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Talanta 51 (2000) 209 224

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Review article

Porphyrins in analytical chemistry. A review


Magdalena Biesaga, Krystyna Pyrzynska, Marek Trojanowicz *
Department of Chemistry, Uni6ersity of Warsaw, Pasteura 1, 02 -093 Warsaw, Poland
Received 15 April 1999; received in revised form 16 September 1999; accepted 1 October 1999

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)

porphyrin complexes with transition metal ions


are very stable, e.g. the stability constant for
ZnTPP (tetraphenylporphyrin) is 1029 [1].
Almost all metals form complexes 1:1, although
Na, K, Li complexes are 2:1 in which the metal
atoms are incorporated slightly below and above
the porphyrin macrocycle plane. When divalent
metal ions (e.g. Co(II), Ni(II), Cu(II)) are
chelated, the resulting tetracoordinate chelate has
no residual charge. While Cu(II) and Ni(II) in
their porphyrin complexes have generally low
affinity for additional ligands, the chelates with
Mg(II), Cd(II) and Zn(II) readily combine with
one more ligand to form pentacoordinated complexes with square-pyramidal structure. Some
metalloporphyrins (Fe(II), Co(II), Mn(II)) are
able to form distorted octahedral with two extra
ligand molecules.

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PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 2 9 1 - X

M. Biesaga et al. / Talanta 51 (2000) 209224

210

Fig. 1. Porphyrin macrocyclic system.

Porphyrin metal complexes play an important


role in biological activities as for instance iron
complex in the haemoproteins, magnesium comTable 1
Abbreviations used for porphyrin compounds
Abbreviation

Name

ATPPS

5-(4%-Aminophenyl)-10, 15, 20-tris(4%sulfonatophenyl) porphyrin


meso-(Tetrapyridyl)porphyrinate
cobalt(III) [bis(bipyridine)(chloro)ruthenium(II)]
Coproporphyrin-I
meso-Tetrakis(3-bromo-4-sulfophenyl)
porphyrin
Octabromo-tetrakis(4-sulfonatophenyl)
porphyrin
Octaethylporphyrin
N-4-Nitrobenzyl-tetrakis(4-sulfonatophenyl)porphyrin
Tetrakis(4-hydroxyphenyl)porphyrin
Protoporphyrin IX
Tetrakis(4-aminophenyl)porphyrin
meso-Tetrakis(4-carboxyphenyl)
porphyrin
meso-Tetrakis(4-N-trimethylaminophenyl)porphyrin
Tetrakis(3-methoxy-4-hydroxyphenyl)
porphyrin
meso-Tetrakis(1-methylpirydinium-4-yl)
porphyrin
Tetrakis(1-methyl-4-pyridyl)porphyrin
Tetrakis(3-N-methylpyridyl)porphyrin
meso-Tetrakis(4-methoxyl-3-sulfophenyl)porphyrin
Tetrakis(4-methoxylphenyl)porphyrin
Tetraphenylporphyrin
Tetraphenylporphyrin trisulfate
meso-Tetrakis(4-sulfophenyl)porphyrin
meso-Tetra(4-pyridyl)porphyrin

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

plexes in the chlorophylls, and a cobalt complex


in Vitamin B12. Complexes of many metals with
various porphyrins have been extensively studied
in order to understand the biosynthetic formation
and biological activity of natural compounds.
Porphyrin derivatives play a key role in essential
biological processes such as photosynthesis,
dioxygen transport and storage. From the perspective of coordination chemistry, the porphyrin
ligand has turned out to be very versatile, and
almost all metals have been combined with porphyrins. Such complexes have been used in a
variety of applications as models for biological
electron transport, oxygen transport and metalloenzymes.
It is well known that porphyrin is also a high
sensitive chromogenic reagent. Porphyrins and
their metal chelates generally exhibit characteristic
sharp and intensive absorption bands in the visible region. The region from 400 to 500 nm, which
is called the Soret band, shows the most intensive
absorption and molar absorptivities of the order
of 105 are often found. The Soret band is widely
used for spectrophotometric determination of
metalloporphyrins.
Owing to its well known photochemical and
redox activity, the porphyrin macrocycle is an
attractive building block on which to append
additional recognition sites for anion binding. The
combination with Lewis acid, such as zinc, complexed in the porphyrin macrocycle cavity, may
produce new selective redox active reagents for
anions. Indeed various metalloporphyrins have
shown a potentiometric response to anions with
selectivity sequences solely dependent on the centrally bonded metal [1,2]. The metalloporphyrins
have a rich redox chemistry since they have the
advantage of including coordination of additional
ligands above and below the porphyrin plane.
Due to strong complexing properties and catalytic behaviour of metalloporphyrins, these compounds have found numerous applications in
chemical analysis. This review presents applications of porphyrin compounds in spectroscopy,
electroanalytical chemistry, flow injection analysis, and chromatography. The names and abbreviations of porphyrin compounds used in this
review are listed in Table 1.

