1537

Review

Chemical Reactivity of Polypyrrole and Its Relevance to

Polypyrrole Based Electrochemical Sensors
Krzysztof Maksymiuk*
Faculty of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
*e-mail: kmaks@chem.uw.edu.pl

Received: March 13, 2006

Accepted: June 1, 2006

Abstract
One of the most frequently used conducting polymers, polypyrrole, can take part in chemical processes with typical
components of ambient media: oxygen, acids, bases, redox reactants, water, and organic vapors; it can also incorporate
nonreactive ions and surfactants from solutions. The influence of such processes on changes of the polymer structure,
composition and on possible degradation is analyzed. The benefits and disadvantages of such processes for analytical
characteristic of polypyrrole based electrochemical sensors are considered. This discussion is focused on
potentiometric ion sensors, where polypyrrole is either a receptor membrane or an ion-to-electron transducer placed
between a solid state electrode support and a typical ion-selective membrane.

Keywords: Polypyrrole, Spontaneous side reactions, Degradation, Corrosion, Electrochemical sensors

DOI: 10.1002/elan.200603573

1. Introduction oxidized polymer under ambient environmental conditions.

The importance of electronically conducting conjugate
polymers (CP) since discovery of highly conducting doped
polyacetylene in 70-ties has been continuously growing.
These materials are interesting from the point of view of
both fundamental and applied research [1, 2]. Studies on
conducting polymers bring answers to some basic questions
of solid state/polymer physics and chemistry. Initially, the
leading compound in this group of polymers was polyacet-
ylene, regarded as a model CP. This has been attributed to its
relatively simple structure, significant for studies of funda-
mental properties as nature of charge carriers, doping
phenomena, relationship between doping and conductivity
etc. However, in the recent two decades, polymers with
heteroatoms: polypyrrole, polyaniline, polythiophenes with
its highly stable representative, poly(3,4-ethylenedioxythio-
phene), became more important. This results from their
stability in the presence of air and water, as well as relatively
simple synthesis by electropolymerization. Owing to com-
bination of unique electrical, optical, mechanical and
membrane properties these polymers are promising for
diverse applications including antistatic coatings, batteries,
supercapacitors, electrochromic devices, displays, LEDs,
corrosion protection etc. The important role of conducting
polymers in modern chemistry has been underlined by
Nobel Prize awarded to their discoverers in 2000.
In the above mentioned group of polymers with hetero-
atoms, one of the most frequently studied and used materials
is polypyrrole. This results both from facile and fast method
of electropolymerization, possible also in aqueous solutions
in a wide pH range, and relatively high stability of the
Recently, this polymer is also available commercially.
Therefore, compared to other polymers, polypyrrole
chemistry is a quite mature subject, properties of this
polymer are relatively well known. However, using the
advantages of conducting polymers requires taking into
account also possible side reactions of the material. These
reactions for polypyrrole are often underestimated, al-
though they involve common environmental components:
air, solvent and dissolved species, facilitating the polymer
decomposition. However, owing to common availability of
such substances, one should be aware of chemical reactivity
of polypyrrole. This reactivity can manifest itself in different
manner, affecting polymer properties, e.g., in gradual
change of conductivity, UV-vis or IR spectra, chemical
composition, mechanical stability, the shape of voltammet-
ric curves, open circuit potentials etc.
Usually, these processes exert a disadvantageous influ-
ence on stability and operation of devices using conducting
polymers as, e.g., plastic electronic devices or batteries,
where losses of accumulated charge occur [3].
An important and particularly promising area of poly-
pyrrole applications are electrochemical sensors: potentio-
metric, voltammetric/amperometric and those using resist-
ance changes measurements. Polypyrrole suitability is based
on using changes of electronic/ionic conductivity, dependent
on the polymer composition and oxidation state, capability
of being reversibly oxidized or reduced as well as membrane
properties. For such kind of devices the role of side chemical
reactions can be crucial, since processes, resulting even in
undistinguishable composition changes, can dramatically
affect the sensor responses, magnitude of the signal, stability

