for phenols [68].
A metalloporphyrin film modified platinum
electrode was prepared by electrochemical polymerisation of Fe(III)TMHPP on the electrode
surface. Wu et al. [64] applied this electrode as an
oxygen sensor at relatively low potential. Also
another oxygen sensor based on a metalloporphyrin modified electrode has been proposed for
electrocatalytic determination of oxygen dissolved
219
220
221
5. Conclusions
This review shows the important role of porphyrin in analytical chemistry. Porphyrins find
many applications as ligands for spectrophotometric determination of cations. The stabile complexes between transition metal cations and
porphyrins enable coordinating interaction with
extra ligands so these compounds are used as
components of membranes of ISE in potentiometry, and in voltammetry. Several porphyrins find
applications as biosensors. Due to the mixed
mechanism of interaction between porphyrin
macrocycle and various solutes, porphyrins find
interesting applications as stationary phases in
HPLC.
222
Acknowledgements
This work was supported by Grant No. 120501/66-GR-1118/99 from the Polish State Committee for Scientific Research.
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224