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

Ag, Hg(II), Zn\10 mg, Pd\5 mg

[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

Co(II), Pd, Fe(III)\2 mg

[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

Cd, Hg(II), Fe(III)


Cu, Hg(II)

[15]
[16]

After dithizone separation

[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]

M. Biesaga et al. / Talanta 51 (2000) 209224

Cu(II)

Condition

211

M. Biesaga et al. / Talanta 51 (2000) 209224

212

Table 3
Potentiometric methods based on the use of porphyrin
Analyte

Electroactive component

Range of response,
pX

Electrode
matrix

Analysed sample Ref.

Inorganic anions
Inorganic anions
Chloride

NO
2 , F
Iodide
Iodide
Iodide
SCN
Salicylate
Ni2+
Co2+

SnTPP, CoTPP, InOEP


GaTPP, GaOEP, InTPP, InOEP, TlTPP
MnTPP, InTPP, MnOEP, InOEP
CoTPP
SnTAPP, H2TAPP
TPPS4
MTAPP
(FeTPP)2O
SnTPP
H2TPP, HTMPP
TPP

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]

SR, silicon rubber.

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]

and L-tryptophan [23] also show a tendency to


accelerate the formation of metalloporphyrins.
These catalysts form intermediate molecular complexes with metal ions and porphyrin reagents. In
the presence of tryptophan, the rate of incorporation of Zn(II) to TPPS4 is about 100 times greater
than in its absence [23].
In the reaction of large metal ions, such as
Hg(II), Pb(II) and Cd(II), with porphyrins, they
cannot fit into the porphyrin nucleus and just sit
on top of the molecule. In this case, reaction is
relatively fast and proceeds through a pathway
involving a mononuclear activated complex [24].
Such sitting-atop complex deforms the porphyrin nucleus favourably for the attack of another metal ion from underneath. At higher
concentrations of larger metal ion, a heterodinuclear intermediate complex results from which
metal is then easily released. The ionic radius of
the metal ion acting as a catalyst appears to be an
important factor. The catalytic effect on the complex reaction of TPPS4 with Mn(II) increases in
the order: Pb(II)B Cd(II)B Hg(II) [24]. Accelerating effect of Cd(II) and Pb(II) on the complex
formation of Zn(II) with TPPS4 was applied to
the determination of zinc at the mg l 1 level in
cadmium salts [25] and also in lead chemicals and
waste waters [26]. The catalytic effect of lead on
the complex formation between Mn(II) and
TPPS4 was applied in the determination of Pb(II)
in rain and drain water [27]. Acceleration of metal

M. Biesaga et al. / Talanta 51 (2000) 209224

ions, which can exist on two different oxidation


states, into porphyrins can also be achieved by
some reducing agents, such as ascorbic acid and
hydroxylamine [6,28]. The ionic radius of the
aquacomplex of Cu(I) is significantly larger than
that of similar ions of Cu(II), so the rapid formation of sitting-atop complex between Cu(I) and

213

porphyrin distorts the symmetry of the ligand


nucleus. In this conditions, Cu(II) ion can attack
the ligand from the lower side of the molecule.
Another problem concerning application of
porphyrins as spectrophotometric reagents for the
determination of metal ions is that the absorption
spectra of the reagent often overlaps with those of

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

CoTPP, CoTMOPP, CoOEP


CuTPP
FeTMHPP
CoTPPS4, CoTMPyP+bCD

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

Dopamine, neu- Graphite


rotransmitters
Dopamine
Glassy carbon

ZnProP
CoTRBP

DVP
DVP
Amperometry
CV

Amperometry,
CV

LOD 27.5 nmol l1

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

M. Biesaga et al. / Talanta 51 (2000) 209224

Fig. 2. Schematic diagram of interaction between NO, nitrites


and iron porphyrin [77].