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1538
and selectivity. Generally, these processes can be either
origin of the analytical signal or can interfere with the signal
of analyte of interest. Therefore, depending on the direction
and rate of spontaneously occurring processes and involved
reactant, they can be either beneficial or deteriorating for
the sensor behavior. On the other hand, irreversible
processes resulting in polymer degradation limit long term
stability of sensing devices.
The subject of this review is description and critical
comparison of chemical reactivity of polypyrrole, the
possible processes are classified taking into consideration
the reactant kind. The chosen reactants are common
components of media, where the polymer is usually applied.
Then the role of polypyrrole reactions for different classes of
electrochemical sensors will be discussed.
2. Classification of Polypyrrole Reactions and
Polypyrrole Based Electrochemical Sensors
Freshly prepared polypyrrole can undergo different pro-
cesses involving medium components. Since this article
concerns only chemical processes involving polypyrrole,
other phenomena related to changes of structure and
physical properties accompanying relaxation and aging, as
well as results of thermal treatment, are beyond the scope of
this review.
The chemical processes involving polypyrrole can be
ascribed to some groups, which will be then described in
detail (Fig. 1). Since conducting polymers are redox active,
these processes can be (i) oxidation/reduction by some
components present in the surrounding medium, mainly
oxidation by oxygen or other species as, e.g., metal ions.
Another group of processes consists in (ii) interaction with
solution components as nucleophilic agents (e.g., OH
ions,
water molecules) leading to polymer degradation. The next
group of reactions is related to (iii) acid/base properties,
involving protonation/deprotonation of the polymer chains,
especially important for polyaniline and its derivatives, but
significant also for polypyrrole. Additional possibility,
important from the point of view of selective sensors
development, is (iv) complexation of metal ions from the
medium by groups/ligands present in the polymer phase.
The last group of interactions can be (v) incorporation of
medium components into the polymer phase owing to ion
exchange or (vi) adsorption (absorption). The ion exchange
case corresponds to spontaneous replacement of doping
ions by ions from the solution, while adsorption relates to
incorporation of surfactant molecules/ions accumulated on
the polymer surface. Under some circumstances the above
processes cannot be regarded separately as in the case when
surfactant anions replace spontaneously the doping species.
Any of the processes (i – vi) can be interconnected, e.g.,
oxidation can be coupled with deprotonation, reduction
with protonation of the polymer film, protonation can be
also regarded as a kind of doping. An additional feature,
which joins the above mentioned phenomena is that they
can be either reversible or irreversible, the latter being
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K. Maksymiuk
Fig. 1. Open circuit reactions of polypyrrole.
usually undesirable from the practical point of view; e.g.,
reversible oxidation is useful in charge accumulation
devices, while irreversible oxidation results in polymer
degradation. On the other hand, reversible incorporation of
surface active molecules can be utilized in surfactant
sensors, while irreversible incorporation results in disap-
pearance of sensor sensitivity and loss of electroactivity of
the polymer.
Owing to diversity of possible interactions, mentioned
above, polypyrrole can be used for construction of sensors.
An important group are electrochemical sensors, which can
be divided into several subgroups, depending on the
measurement mode (Table 1). Since these applications
were subject of some reviews published in recent years
[4 – 19], a detailed characteristic of these sensors is outside
the scope of the present paper. The present review is focused
on selected main factors affecting the sensors properties,
strictly related to polypyrrole reactivity and discussed from
the point of view of reactant kind. Comparing possible
reactions of polypyrrole and kinds of electrochemical
sensors, given in Table 1, two cases can be distinguished:
(a) reactions involving species being detected by the
electrochemical sensor, (b) reactions of other species, not
directly involved in the sensing process. In the case (i)
chemical reactivity of polypyrrole can be beneficial; how-
ever, in case (ii) it usually exerts disadvantageous influence
on sensor characteristics. Significance of these two cases will
be described below for various reaction types.
3. Interactions with Oxygen
Compared to other conducting polymers, pristine neutral
polypyrrole can be easily oxidized, owing to its rather low
redox potential. The most common oxidizing agent, en-
countered in typical applications of polypyrrole, is oxygen.
Although oxidized polypyrrole is relatively stable, the
neutral polymer is readily oxidized by oxygen present either
in air or in aqueous solution [20 – 26]. The mechanism of
interactions with oxygen is quite complicated, depending on
time, oxygen pressure and water presence. In such a case
polypyrrole properties change, confirming transition from
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemical Reactivity of Polypyrrole
Table 1. Classification of polypyrrole based electrochemical sensors.
Kind of sensors
Potentiometric sensors of ions and neutral molecules
Amperometric/voltammetric sensors of electroinactive ions
Voltammetric (stripping) sensors of heavy metal ions
Biosensors
Conductometric sensors (of , e.g., ambient gases and organic vapors)
Redox switching sensors of solute species
the state typical for neutral polymer to that of doped
polypyrrole, accompanied by doping and weight uptake
[22]. Some evidences point to multistep process; for
instance, the conductivity of pristine neutral polypyrrole
rapidly increases in the early stages of oxidation, while
optical changes are observed later [22]. Open circuit
potential increase for neutral polypyrrole in aqueous
solutions is also observed, pointing to polymer oxidation
[24, 27], Figure 2. Changes in UV-vis, IR [25, 28 – 31] and
ESR spectra [22, 32 – 34] have been also recorded. In the
UV-vis spectrum of neutral polypyrrole, after short contact
with aqueous solution containing oxygen, absorption at
560 nm (related to polarons) and at 800 nm (related to
bipolarons) increases, whereas absorption at 420 nm (p – p*
transition), typical for neutral polymer, decreases [28].
Moreover, for longer times, absorption at 560 nm starts to
decrease, indicating a decreasing contents of polarons, and
that at 800 nm increases as a result of bipolaron presence.
The oxidation process of polypyrrole can be also followed
using IR spectroscopy. In the presence of oxygen the
spectrum typical for neutral polymer gradually transforms
to that characteristic of oxidized polypyrrole, additionally
bipolaron bands appear in the range of 1000 cm
1 [25, 30].
Combination of different techniques gives opportunity to
elucidate the mechanism of oxygen – polypyrrole interac-
tions. ESR spectroscopy has enabled visualization of polar-
on creation and their decay upon transformation to
bipolarons, as shown by the signal increase and decrease,
Fig. 2. Changes of the open circuit potential (line) [27] and UV-
vis absorption peak at 420 nm [28] (points) of neutral polypyrrole
in the presence of oxygen.
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1539
Literature (reviews)
[4, 5, 6, 8, 9, 10, 11, 12, 15, 16, 17, 18]
[6]
[4, 6]
[4, 6, 7, 9, 15, 16]
[13, 14, 15]
[4, 15, 19]
respectively. On the basis of ESR results it has been also
postulated that the first step of polypyrrole – oxygen inter-
action is oxygen reversible adsorption both on the polymer
surface and inside the film [35]. Accordingly, broadening of
the ESR signal with time and rising oxygen pressure in air is
observed. After reaching the maximal value, the ESR signal
width gradually decreases as a result of oxygen replacement
by other molecules, e.g., water if available. Basing on FT-IR
and XPS results, Lei and Martin [25] have postulated
existence of two forms of oxygen interacting with pristine
PPy. The first oxygen form are O
2 anions (present only in
anhydrous media) as a result of charge transfer between the
polymer and oxygen molecule. The O
2 anions play a role of
the dopant [25]:
xO2 þ
(Py)n
!
[Pyn-x
(PyþO
2 Þx]
(1)
where Py represents the neutral (unoxidized) pyrrole unit in
the polymer chain, Pyþ is the oxidized unit.
However, the obtained doping level is lower than for a
fully doped polymer as the conductivity is ca. 2 orders of
magnitude lower than for a typical doped polymer. The low
doping degree is also confirmed by significantly lower
absorbance in the free-carrier region. The second form of
oxygen, being in major excess compared to O
2 , are
molecular association complexes between O2 and polypyr-
role. In a relatively short time scale (30 minutes), exposure
of polypyrrole to oxygen does not result in formation of
carbonyl or hydroxyl groups in the polymer, which are
characteristic for irreversible degradation of the material.
However, after longer exposure (hours) the superoxide
anions participate in irreversible process of deprotonation
of the pyrrole nitrogen atom, yielding an imine derivative of
polypyrrole [22, 25]. On the other hand, the ring oxidation
can result in appearance of C
O and C¼O groups [36].
A prolonged exposition to oxygen can lead also to N
O
and peroxide species formation [37, 38]. The stability
enhancement for polypyrrole in the presence of oxygen can
be obtained by introduction of copper (which was retained in
the film after Cu deposition and following oxidation) or
polyethylene oxide [39, 40]. Their presence is attributed to
electron transfer from Cu to Nþ centre or a more compact
structure and hydrogen bonds forming, respectively. Addi-
tion of Al2O3 nanocomposites to the polymer also results in
increased stability towards oxygen, as XPS and SERS results
have shown [41]. This improvement is related to the increase
of polymer oxidation state in the presence of Al2O3.
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1540 K. Maksymiuk

Polypyrrole interactions with oxygen can result in for-

mation of oxygen – polypyrrole charge transfer complexes
with diverse stoichiometry, as discussed by Kankare and
Vinokurov [26]. These processes result in linear dependence
of the open circuit potential on oxygen concentration higher
than 10
5 M, useful for applications in potentiometric
oxygen sensors.
However, taking into account influence of polypyrrole
oxidation for general sensing purposes, another conclusion
needs to be added. Owing to common presence of oxygen in
real samples, its interactions with polypyrrole can be even
more important for polypyrrole based sensors used for
analysis of other substances. Moreover, interactions with
oxygen can result also in the polymer degradation. These
issues will be discussed later in this review.
Polypyrrole can be also oxidized by ozone, O3, resulting in
the polymer degradation [42]. This process is rather slow, but
can be accelerated in the presence of surfactants-dopants.
Probably surfactants favor the solubilization and transport
of the reactant in the polymer. In this case FT-IR spectra
reveal a strong band related to C¼O group [42].