Fig. 3. Scheme of electrocatalytic dioxygen sensing at the gold


electrode coated with b-CDP or b-CDPA film containing
cobalt porphyrin [65].

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-

M. Biesaga et al. / Talanta 51 (2000) 209224

um(tin) oxide glass slides has a linear response


from pH 8 to 12 [37]. It was found that the
inorganic matrix, such as silica glass, was superior
to the polymeric one as a surface oxygen sensing
material, especially under cryogenic aerodynamic
test conditions [40]. The optical oxygen sensor
based on the phosphorescence quenching of
PtOEP responded in the range of 0.5 100% O2
[41].
The optode for the detection of Hg(II) and
Cd(II) was prepared by covalent coupling of
monofunctionalised
porphyrin
derivative
ATPPS to the hydrophilic methacrylate matrix
[43]. It was shown that in the optochemical

215

sensors, complexation of metals by porphyrin


derivative with sulfonic acid residues was
fastest compared to porphyrins with amino- or
carboxy-groups. In addition, the sensor
response time was influenced by steric accessibility
to porphyrin molecules in the immobilisation matrix. For a measuring time of 10 min, the
detection limit of 20 mg l 1 for Hg(II) was reported [43]. The spectral differences of porphyrinHg and porphyrinCd complexes allow
simultaneous detection using appropriate procedures.
The application of metalloporphyrins as a coating material for quartz microbalance-based chem-

Table 5
Application of porphyrins in metal analysis by HPLCa
Analyte

Sample

Porphyrin

Column

Eluent

Ref.

Ni(II), Cu(II), Zn(II)

Bovine liver

TPP

Acetone/ACN

[103]

Cu(II), Pb(II), Zn(II), Cd(II)

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]

Cu(II), Zn(II), Mn(II), Co(II)

Tangerine skin, purple


rice
Aqueous sample

TCPP

Co(II), Cu(II), Mn(II)

Tap water

TCPP

Cu(II), Zn(II), Fe(II), Mn(II)

Peach leaves

TPPS4

Cu(II), Zn(II)

Peanuts

TPPS4

Mn(II), Zn(II), Cu(II)

Tea

TPPS4

Cu(II), Zn(II)

Peanuts

TPPS4

Hg(II), Cd(II), Zn(II)

Waste water, silicate,


corn samples
Tangerine skin, purple
rice

TPPS4

Y(III), Nd(III), Sm(III), Eu(III),


Gd(III), Tb(III), Dy(III),
Ho(III), Er(III), Tm(III),
Yb(III), Lu(III)
Cu(II), Zn(II)
Mn(II), Fe(III), Zn(II), Pd(II),
Cu(II)
Co(II), Zn(II), Cu(II)
Co(II), Zn(II), Cu(II)

Co(II), Zn(II), Cu(II)

T(4-MOP)PS4

Radial Pak C-18


Lichrosorb RP18
Lichrosorb RP18
Lichrosorb RP18
Lichrosorb RP18
Bondapak C 18
Lichrosorb RP18
Shimpack CLCODS
Shimpack CLCODS
Shimpack CLCODS
Silica gel cation
exchanger
Zorbax ODS

ACN/acetate buffer [107]


Lactic acid/ACN/
TBP
ACN/H2O/TBABr

[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

M. Biesaga et al. / Talanta 51 (2000) 209224

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].

Fig. 4. Schematic diagram of the interaction mechanism for


PAHs on ProP stationary phases [118]: (A) High selective
interaction on 2.9 mmol m 2 protoporphyrin coverage. (B)
Less selective interaction on low 0.6 mmol m 2 protoporphyrin coverage.

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.

3. Porphyrins in electroanalytical chemistry


The electroanalytical applications of porphyrins
can be found in various measurement techniques
such as potentiometry, voltammetry and electrochemical biosensors. Tables 3 and 4 contain literature data from 1991 to 1998.

Fig. 5. HPLC chromatogram of higher fullerens on ZnTPP


stationary phase with mobile phase carbon disulfite toluene
(45:55, v/v); injection 50 ml of toluene solution of a pyridine
extract of graphite soot; flow rate 2 ml min 1; detection UV
430 nm (0.15 AUFS); temperature 90C [117]. Peak identity 1,
C60; 2, C70; 3, C76; 4, C78; 5, C82 and C84; 6, C86; 7, C88, C90
and C92; 8, C94.

M. Biesaga et al. / Talanta 51 (2000) 209224

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].

Membranes doped with metalloporphyrins have


shown a potentiometric response to anions different from the classical Hofmeister selectivity series

(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.

Bekker et al. [51] have shown that the nature of


the ionophore anion interaction mechanism correlates with the charge of a metal ion chelated by
porphyrin. Divalent metal ion complexes with
porphyrin were found to serve as neutral carriers,
complexes with tetravalent ions as charged carriers, whereas metalloporphyrins with trivalent
ions as either neutral or charged ones depending
on the existence and number of bound axial ligands.

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

M. Biesaga et al. / Talanta 51 (2000) 209224

For preparation of ISE membranes, metalloporphyrins can be immobilised in PVC films


[5153,5961], electropolymerized on polysiloxane [55], carbon [56] or on Ag [57] electrode or on
Pt [58].
Yoon et al. [54] reported the use of the manganese(III) TPP, manganese(III) octaethylporphyrin, indium(III) TPP and indium (III) OEP as
ionophores in all-solid state chloride selective electrodes. Electrodes based on InOEP have been
used for determination of chloride in human
serum samples. The presence of salicylate does
not significantly influence these measurements.

Sun et al. [57] described the application of


electrode TPPS4 for the determination of iodide in
edible seaweed. The results obtained in potentiometric determination were in good agreement
with those obtained by spectrophotometric
methods.
Steinle et al. [53] described the anion selective
polymer membrane electrodes based on gallium(III), indium(III) or thallium(III) porphyrins.
The GaTPP and GaOEP electrodes have exhibited a significantly enhanced response toward
fluoride, whereas electrodes based on indium or
thallium porphyrin have shown some preferences
for chloride. Jain et al. [61] described the possibility of application ISE based on TPP as the indicator electrode in potentiometric titration of Co2 +
with EDTA.

3.2. Voltammetry

Fig. 7. Gradient separation of a mixture of bovine insulin (2


mg ml 1) and C-peptide (0.5 mg ml 1) with 5 cm CuTPP
column [123]. Peak assignment: 1, acetate; 2, C-peptide; 3,
insulin. Eluent A, 50 mM phosphate buffer, pH 7.0; B, 60%
ACN in A, gradient B from 10 to 70% in 60 min, flow rate 1
ml min 1, injection volume 100 ml, UV detection 210 nm.

The remarkable sensitivity of controlled potential voltammetric techniques is often hindered by


their low selectivity in biological media. The
chemical modification of electrode surfaces often
provides a means for enhancing the ability of
these techniques to handle samples of complex
matrices. The electrocatalytic action of such surfaces led to useful applications including for example, the detection of nitric oxide in biological
samples.
Electrodes coated with films of electroactive polymers including electropolymerized
porphyrin film, have received considerable attention in recent years. Several authors have
shown the use of these films as new electrode
materials for detection of anions and pH measurements.
Cobalt porphyrin modified electrodes were used
for rapid screening of toxic organohalides in
aqueous samples [62]. The electrochemical detection of these compounds was possible without the
need for deoxygenation.
Nickel TMHPP complex has been used as an
agent to modify the carbon fibre microelectrodes
[7173,8082]. Initial oxidation of monomeric
NiTMHPP leads to polymerisation and formation
of highly conductive polymer film on electrode
surface. Quantitative measurements of NO and its

M. Biesaga et al. / Talanta 51 (2000) 209224

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

in aqueous and aqueous organic solutions [65].