4. Interactions with Other Redox Reactants

Polypyrrole can be either chemically reduced or oxidized in

the presence of other redox reactants. These reactants can
be accumulated in the polymer phase, e.g., redox active
dopants as I
[43] or hexacyanoferrate ions [44, 45]. An
important example of redox reactant is hydrogen peroxide
[46], playing a dominant role in glucose biosensors. In
polypyrrole based glucose sensors, oxidation of the analyte
is accompanied by oxygen reduction to hydrogen peroxide,
being then detected amperometrically on platinum elec-
trode. Hydrogen peroxide in concentration higher than
0.1 mM can irreversibly oxidize polypyrrole [47, 48], result-
ing in loss of its electroactivity. Therefore, the polymer
degradation strongly limits long term stability of biosensors
involving H2O2 [47 – 49]. Some strong oxidants, as MnO
4 ,
can also seriously deteriorate polypyrrole [50].
Matsue et al. have used polypyrrole in microarray elec-
trode redox switching devices for detection of solution
redox species ([51] and a review [19]). This method utilizes
conductivity changes accompanying oxidation (conductiv-
ity increase) or reduction (conductivity decrease). Addition
of an oxidizing agent (Fe(CN) 3
6 , anthraquinone-2-sulfonic
acid) or a reducing one (S2O 2

4 Þ results in fast and reversible
increase or decrease, respectively, in drain current flowing
between two polypyrrole electrodes (Fig. 3) [51]. A similar
concept has been used for a biosensor arrangement, where
the enzyme diaphorase reduces the CP to an insulating form
(composite of polypyrrole and poly(N-methylpyrrole) upon
addition of NADH [52]).
A series of papers is related to polypyrrole interactions
with gases, focusing on applications in gaseous samples
analysis and volatile organic compounds detection, e.g.,
ammonia, nitric oxide, methanol, hydrazine, hydrogen
sulfide (e.g., see references in [13]). Gas – polypyrrole
Fig. 3. A) Configuration of electrochemical system for in situ
conductivity measurements. BPS: bipotentiostat, CE: Pt counter
electrode, RE: reference electrode, VG: gate voltage, VD and ID:
drain voltage and current, Sw: switch. B) Switching responses of
microarray electrode coated with polypyrrole. Concentrations of
redox reactants: 10 mM, VD ¼ 20 mV, flow rate ¼ 2.0 mL/min, A:
rinsing with buffer solution. Reprinted from [51] with permission
from Elsevier.
interactions are also accompanied by conductivity changes
what can be easily measured. The sensing mechanism can be
explained by change of concentration of the charge carriers
in the polymer resulting from partial charge transfer [53].
Electron donating gases, e.g., NH3 [15, 54] cause conductiv-
ity decrease, in contrast to electron accepting ones, as, e.g.,
PCl3, SO2, NO2 [15, 55, 56]. This effect is dependent on
electronegativity magnitude of the gas/vapor and work
function of the polymer [53]. The influence of H2S [13, 54] is
exceptional. Although it exerts a reductive effect on
polypyrrole, as shown by UV-vis and FTIR spectra, the
polymer conductivity increases [13]. This unexpected in-
crease was explained by partial dissociation of H2S with
release of protons, enhancing ionic conductivity of the
polymer. Interactions of polypyrrole with gases or vapors,
resulting in partial charge transfer between the polymer and
guest molecule can be also utilized in potentiometric gas/
vapor sensors [18, 57].
Interaction of noble metals: Au [58], Pd [59 – 61], Pt [62]
and Ag [63 – 65] can occur after contact of metal ion
solutions with neutral or semi-oxidized polypyrrole. Metal
ions reduction is coupled with oxidation of the polymer.

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Chemical Reactivity of Polypyrrole
Electroless metal deposition can be used, e.g., to metalliza-
tion of conducting polymer patterns [61].
Metal deposition efficiency is additionally affected by
complexation reaction between metal ions and NH groups
of pyrrole rings [58, 64, 66 – 68]. Metal uptake (e.g., silver)
can be easily detected by microscopic observation, spectro-
scopic and electrochemical methods (in the latter case by
presence of voltammetric peak of deposited metal oxida-
tion).
Pickup et al. [63] have used electroless silver deposition to
accumulate the metal in the polymer phase. The deposited
metal was then oxidized using differential pulse stripping
mode to give improved detection limit (close to 5 ppb).
Applicability of this method to real sample analysis, e.g.,
jewelry processing wastes, has been shown [63].
Some authors were interested in kinetics of such sponta-
neous redox reactions. Generally, potential changes accom-
panying charge transfer reactions of solution redox species
at electrodes coated by polypyrrole films are slower
compared to those at classical metal electrodes [69]. Two
main mechanisms of redox reaction with the polymer can be
specified [69], Figure 4. Mechanism 1 relates to chemical
reaction between the polymer (oxidized: Polyþ or reduced:
Poly) and the reactant (Ox or Red), as:
Poly þ Ox ! Polyþ þ Red
or
Polyþ þ Red ! Poly þ Ox
Since the oxidation state of the polymer and, simultane-
ously, the amount of positively charged polarons/bipolarons
changes, electroneutrality condition requires incorporation
or release of mobile dopant ions.
However, if ion-exchange process is hindered, as e.g., for
polypyrrole doped by dodecylsulfate ions, the mechanism 2
Fig. 4. Schematic representation of polypyrrole oxidation (A)
and protonation (B) process, accompanied by polymer chemical
transformation with doping anions incorporation (a) or polymer
film polarization (b).
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1541
prevails. In this mechanism, polarization of the polymer,
similarly as for metals, is postulated [69]. These mechanisms
can be distinguished by the shape of potential vs. time
dependences, some evidences can be also given by results of
elemental analysis of the film, concerning dopant contents
in the film. For the mechanism 1 the electrode potential
slowly approaches the redox potential of the reactant/redox
couple and the amount of doping ions changes in time. This
slow change is related to a high redox capacitance of the
polymer. The process rate is dependent on transport
phenomena in solution and polymer film thickness. In the
case of mechanism 2 the potential instantaneously stabilizes
at a new value, as for typical metal electrodes, owing to low
capacitance of the polymer, as a result of inhibited ion
exchange. Moreover, the doping ions contents does not
change.
Open circuit redox transformation of polypyrrole can be
utilized in potentiometry. Potentiometric electrodes with
polypyrrole layers were proposed to be applied in con-
struction of potentiometric redox electrodes used for
titrations [70, 71] as well as “dual” electrodes [71] sensitive
to both redox species and electrolyte ions (resulting from
ion-exchanging properties of the polymer).
(2) 5. Influence of Solution Acidity/Basicity
Properties of polypyrrole are strongly affected by solution
acidity, this polymer can be either protonated or deproton-
(3) ated [72 – 78].
5.1. Deprotonation
As found by Inganäs et al. [79], in highly alkaline media,
deprotonation of oxidized polypyrrole readily occurs.
resulting in significant decrease in conductivity (up 3 – 4
orders of magnitude). A scheme of this reaction is presented
in Figure 5A [80]. This effect results in conjugation breaking
and release of doping anions, confirmed by different
techniques: XPS [36, 79], quartz crystal microbalance [77],
IR spectroscopy [75, 81, 82], and elemental analysis studies
[73, 83]. It results also in changes in typical electrochemical
characteristic, as e.g., electrochemical impedance spectros-
copy results show [84]. Deprotonation in alkaline solutions
can occur because pKa value of doped polypyrrole is near 10
[73].
The above mentioned processes are reversible, the initial
state can be regained after contact with acidic solution.
Deprotonation process in alkaline solutions results also in
UV-vis spectrum changes, e.g., red-shift of the band at
420 nm to 390 nm was observed, typical for bandgap
transition [73]. As the spectrum of deprotonated polypyr-
role differs from those recorded either for doped or neutral
polypyrrole, changes in the electronic structure are prob-
able, resulting in the quinoid form presence [73]. This has
been confirmed by 13C NMR investigations [80]. Incorpo-
ration of OH
ions in the film is also possible [80, 85 – 88],
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1542
Fig. 5. A) Deprotonation of polypyrrole in alkaline solutions.
(B) Transformation of polypyrrole in the presence of OH
or Hþ
ions. Reprinted from [80] with permission from Elsevier.
Figure 5B [80]. However, after conditioning in strongly
alkaline solution, the quinoid form disappears, pointing to
OH
attack on the pyrrole ring [80, 89]. The effect of
structural changes observed in alkaline solutions, shown,
e.g., by conductivity decrease, is also reversible. After
conditioning in acidic solution the initial value of conduc-
tivity can be regained [90]. However, the studies of Neoh
et al. [91] and Xie et al. [92], using different spectroscopic
techniques, have revealed that after prolonged contact with
alkaline solutions pyrrole ring opening and oxidation can
occur, resulting in C
O and C¼O bonds formation. The
latter process is irreversible, after contact with acidic
solution (reprotonation) the initial conductivity cannot be
Fig. 6. Protonated structures of polypyrrole. Reprinted from [73] with permission from Elsevier.
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K. Maksymiuk
regained. Basing on FT-IR studies, a pseudo-first-order rate
law of hydroxide ion attack on polypyrrole molecule has
been found [92].
The process of spontaneous deprotonation is attributed
rather to oxidized polypyrrole only, due to presence of
positive charge facilitating release of positively charged Hþ
ions [73, 75]. For neutral polypyrrole the rate of this process
is much lower.
After polymerization, if occurring in aqueous solution,
deprotonation process and release of doping anions can be
coupled with partial dehydration [93]. Additionally, con-
ductivity increase can be observed, owing to more favorable
charge distribution along the chains and formation of
chain – chain interactions. As proposed by Krivan et al.
[81, 93] relaxation of polypyrrole doped by dodecylsulfate,
DS
, ions can occur, according to formula:
PPyþDS
þ (HPPy)2þ2DS
! PPy 2þ
þ
2 2DS þ H (aq)