The sensor was made of a gold electrode coated
with a thin polymer film matrix of b-cyclodextrin
polymer hosting cobalt porphyrins. The proposed
reactions for such sensors are shown in Fig. 3.
A mercury electrode has been used for determination of DNA concentration, when TMAP or its
complex with Cu(II) or NiTMPyP is present in
the solution [8688]. The porphyrin interacting
with DNA produced an electrochemical non-active complex, which resulted in a decrease of the
peak current of porphyrin. The good correlation
between electrochemical and UV methods for all
natural and synthetic samples were presented.
Modified electrodes, suitable for use in flow
injection analysis, have been obtained by electrostatic assembly of films constituted by two different metalloporphyrins CoTRBP and ZnTPPS4 on
glassy carbon surfaces [78]. Such electrodes found
an application in FIA as amperometric detectors
for sulphite and nitrite determination in water
samples containing phenols.
Araki et al. [79] proposed the application of a
carbon electrode modified with CoTPyP as a suitable sensor for amperometric detection of nitrite
and sulphite.
Guerra et al. [67] constructed a sensor for hydrazine based on CuTPP mixed with carbon
paste. The response time was only 1 s in
chronoamperometry experiments, and the sensor
was used in a flow system. The limit of detection
for hydrazine was 10 7 M.
Modified electrodes with a molecular film of
tetraruthenated cobalt porphyrin complex have
been employed in the amperometric detection of
NADH and dopamine in flow analysis. The detection limit of these species has been obtained in the
mg l 1 range [90].
Ti(IV)TPyP reagent has been used in FIA determination of trace amounts of oxalate [91]. The
oxalate oxidase column was used and formed
H2O2, which reacted with Ti(IV)TPyP. This
method has been used for the determination the
oxalate concentration in various food such vegetables, beverages and fruits. A good correlation
was observed between the FIA and batch
methods.

220

M. Biesaga et al. / Talanta 51 (2000) 209224

3.3. Biosensors and biomimic systems


Biosensors based on coupling the high specificity of biocatalytic reactions with electrochemical
transducing of recognition event, continue to receive much attention. Research in recent years
has focused on the improvement of methods
for metabolites, novel electron-transfer relays,
new coatings and strategies for minimising
electroactive interferences, electrodes for in vivo
monitoring, microfabrication of disposable
electrodes, and miniaturised devices, and new
methods for enzyme immobilisation or stabilisation.
An amperometric needle-type glucose biosensor
employed non-platinum catalytic electrodes made
of pyrolyzed CoTMOPP [92]. A carbon electrode
modified by a Nafion film containing CoTMPyP
can be used to monitor oxygen in enzymatic
determination of glucose [93]. The electrocatalysis
of electrooxidation of thiocholine by CoTPP was
used for amperometric detection of acetylcholinesterase [94].
Porphyrins have also been used as mimic compounds for several biological applications. Some
of the ion exchange resins modified with metalloporphyrins have been found to exhibit glutathion
peroxidase
(GSHPx)-like
catalytic
activities for hydrogen peroxide and cumene hydroperoxide in the oxidative reaction of glutathion (GSH) to disulphide (GS-SG) [95]. In
particular, the anion exchange resins modified
with MnTPPS4 exhibit stronger activity, than
(GSHPx) and MnTPPS4, therefore they were expected to be a good mimetic compound instead of
GSHPx.

4. Application of porphyrins in HPLC


Porphyrins have also found numerous applications in HPLC as complexing agents for the determination of transition metals and as stationary
phases in immobilised metal ion chromatography
(IMAC).
Complexes of transition metal ions with porphyrins were separated using HPLC with spectrophotometric detection [102 107]. The role of

porphyrins in the determination of metal ions by


HPLC was recently reviewed [102]. The main
problem in the application of porphyrins as
chelating agents for chromatographic determination of metal ions is the slow rate of formation of
metal complexes. When porphyrin reacts
sufficiently quickly and quantitatively with metal
ion, then it can be useful as a sensitive spectrophotometric reagent. Although several articles
were published on the possibility of porphyrins
for the determination of metal ions, only a
few methods have found practical applications
(Table 5).
Complexes with meso-tetraphenylporphyrin
were used to determine Cu, Zn, and Ni in bovine
liver [103]. The chromatographic separation of
TPP complexes with Co, Ni, Cu, Zn based on
coordination interaction between the central
metal and modified silica gel stationary phases
was described by Suzuki et al. [106] in the normal
phase mode.
Complexes with (p-OH)TPP were used to determined Cu and Zn in tap water [104].
Complexes with m-BrTPPS4 were used for determination of Mn, Fe, Zn, Pd and Cu [105,107].
This method was successfully applied to the determination of the metals in peach leaves with detection limits from 30 to 160 pg and in water samples
with linear calibration over the range 4 10 8
10 6 M.
Lei et al. [108,109] described the application
of TPPS4 to the determination of Cu, Zn in
peanuts and Mn, Zn, Cu in tea. Yan et al. [110]
used TPPS4 as a post-column reagent for the
determination of Hg, Cd, Zn by ion chromatography.
The application of T(4-MOP)PS4 as a precolumn chelating reagent for the determination of
Co, Zn and Cu in tangerine skin and purple rice
was described by Xu et al. [111].
TCPP has been used as a complexing agent for
Co(II), Cu(II), Mn(II), and Zn(II) for their HPLC
determination after preconcentration by solvent
extraction with tributyl phosphate [112]. This
method has been applied for the determination of
cations in tap water samples with detection limits
from 0.2 to 0.6 mg l 1.