þ DS (aq) (4)
This equation points both to increased conjugation length
(PPy 2þ
2 Þ and deprotonation from the protonated units
(HPPy)2þ, accompanied by release of doping DS
anions.
Proton release can result in change of the electronic
structure of the polymer and its conformation. These
processes are quite slow because they occur in a solid state.
Removal of protons, anions and solvent results in stacking of
the polymer chains as well as increase of density and
anisotropy.
5.2. Protonation
For pH lower than 3, for doped polypyrrole process of
protonation occurs (pKa of protonated polypyrrole is near to
3, [73]) accompanied by intercalation of doping anions [73].
No significant changes in the electronic structure are
recorded, this process is accompanied only by small
conductivity increase and small batochromic effects in the
vis spectrum. Therefore, the structure I (Fig. 6) is more
probable, where additional protons are not incorporated
into the double bond conjugation [73].
However, the protonation process can be more advanced
for neutral polypyrrole, as demonstrated by more pro-
nounced conductivity increase, and increase of content of
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemical Reactivity of Polypyrrole
doping (chloride) ions, observed even in the absence of
oxygen [76]. This process is called “protonic doping”,
analogous to phenomena well known for polyaniline (e.g.,
[94]). In the presence of oxygen, the amount of incorporated
dopant is higher due to parallel occurrence of oxidation of
the polymer. For doped polypyrrole, electrostatic repulsion
between positive charge of the polymer chain and hydrogen
ions makes this process more difficult to occur.
Protonation of polypyrrole occurs also during polymeri-
zation in unbuffered media [73, 95, 96]. Then, in alkaline or
neutral solutions the excess hydrogen ions can be sponta-
neously removed, owing to pH higher than pKa of proton-
ated polypyrrole [73]. Just after electrochemical polymeri-
zation of pyrrole a relaxation process can occur accompa-
nied by changes of composition and structure of the polymer
[1, 2]. It is also accompanied by 10 % mass decrease.
5.3. Influence of Acidity on Open Circuit Potentials and
Conductivity
Protonation/deprotonation processes affect also the open
circuit potential of an electrode coated by polypyrrole [72,
74]. Immersion of such electrode in more alkaline solution
results in potential decrease, while after immersion in acidic
solution a potential increase is recorded. Potential changes
are relatively slow and the rate of potential change
decreases with rising film thickness. This effect shows that
protonation/deprotonation processes take part in the whole
volume of the polymer and are the rate determining
processes. They occur in the presence of anions which can
be easily exchanged with the polypyrrole layer to compen-
sate the charge changes [84, 97, 98]. From the potential vs.
time dependences the first order rate law for deprotonation
reaction has been found [99].
Protonation can occur according to mechanisms 1 and 2,
typical for redox reactions [98], Figure 4. In the case of
hindered ion exchange only polarization of the layer occurs.
After immersion in acidic solution the open circuit potential
increase is instantaneous [98]. On the other hand, for facile
ion exchange, protonation can occur in the polymer bulk.
This process, accompanied by counter-ion flow, results in
slow potential increase after contact with acidic solution.
The pH influence on open circuit potential can also result
from the influence of redox reactants, for which the redox
potential is pH dependent [97].
Analytical applications of polypyrrole protonation/de-
protonation are obviously related to pH sensors or biosen-
sors (e.g., [100]), where the enzymatic reaction is coupled
with pH changes. However owing to common presence of
Hþ/OH
ions, the above discussed processes can be of more
general significance, affecting also properties of other
polypyrrole based sensors, where the reaction with Hþ/
OH
ions is not of interest. This problem will be discussed
later in the present review. The above described influence of
solution acidity on the open circuit potential dependence on
pH is potentially applicable for solid state pH sensors. The
slope of the dependence recorded for thin films (below
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1543
2 mm) reaches sub-Nernstian values (close to 50 mV/dec),
within the pH range from 2 to 12 (0.1 M phosphate buffers),
as a result of relatively fast protonation process occurring on
the surface [101]. However, for thicker films diffusion of ions
into the film can limit the response time and additionally
anionic response of the polymer can lower the slope.
As mentioned above, the influence of pH on polypyrrole
conductivity can be also utilized for sensor purposes [90,
102]. Nishizawa et al. [102] proposed a penicillin biosensor
using an arrangement similar to that presented in Figure 3.
The polypyrrole layer was coated by a membrane containing
enzyme: penicillinase. The enzyme catalyses hydrolysis of
penicillin, resulting in pH decrease. Consequently, conduc-
tivity of polypyrrole increases, resulting in higher ID current
(Fig. 3). Applications of polypyrrole in other pH-based
potentiometric biosensors is described in review [6].
6. Interactions with Ammonia
A common alkaline agent which can react with polypyrrole
film is ammonia, both gaseous phase and in aqueous
solution. Its influence differs from a typical effect observed
in the presence of OH
ions, thus, it will be described
separately. As discovered by Kanazawa et al. [103] ammo-
nia causes a conductivity decrease of oxidized (doped)
polypyrrole. This result has been confirmed by numerous
authors as Miasik et al. [54], Gustafsson et al. [104, 105] etc.
[106 – 108]. XPS analysis has revealed expulsion of dopant
chloride ions upon contact with ammonia [109]. The
influence of increasing ammonia contents has been claimed
to be reversible, as shown, e.g., by repetitive treating of the
polypyrrole film with gaseous ammonia (conductivity
decrease) and gaseous HCl or CO2 (conductivity increase)
[110]. Pei and Inganäs [111] pointed also to effect of
reversible bending of a polypyrrole strip exposed to NH3.
According to Gustafsson et al. [105] polypyrrole – NH3
interactions can be represented by simple acid – base
equilibrium:
PPyHþCl
þ NH3 > PPy þ NH4þ þ Cl
(5)
or electron transfer:
PPyþA
þ NH3 > PPy0
NH þ3 , A
(6)
However, either for dry or wet NH3 of pressures higher than
1 atm or for prolonged exposition time, the NH3 influence
seems irreversible [105]. This has been initially explained by
the nucleophilic attack of either NH3 molecules or OH
ions
on the polymer chain, resulting in conjugate chain disrup-
tion or even pyrrole ring opening [104, 105]. Basing on
results of spectroscopic studies (UV, IR) Trojanowicz et al.
[109] have postulated that the reversible polymer deproto-
nation is accompanied by some irreversible processes. The
conjugation length lowering and creation of carbonyl and
amine groups in the polymer have been reported; however,
the products of these irreversible reactions have been not
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1544
identified. On the other hand, Heiduschka et al. [112] have
demonstrated that the polymer properties can be recovered
after prolonged (60 h) conditioning in acidic solution or a
joint treatment: short conditioning in acidic solution and
then oxidative polarization at a constant potential. Raman
spectroscopy experiments, as well as results obtained for
poly(N-methylpyrrole) have not confirmed the Gustafsson
reaction (Eq. 5). Moreover, for high concentration of
ammonia and long exposition times no significant changes
in polymer structure have been found (except for N
H band
intensity decrease) [113]. Using on-line differential electro-
chemical mass spectroscopy technique, Córdoba de Torresi
with coworkers [114] have identified NO as the only product
of NH3 oxidation at polypyrrole electrodes.
Interactions of polypyrrole with ammonia have been
utilized in piezoelectric gas sensors [108] as well as
amperometric sensors and biosensors [109, 113, 115 – 119],
where NH3 is in situ generated as a product of enzymatic
reaction. In this case, NH3 can be oxidized by the polymer
and the polymer reoxidized due to applied potential,
resulting in analytical signal generation. Trojanowicz et al.
[109] and Lahdesmaki et al. [117] have reported extension
of the linear range down to micromolar level. For NH3
concentrations higher than 1 mM they reported irreversible
effects on the polypyrrole electrode response [117]. The
main interference was concomitant effect of doping by small
anions as chloride or nitrate ions giving also amperometric
response at the millimolar level. This interfering influence
has been reduced by using dodecylsulfate ions, which inhibit
ion exchange [117]. The sensitivity of Langmuir – Blodgett
polypyrrole layer has been found higher (in the range 0.01 –
1%) than for polypyrrole obtained by electropolymeriza-
tion [120].
7. Irreversible Degradation (Corrosion) Under
Ambient Conditions
A prolonged exposure of polypyrrole films to, e.g., water,
and particularly alkaline media, results in irreversible
transformation of the polymer. A degradation (corrosion)
process can be observed as, e.g., conductivity decrease, mass
increase (which can be detected using quartz crystal micro-
balance technique) or decreased electroactivity of the film,
demonstrated by lowering of voltammetric current. Long
term conductivity decrease related to polypyrrole degrada-
tion under influence of air has been also reported [121 –
124]. Corrosion of polypyrrole in solutions was studied by
Beck et al. [125 – 127]. These authors have found two time
ranges of the reaction and thus proposed two mechanisms of
the corrosion process: electrochemical and chemical. The
process dominating for shorter times is electrochemical
corrosion. It is related to polymer reduction, accompanied
by release of doping anions. This reduction reaction is
coupled with overoxidation, usually occurring at potentials
higher than 0.6 V vs. SCE. However, in the alkaline
solutions the onset of irreversible oxidation can be shifted
to lower potentials, also corresponding to the open circuit
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K. Maksymiuk
potential of the polymer in these media. Overoxidation
resulting in quinoid structure formation has been postu-
lated, both hydroxyl- and carbonyl-substituents have been
detected using IR spectroscopy [128 – 130] and XPS analysis
[131, 132]. Overoxidation has been also confirmed by
electrochemical impedance spectroscopy. This method
points to charge transfer resistance increase and low values
of diffusion coefficients in the overoxidized film [133].
The above mentioned polymer reduction process cannot
be completely balanced by oxidation of water to oxygen,
owing to its high oxidation potential. A contribution from
this process can be expected only in alkaline solutions [127].
The kinetics of the electrochemical corrosion process has
been analyzed by recording voltammetric curves after given
time period. A gradual decrease of the polypyrrole anodic
peak current was observed, resulting in lowering oxidation
charge obtained by integration of the voltammetric curve.
From the charge change vs. time plots, the corrosion kinetics
could be evaluated. Exponential rate law has been found
with half-time, which significantly lowers with increasing
solution pH (from 102 to 105 s within pH range from 13 to 1
[126, 127, 134]).
For longer times, chemical corrosion step affects the
polymer properties. In this process interaction of positively
charged centers of polypyrrole (polarons and bipolarons)
with nucleophile agents as water, OH
ions or other anions
with lone electron pairs can occur. The rate of corrosion
process is significantly high in aqueous media. It is much
lower in some organic solvents, e.g., in acetonitrile or
methanol, resulting from weaker nucleophile properties of
organic solvent molecules. If the nucleophile agent is water,
hydroxylation of pyrrole ring in the b-position is possible.
The half-time of the chemical corrosion occurring in
aqueous solutions is also pH dependent (from 103 to 106 s
within the pH range from 13 to 1) [126, 127].
The stability of the polymer is dependent on polymeri-
zation conditions; e.g., longer polymerization time, lower
potential, lower temperature, higher concentration of both
the monomer and supporting electrolyte and bulky organic
dopants are recommended to obtain polymer of higher
stability and conductivity [37, 41, 135 – 141] pointing to
rather complex mechanism of polymer aging. Highly doped
films were found to be more stable in air [140, 142], the FTIR
spectra revealed presence of carbonyl peaks, correlated with
loss of conductivity [140]. The degradation of polypyrrole in
air or water vapor was studied in 80-ties; however the
mechanism was not quite clear.
The aging of polypyrrole results in conductivity, s,
decrease with time, t. Chen et al. [143] have proposed the
equation, related to first order kinetics:
log s ¼ log s0
kt (7)
where s0 is the initial conductivity and k is constant:
k ¼ B
E/RT (8)
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemical Reactivity of Polypyrrole
with a B constant and activation energy, E. Other authors
have pointed to a dependence on t1/2, suggesting diffusion
(of, e.g., oxygen) as the rate limiting step [142, 144]. Even
more complicated forms of conductivity vs. time depend-
ences, additionally changing in different time ranges have
been proposed [124, 136, 140, 142]. The conductivity
decrease in time is faster for the polymer doped by small
inorganic anions than for polypyrrole doped by bulky
organic ions, e.g., dodecylsulfate, dodecylbenzenesulfonate,
poly(p-styrenesulfonate), 2-naphthylsulfonate, 2,6-naph-
thalenesulfonate [145] or p-toluenesulfonate ions
[123,137,145]. The slower conductivity decrease observed
for organic ions has been ascribed to water (and reactants
soluble in water) repelling properties of hydrophobic
organic ions. For p-toluenesulfate a slight initial conductiv-
ity increase has been ascribed to decrease in the solvent
contents of the film [137]. Conductivity decrease in time is
also faster for chemically synthesized polypyrrole, com-
pared to electrochemically obtained polymer [143]. This can
result from higher surface area of the former material.
Recent studies point to responsibility of surface related
phenomena for the observed aging and particularly the
conductivity decrease. FT-IR studies using the isotopic
effect of deuterium have revealed a two dimensional
structure of polypyrrole suggesting that the hydrolysis
process occurs rather on the surface [146].
Atomic force microscopy with current-sensing mode has
brought additional information on polypyrrole aging [147].
These studies have proven that the degradation process
caused by oxygen and water vapor present in the ambient
atmosphere, and leading to the conductivity decrease,
occurs mainly on the surface. It results in formation of a
thin insulating layer. The degradation products have been
shown to contain C¼O groups which can be eventually
transformed to fumaric acid [147].
It has been found that modification of polypyrrole by
copper enhances its stability [39, 40, 139]. The aging of the
polymer in humid atmosphere has been ascribed to nucle-
ophilic attack of water on positively charged nitrogen atom.
In the presence of copper the aging rate is lower due to
electron transfer from Cu atom to positively charged N atom
[139].
8. Spontaneous Ion Exchange, Potentiometric Ion
Sensors
8.1. Ion Exchange
Anions originally present in the polypyrrole films, which
compensate the charge of the polymer backbone (primary
ions) can be spontaneously exchanged by other anions
(secondary anions) present in the solution. Generally, the
possibility of this spontaneous replacement is limited to
relatively small ions, mobile in the polymer film. If mobile
ions are replaced with less mobile ones, irreversible
incorporation of this secondary dopant can be observed
[50, 83]. It has been also postulated that incorporation of
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1545
Table 2. Replacement of ClO
4 anions by other anions in 0.25 mm
polypyrrole film after 1 h soaking in 0.1 M solution of correspond-
ing anion at 25 8C [50].
Group Anions Replacement
I BF
4 , I
, SO 2
2