M. Biesaga et al. / Talanta 51 (2000) 209224

In recent years Meyerhoff and coworkers [113


118] have pioneered new stationary phases based
on porphyrins immobilized onto silica-gel through
a peptide bond, as useful phases in IMAC. They
employed TPP or ProP complexes with Fe(III),
Ni(II), Cu(II), Zn(II), In(III), Sn(IV) for this
purpose.
Meyerhoff and coworkers described the applications of porphyrin stationary phases for the
separation of aromatic carboxylates and
sulphonates, polycyclic aromatic hydrocarbons
(PAHs) [113 115] and fullerens [116,117]. Various
tetraphenylporphyrin and metalloprotoporphyrins
(MProP) were examined for the separation of
planar and non-planar PAHs [113,114,118]. Capacity factors for planar PAH solutes on these
supports were significantly greater than for nonplanar polyaryls having the same number of carbon atoms (Fig. 4). The advantage of immobilised
tetraphenylporphyrin on silicas for separation of
fullerens compared to several other stationary
phases was recently demonstrated [119] (Fig. 5).
In preliminary studies, it has been shown that
ZnTPP retained imidazoles and histidine via
strong cation solute interaction [113]. This has
implied the application of porphyrin stationary
phases for the separation of amino acids
[120,121]. Various metalloprotoporphyrins [121]
and metallotetraphenylporphyrins [122] covalently
linked to aminopropyl silica gel were investigated
for the separation of several amino acids with
phosphate buffer as eluent. The double mechanism of retention has been observed including the
coordinative interactions via metallic centre of
porphyrin and p p interactions between p electrons of macrocycles of porphyrin and p electrons
of solute. The comparison of the retention factors
obtained for different protoporphyrin and tetraphenylporphyrin are presented in Table 6. All
retention factors obtained for ProP stationary
phases are greater than for TPP phase. The retention factors obtained on ZnTPP are not correlated with stability constants values of their
complexes with Zn(II) [122].
In papers mentioned above, porphyrin stationary phases were also employed for the separation
of low molecular peptides [120,122]. Protoporphyrin IX yielding less hydrophobic phase than

221

TPP, when used in metalated stationary phase,


showed a cumulative binding affinity for small
peptides containing amino acids that individually
exhibit strong interactions with a given stationary
phase [120]. In preliminary studies on separation
of peptides with metalated TPP silicas, it was
shown for several peptides containing histidine
and one phenylalanine, that retention decreases
with increasing distance between these amino
acids in the peptide molecule [122].
The separation of several dipeptides and tripeptides of tyrosine and several insulins was investigated with unmetalated and metalated with Zn(II)
and Cu(II) TPP [123]. Greater retention factors
obtained on metalated column than on the unmetalated one confirm the coordinative interaction between metallic centre of porphyrin and
peptide (Fig. 6). It was found that the diversification of retention of tripeptides containing Tyr or
Phe was greater than for individual Tyr and Phe,
obtained on the same ZnTPP column with 1%
ACN addition to the phosphate eluent [121]. It
was indicated that the differences in the retention
of tripeptides also depend on the structural conformation of the molecule.
Bovine, ovine, swine and human insulins
present greater interaction for Zn(II) than for
Cu(II) TPP. They show good separation from
C-peptide (Fig. 7), but their separation from each
other is much more difficult to achieve.

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

M. Biesaga et al. / Talanta 51 (2000) 209224

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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