4 , S2O 8 Complete
II Cr2O 2
, CrO 2

, Fe( CN ) 3
Partial
7 4 6
III

F , PO 4 3

None
IV MnO 4

Film destruction
anions larger than the primary ones, present in the polymer,
is difficult and ion exchange can result in structural changes.
However, it is hard to compare results presented in the
literature due to diversity of experimental methods applied,
polymer morphology and polymerization procedures, af-
fecting the ion exchange kinetics. Schlenoff and Chien [148],
using radiotracer (ClO
4 Þ method, have observed a signifi-
cant influence of the solvent on the diffusion coefficient of
the doping ion. They have postulated dependence of this
process on the solvent used. Tsai et al. [149] have related the
rate of the process to the solution composition and structure
of the polymer. Spontaneous ion exchange has been also
studied by other authors [96, 150 – 153].
Table 2 presents results obtained by Curtin et al. [50]
concerning polypyrrole doped by perchlorate ions. Auger
spectra have shown that iodide, fluoroborate, sulfate and
peroxodisulfate ions can easily replace ClO
4 ions. Replace-
ment by chloride ions is faster than by bromide ones;
however, fluoride anions are not incorporated into the
polymer structure.
8.2. Potentiometric Ion Sensors
Processes of ion exchange and spontaneous ion replacement
can be utilized in potentiometric ion sensors with conduct-
ing polymer membranes. Conducting polymers, mainly
polypyrrole, are promising materials for this purpose
because of facile and cheap fabrication of solution free
sensors ([154, 155] and recent review [11]). The conducting
polymer film, coated on an electrode support, plays a role of
a receptor ion exchanging membrane. Owing to Donnan
equilibrium on the polymer/solution interface, the potential
of the electrode coated by this membrane is linearly
dependent on logarithm of ion activity. A negative slope,
close to Nernstian
0.059/n V is recorded for anion-
exchanging membranes, i.e. those containing mobile, ex-
changeable doping anions. On the other hand, the polymer
with immobilized dopants (bulky and/or multicharged
anions, as e.g., hexacyanoferrate or poly(4-styrenesulfo-
nate) ions) or the polymer in solution of bulky anions is a
cation exchanger. In such a case the slope of the potentio-
metric characteristic is positive [156 – 158]. The linear
response is observed for ion concentrations higher than
10
5 M. Also anionic forms of organic acids [15, 159] can
participate in ion-exchange processes.
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1546
Different affinity of ions to the polypyrrole membrane
results in various potential values being the origin of
selectivity. The influence of spontaneous ion exchange on
open circuit potentials and selectivity of polypyrrole based
potentiometric has been modeled theoretically [153]. Se-
lectivity was discussed in terms of formation of sparingly
soluble salts: polypyrrole-anion. However, these sensors
suffer from relatively low selectivity in the case of mono-
valent ions [154]. Selectivity coefficients in the range of 10
1
have been reported [152, 154]. A higher selectivity is
observed comparing monovalent and multivalent ions
(e.g., SO 2

4 ions) [154]; however, interactions with multi-
valent ions can result in irreversible binding, especially after
longer exposure of the electrode to these ions [160].
Enhanced selectivity can be also obtained by “molecular
imprinting” procedure. An example is polypyrrole doped by
nitrate ions, being a nitrate-selective potentiometric elec-
trode (selectivity coefficient for ClO
4 or I
is in the range of
10
2) [161].
Although some cations can directly form complexes with
polypyrrole, as e.g., copper ions [15, 162], selective sponta-
neous ion-exchange process can be stimulated by polypyr-
role doping with complexing ligands (as e.g., Tiron, Calcon
etc.), facilitating accumulation of cations. The studies were
carried out by Lewenstam and his coworkers, mainly for
Cu2þ, Ca2þ and Mg2þ cations, interacting with the ligands
[163 – 167]. The processes with complexing ligands can be
applied for potentiometric sensing of the above cations. The
enhanced sensitivity is observed after soaking in primary
ions solution, this step is necessary to obtain primary ions –
ligand complexes in the polymer phase. A linear response
range was observed for analyte ions concentration higher
than 10
5 M. However, these polypyrrole sensors suffer
from high pH interferences related to polymer and doping
ion protonation/deprotonation.
Lewenstam with coworkers have tested also ligands of
biological importance as adenosine triphosphate [168],
heparin [169] and studied kinetics of Ca2þ and Mg2þ ions
binding, as a model of processes occurring in real biological
membranes.
9. Interactions with Surfactants
As demonstrated by electrochemical quartz crystal micro-
balance, voltammetric and EDAX measurements some
large or multicharged anions and surfactant ions can
spontaneously replace primary dopants (Cl
or ClO
4
anions). These anions, as e.g., SO 2
4 , can be irreversibly
placed in the polypyrrole film [160, 170 – 173]. For instance,
while polypyrrole is conditioned in dodecylsulfate ions
solution, these anions can be adsorbed, decreasing ion
exchange ability of the polymer [69]. It has been recently
shown that the surfactant influence depends on the kind of
doping ion present in the polypyrrole film [173]. Surfactants
accumulated at the polymer/solution interface inhibit ion
exchange and thus result in decrease of voltammetric
current accompanying polymer oxidation/reduction. For
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K. Maksymiuk
anion-exchanging polypyrrole doped by chloride ions, the
interactions with surfactants (independently of their
charge), are observed for micromolar concentrations of
surfactants, as shown by lower voltammetric currents. On
the other hand, for the polymer doped by hexacyanoferrate
anions immobilized in the polymer structure (i.e. for cation
exchanger) the influence is much smaller, even at millimolar
concentration. This difference can be ascribed to different
surface morphology and hydrophobicity of the polymer.
Polypyrrole doped by chloride ions is more hydrophobic in
the neutral state and its structure is more porous, enabling
stronger interactions with surfactant molecules.
Polypyrrole interactions with surfactants can be used in
determination of these substances. Potentiometric method
of dodecylsulfate anions determination has been proposed
[174], with detection limit 2  10
6 M. Amperometric meth-
ods of surfactants ion determination are characterized by a
lower detection limit. The accessible concentration range is
10
7 – 10
2 M, based on measuring the current decrease
caused by ion exchange inhibition [173]. It has been also
found that surfactants presence does not affect significantly
the open circuit dependence on logarithm of electrolyte ions
(Naþ, Cl
) concentration.
10. Influence of Polypyrrole Reactivity on
Analytical Characteristics of Potentiometric Ion
Sensors
As already mentioned above, chemical processes of poly-
pyrrole can find applications to construct sensors, provided
that the analyte of interest is involved in the process.
However, if the analyte is not directly involved in the
spontaneous transformation of the polymer, such processes
can be usually considered as undesirable. Nevertheless, their
significance is very often underestimated. In the absence of
external polarization, as in open circuit potentiometry, these
processes can be the only charge transfer reactions and thus
can even crucially affect the potentiometric characteristics
and/or apparent signal stability. The most significant pro-
cesses in this case are protonation/deprotonation phenom-
ena and redox reactions, mainly with commonly present
oxygen. Therefore, owing to common presence of possible
reactants (Hþ, OH
, O2), this topic will be discussed here as
very important for practical applications of polypyrrole in
sensors.
10.1. Potentiomeric Sensors with Polypyrrole Ion
Receptor Membrane
From the point of view of potentiometric applications it is
useful to relate the spontaneous processes to changes of the
open circuit potential in time [27]. Terms “cathodic” and
“anodic” ionic local currents, across the polymer/solution
interface, can be ascribed to direction of doping ions flow
between the polymer and solution. Decrease of the potential
represents a “cathodic” process. An example of such
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemical Reactivity of Polypyrrole
Fig. 7. Schematic representation of A) “cathodic” spontaneous
process: deprotonation accompanied by anion flow from the
polymer and B) “anodic” spontaneous process: oxidation by
oxygen, accompanied by anion flow to the polymer, and
corresponding open circuit potential changes.
reaction is polypyrrole deprotonation (Fig. 7A). The
“cathodic” local current is represented by a flow of dopant
anions from the polymer to the solution (or flow of doping
cations to the polymer in the case of cation-exchanging
polymer). On the other hand, potential increase represents
an “anodic” process, an example is polypyrrole oxidation by
oxygen (Fig. 7B). Now, the “anodic” local current is
represented by flow of doping anions to the polymer (or
flow of doping cations from the polymer to the solution for
cation-exchanger). A stable open circuit potential is re-
corded if the sum of local “cathodic” currents is equal to that
of “anodic” ones.
However, this is not the case in dilute solutions [175, 176].
For low concentration of the bathing electrolyte, ion flow
from the polymer to the sample solution is preferred. The
flow in the opposite direction is hindered due to low
accessibility of ions in the solution (Fig. 8). Thus, doping ion
flow from the polymer to the solution predominates. This
results in a concentration gradient near the polymer/
solution interface, and the concentration next to polymer
layer is higher than in the bulk (Fig. 8). In the case of anion
exchanging polypyrrole, e.g., doped by chloride ions, the
preferred process will be “cathodic” one (e.g. deprotona-
tion) accompanied by release of doping (chloride) anions.
On the other hand, for cation exchanging film the preferred
process will be “anodic” one (e.g. oxidation by oxygen)
accompanied by release of mobile cations. In both cases the
flow of ions, from the polymer to the sample solution, leads
to locally increased concentration of ions, compared to
solution bulk. If these ions are “analyte” ones, this effect can
lead to a higher value of the detection limit. To evaluate the
detection limit, a relation between flux of ions and their
concentration gradient between bulk solution and interface
area [177] can be used. Assuming that the detection limit can
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1547
Fig. 8. Schematic representation of anion flow on the interface:
anion exchanging polypyrrole and electrolyte solution. Depend-
ence of the anion concentration in solution on the distance from
the polymer surface. A) concentrated, B) diluted electrolyte
solution.
be ascribed to surface concentration, c(0,t), for bulk
concentration equal to zero, the following equation has
been derived [175]:
c(0,t) ¼ 2 J [t/Dp]1/2 (9)
where: J is the flux of analyte ions, D is the diffusion
coefficient of ion in solution, t is time.
Results presented in [175, 176] show good concordance of
theoretical and experimental values of detection limit. Thus,
spontaneous processes exert undesirable effect, leading to
rather narrow linear range of the potentiometric responses.
This undesirable ion flow can be compensated by external
current, anodic in case of anion exchanger and cathodic for
cation exchanging film. If the applied current is near to that
corresponding to spontaneous process, this procedure
results in a significant decrease of the detection limit [175,
176].
Spontaneous processes of polypyrrole not only affect the
detection limit, they are also origin of serious redox
interferences. Redox reactant present in the sample solution
can give rise to disappearance of the dependence: potential
vs. logarithm of electrolyte activity. Assuming that the
spontaneous process (in the absence of redox reactants) is
represented by a local “anodic” or “cathodic” current, icharge
and idischarge, respectively, flowing across the polymer/solu-
tion interface [178], the stable open circuit potential can be
described by equation:
icharge þ ired ¼ idischarge þ iox (10)
where iox and ired are oxidation and reduction currents,
respectively, of the redox couple present in solution. In the
case of polypyrrole, currents icharge and idischarge are relatively
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1548
Table 3. Slopes of potentiometric dependences: potential vs.
logarithm of KCl concentration for polypyrrole films doped by
chloride ions, in the absence and presence of redox couple
K3Fe(CN )6/K4Fe(CN )6 with equal concentrations of both forms
[179].
Redox couple concentration Slope  S.D. (mV · dec
1)
0
59.8  0.4
10
5
43.1  1.5
10
4
30.5  0.4
10
3
15.9  0.4
10
2
1.8  1.1
high, in the range of mA cm
2 [27, 175, 176], thus the addition
of redox reactant (resulting in appearance of ired and iox) does
not change significantly the measured potential, if the redox
reactants concentration is not high [179 – 181]. The sponta-
neous processes of charging/discharging exert a leveling
effect on the potential. In this context, spontaneous
processes are beneficial since they diminish the influence
of redox interferences. An example of redox couple
Fe(CN) 3
6 /Fe(CN) 6
4

concentration influence on slopes of
potentiometric dependences (potential vs. logarithm of
electrolyte concentration) is presented in Table 3 [179]. For
the redox couple concentration higher than 10
3 M the
potential dependence on electrolyte concentration practi-
cally disappears.
The influence of redox reactants depends on the kinetics
of charge transfer. For reactants characterized by low charge
transfer rate, a slow change of the potential is observed. The
final potential value is higher or lower in the presence of
oxidizing (e.g. oxygen) or reducing agent, respectively [179].
However, the slope of potential vs. logarithm of electrolyte
concentration does not change, compared to absence of
redox reactant, as observed in the presence and absence of
oxygen [179]. Thus, the plots: potential vs. logarithm of
electrolyte concentration recorded in the presence and
absence of oxygen are parallel shifted.
Application of overoxidized polypyrrole significantly
diminishes the influence of redox interferents in potentio-
metric applications [182].
10.2. Potentiometric Sensors with Polypyrrole Transducer
Conducting polymers can be also successfully applied in all-
solid-state potentiometric ion sensors, if the CP is used not
as a receptor membrane, but as so-called ion-to-electron
transducer placed between the electrode support and a
typical ion-selective membrane [11, 12, 183], Figure 9.
Because semi-oxidized or oxidized CP, e.g., polypyrrole, is
a mixed electronic and ionic conductor, it assures reversible
charge transfer on interfaces: (i) electron transfer between
the CP and electronically conducting support, (ii) ion
transfer between the CP and ionically conducting ion-
selective membrane. The reversible charge transfer at all
interfaces results in stable potentiometric responses of the
sensor.
Electroanalysis 18, 2006, No. 16, 1537 – 1551 www.electroanalysis.wiley-vch.de
K. Maksymiuk
Fig. 9. Scheme of all-solid-state ion-selective electrode with
conducting polymer solid contact. Solid arrows represent inter-
facial ion exchange processes, while dashed arrows: ion flow
between polypyrrole layer and the solution, compensating charge
changes resulting from spontaneous processes of the polymer.
However, ion-selective membranes are permeable not
only for analyte ions but also for water, Hþ and/or OH
ions
as well as oxygen [183]. Therefore, even in the presence of
ion-selective membrane, chemical spontaneous processes
typical for the CP transducer can affect the potential as in
the case, where the conducting polymer acts itself as
receptor membrane. Generally, these processes are coupled
with ion flow from/to the transducer phase, affecting the
analyte ions concentration in solution near the membrane
surface, in an analogous way as for sensors with CP
membranes [175] (eq. 9). In the case of analyte ions flow
into the sample solution, this results in a higher detection
limit. For instance, deprotonation process of polypyrrole
transducer, coupled with release of chloride doping ions
leads to increase of chloride ions concentration in sample
solution layer, close to the membrane solution. This is the
origin of detection limit of electrode with chloride-selective
membrane [175], because the ion transfer across the
membrane is generally favored for the primary (analyte)
ions. The undesirable effect of analyte ions leakage can be
reduced or eliminated by external galvanostatic polariza-
tion, compensating the analyte ion flux [12, 175] or by a
carefully chosen method of conditioning, reducing the
amount of analyte ions in the CP transducer phase [184,
185]. Lowering of the detection limit enables also determi-
nation of unbiased selectivity coefficient, lower than those
obtained earlier, when their determination was affected by
analyte ions released from the membrane [175, 186].
11. Conclusions
Polypyrrole can undergo various side reactions with envi-
ronment components and common reactants as Hþ/OH

ions, ammonia, metal cations etc. The susceptibility to such
reactions is highly dependent on the oxidation state of the
polymer. Polypyrrole in the neutral (non-oxidized) state
easily undergoes oxidation by oxygen or other oxidizing
agents (e.g. noble metal cations), it can be also protonated.
On the other hand, oxidized polypyrrole can be easily
deprotonated, reduced (e.g. by ammonia) or involved in
spontaneous exchange of dopant anions. Both oxidized and
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemical Reactivity of Polypyrrole
neutral polypyrrole can undergo irreversible aging (degra-
dation) in a longer time scale. The above processes, leading
to change of the stored charge, composition and structural
changes and in some cases degradation, are usually undesir-
able.
On the other hand, under appropriate conditions they can
be used for analytical purposes in electrochemical sensors of
species participating in the spontaneous processes.
Spontaneous processes of polypyrrole protonation/de-
protonation and oxidation/reduction seem especially im-
portant owing to common presence of such reactants as (Hþ,
OH
and oxygen) in real samples. These processes can affect
adversely properties of polypyrrole based electrochemical
sensors. The most significant influence relates to polypyr-
role based potentiometric ion sensors, where the conducting
polymer is used as either ion-sensitive receptor membrane
or ion-to-electron transducer. This significant influence of
side reaction on the potential results from absence of other
charge transfer processes occurring under open circuit
conditions. The parameter, which is most seriously affected
by the spontaneous processes, is detection limit of the
sensor. It is important that the influence of undesirable side
reactions can be tuned by proper conditioning and mea-
surement procedure.
12. Acknowledgements
Author is grateful to Prof. Zbigniew Galus and Dr. Agata
Michalska for their helpful comments and discussions.
Financial support of the research project 3T09A 017 27 in
the years 2004 – 2007, from KBN, Poland, is gratefully
acknowledged.
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Biographical Sketch
Krzysztof Maksymiuk was born in 1959. He received his
MSc degree in chemistry from Warsaw University (Poland)
in 1983 and became a member of Professor Z. Galus
research group. His early research interests revolved around
electrode reactions in organic and aqueous-organic mixed
solvents, inhibition of electrode reactions by adsorbed
substances and stereo-electrochemistry. He received his
PhD degree in 1990.
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97.
In the years 1992 – 93, he was a fellow of Alexander von
Humboldt Stiftung (Germany) and worked as a guest
scientist at Fritz-Haber-Institut der Max-Planck-Gesell-
schaft in Berlin. His research was focused on electrochem-
istry of conducting polymers, with emphasis on kinetics and
mechanisms of charge transfer reactions. On completing his
post doctorate, he went back to Warsaw University. His
current research interests concerns various aspects of
conducting polymers applications in electrochemical sen-
sors and reference electrodes as well as optimization of ion-
selective electrode parameters.
He has published over 60 scientific papers.
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim