Polyaniline/Fe3O4 Nanoparticle Composite: Synthesis and Reaction

Mechanism

Polyaniline/Fe3O4 nanoparticle composite was prepared by polymerizing aniline in the presence of

Fe3O4
nanoparticles upon the use of H2O2 as oxidant. The polymerization was monitored by ultraviolet-visible
absorption spectroscopy. The microstructure of the resultant composite was characterized by
transmission
electron microscopy. The molecular structure of the resultant polyaniline in the composite was
investigated
by both Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, while the
magnetic
property of the composite was characterized by vibrating sample magnetometer. Furthermore, the
microwave
absorption property of the resultant composite was measured in a frequency range of 2-18 GHz.
Systematic
investigations revealed that carboxylic acid in the buffer presented a determined role in the
polymerization
of aniline. To discover the role of carboxylic acid in the polymerization of aniline, more control
experiments
were designed and carried out by theoretical calculation in combination with electron spin resonance
measurements. It was for the first time found out that carboxylic acid such as acetic acid and succinic
acid
can not only catalyze the polymerization of aniline but also facilitate the generation of hydroxyl radical
via
the decomposition of H2O2.

Polyaniline (PANI) as a conducting polymer has become very

attractive because of its facile synthesis,5 stable chemical and
environmental properties,6 and inherent reversible doping/
dedoping states.7 Therefore, it is a suitable matrix for achieving
electromagnetic shielding or absorption materials by doping with
magnetic iron oxide nanoparticles. PANI is commonly synthesized
by oxidizing aniline monomer in acid solution via either
chemical or electrochemical method.5 In comparison with
electrochemical method, the chemical synthesis of PANI is
widely used for mass production.5 Various types of oxidants
such as (NH4)2S2O8,6,8,9 FeCl3,10,11 K2Cr2O7,9,12 KIO3,9 and H2O2,9
can be used in the chemical synthesis of PANI. Among these
oxidants, (NH4)2S2O8 is the most commonly used one, but the
resultant PANI is often neither soluble nor fusible. In addition,
the posttreatments of the products for eliminating inorganic
byproduct, such as ammonium sulfate, are rather complicated.
Therefore, from the point of view of environmental friendliness,
H2O2 is an ideal oxidant since its reduction product is only water.
However, when H2O2 is used alone, the reaction rate for forming
PANI is extremely slow. Therefore, it is generally believed that
it is impossible to prepare PANI through the oxidation of aniline
by using H2O2 alone at room temperature.13
Polyaniline glucose oxidase biosensor prepared with
template process
Abstract
A new method of preparing polyaniline (PANI) glucose oxidase sensor, which is called template process, is
reported in this paper. The
process is as follows. First, PANI glucose oxidase electrode is obtained using one-step process, i.e. enzymes were
entrapped into a polymer
film directly during electrochemical polymerization of aniline. Then the electrode is hydrolyzed in 6.0 mol/dm 3
hydrochloric acid solution
to remove the glucose oxidase from the PANI film, for part of the glucose oxidase affected by monomer of aniline
were denatured and
inactive. Finally, fresh glucose oxidase is immobilized into the PANI film again to obtain an active PANI glucose
oxidase sensor. Some
factors that affect response current are studied, such as temperature, pH, potential and substrate concentration. The
response current of the
biosensor prepared by template process reaches to a maximum at the first 2 days, then decreases by only 4.6% for
30 days, while that of the
sensor prepared by two-step process decreases by approximately 55.4%. The two-step process is that an enzyme is
introduced during the
oxidation stage of the reduced polyaniline in a buffer solution containing active enzymes. Characterization of the
PANI glucose oxidase
sensor prepared by the template process with FT-IR, UV-Vis and SEM suggests that the glucose oxidase mainly
locates at the nitrogen
sites of the quinoid ring.
© 2004 Elsevier B.V. All rights reserved

1. Introduction
Enzyme-based biosensors are becoming more and more
important as an analytical tool, for enzymes have an
unique ability of quickly and accurately recognizing target
molecules in a complicate system. Since Clark and Lyons
developed the first enzyme sensor in 1962 [1], there have
been many researches about the materials and methods of
immobilizing enzymes [2,3]. However, research for new
materials and methods is still a very important subject to
get more active and stable biosensors [4].
With the appearance of conducting polymers, immobilization
of enzymes in conducting polymers has received a
great deal of interest [5–10]. There are many advantages in
preparing biosensors with conducting polymers, such as efficient
transfer of electric charge [11], considerable flexibility
in available chemical structure [12] and rather high stability
of conducting polymers themselves. Immobilization of enzymes
in conducting polymers to form biosensors has been

made mainly by one-step process [13] or two-step process

[5–8]. In the one-step process, an enzyme was entrapped into
a polymer film directly during electrochemical polymerization
of aniline. The one-step process is simple and cheap,
but parts of the glucose oxidase affected by monomers of
aniline were denatured and inactive [7]. In the two-step process,
on the other hand, an enzyme is introduced during the
oxidation stage of the reduced polyaniline in a buffer solution
containing active enzymes. This method can be done
under a moderate condition, so that the activity of an enzyme
is not so significantly denatured. However, the stability
of immobilized enzyme is affected by the size of the
polyaniline particles performed. The particle size is smaller
than of the enzyme molecule, the enzyme molecule can only
be adsorbed on the surface of the conducting film, and then
the enzyme may easily desorb from the film during sensing
measurement [8].

Electrospinning polyaniline-contained gelatin nanofibers for

tissue engineering applications
Abstract
Polyaniline (PANi), a conductive polymer, was blended with a natural protein, gelatin, and co-electrospun into
nanofibers to
investigate the potential application of such a blend as conductive scaffold for tissue engineering purposes.
Electrospun PANi–contained
gelatin fibers were characterized using scanning electron microscopy (SEM), electrical conductivity measurement,
mechanical tensile
testing, and differential scanning calorimetry (DSC). SEM analysis of the blend fibers containing less than 3%
PANi in total weight,
revealed uniform fibers with no evidence for phase segregation, as also confirmed by DSC. Our data indicate that
with increasing the
amount of PANi (from 0 to _5%w/w), the average fiber size was reduced from 8037121nm to 61713nm (po0:01)
and the tensile
modulus increased from 4997207MPa to 13847105MPa (po0:05). The results of the DSC study further strengthen
our notion that the
doping of gelatin with a few % PANi leads to an alteration of the physicochemical properties of gelatin. To test the
usefulness of PANigelatin
blends as a fibrous matrix for supporting cell growth, H9c2 rat cardiac myoblast cells were cultured on fiber-
coated glass cover
slips. Cell cultures were evaluated in terms of cell proliferation and morphology. Our results indicate that all
PANi-gelatin blend fibers
supported H9c2 cell attachment and proliferation to a similar degree as the control tissue culture-treated plastic
(TCP) and smooth glass
substrates. Depending on the concentrations of PANi, the cells initially displayed different morphologies on the
fibrous substrates, but
after 1week all cultures reached confluence of similar densities and morphology. Taken together these results
suggest that PANi-gelatin
blend nanofibers might provide a novel conductive material well suited as biocompatible scaffolds for tissue
engineering.
r 2005 Elsevier Ltd. All rights reserved.

Since their discovery some 30 years ago, electrically

conductive polymers, also known as ‘‘synthetic metals’’ are
finding increasing number of applications in many areas of
applied chemistry and physics, such as light emitting diodes
[18]. More recently, there is a growing interest in
conductive polymers also for diverse biomedical applications,
including for tissue engineering. We like others, have
based our rationale for using conductive polymers on the
hypothesis that a multitude of cell functions, such as
attachment, proliferation, migration, and differentiation
could be modulated through electrical stimulation [19].
Common classes of organic conductive polymers include
polyacetylene, polypyrrole (PPy), polythiophene, polyaniline
(PANi), and poly(para-phenylene vinylene). Some of
these conductive polymers, especially PPy, have found
some intriguing biomedical applications, such as for the
synthesis of nanoparticles [20], immobilization of proteins
[21], and coating devices with PPy materials [22]. Schmidt
and her coworkers were the first ones to employ PPy for
tissue engineering purposes, demonstrating that electrical
stimulation enhanced NGF induced neuronal differentiation
of PC 12 cells [23]. Subsequently the same group also
functionalized the surface of chlorine-doped PPy to anchor
peptide molecules that promote nerve regeneration, blood
vessel growth or other biological processes [24]. Lakard
et al. cultured olfactory cells on PPy to investigate cell
adhesion and proliferation [25]. George et al. examined
PPy biocompatibility and found neurons and glial cells
enveloped the PPy implant [26]. Several other scaffolds
containing PPy have been used for a variety of other
applications of tissue engineering [27,28].
By comparison, only few groups have considered PANi,
one of the otherwise most studied organic conducting
polymers, as potential conductive substrates for tissueengineering
applications [29,30]. In the past two decades,
the ability of varying oxidative state has allowed the
conducting polymer PANi to be studied in wide range of
research fields, such as corrosion protection of metals [31],
as substrates for light-emitting devices [32] or as the
electrode in the battery [33]. It is only quite recently that
the tunable electroactivity of PANi has been explored in
the realm of diverse biological application such as for
biosensors [34] or as scaffolds in tissue engineering [35].
Mattioli-Belmonte et al. were the first ones to demonstrate
that PANi is biocompatible in vitro and in long-term
animal studies in vivo [36]. Nevertheless, most of those
groups investigated the biological properties in the form of
films, instead of nanofibers. Dı´az. et al. reported that
doped, conductive PANi blended with polystyrene (PS)
and/or polyethylene oxide (PEO) could be electrospun
yielding nanofibers [37]. In this paper, we describe our
study on electrospinning a novel blend of conductive
camphorsulfonic acid-doped emeraldine PANi (C-PANi)
and gelatin and provide detailed investigations of the
ensuing submicron sized fibers. Gelatin is a frequently used
biomaterial for tissue engineering application, especially in
cardiac tissue engineering [38,39]. Our data indicate that
the addition of PANi to gelatin results in homogeneous
electrospun fibers and that with increasing PANi concentration concentration,
the fiber size is reduced from approximately
800nm to less than 100nm concomitant with an increase
in the tensile modulus of fibrous scaffolds. H9c2 rat cardiac
myoblast cells were selected and cultured on these fibrous
substrates, in view of our long-term goal to generate
scaffolds for engineering cardiac tissues in vivo. Cell
culture result demonstrates that PANi-gelatin blend fibers
are biocompatible, supporting cell attachment and proliferation.
Enhanced specific capacitance and supercapacitive
properties of polyaniline–iron oxide (PANI–Fe2O3)
composite electrode material
ABSTRACT
In the present work we report ferric oxide (a-Fe2O3) and conducting polyaniline–
ferric oxide (PANI–Fe2O3) composite thin films prepared using simple
electrodeposition technique. The structural and morphological analysis was
carried out by X-ray diffraction and scanning electron microscopy. The supercapacitive
properties of these films were examined using cyclic voltammetry,
charge–discharge studies, and electrochemical impedance spectroscopy in 0.5 M
Na2SO4 electrolyte. It is observed that the PANI–Fe2O3 composite electrode
delivered higher specific capacitance than individual a-Fe2O3. Also the composite
thin film electrode exhibits excellent specific capacitance retention of
about 87 % over 1000 CV scan cycles as compared to a-Fe2O3 electrode, which
exhibits only 84 % retention capacity.
Preliminary Studies for Obtaining Polyaniline on Nickel
Electrode
Abstract: In our studies the possibility of obtaining polyaniline films on the nickel electrode through
electrodeposition
was investigated. The method used was cyclic voltammetry. The working electrode (anode) was glossy
nickel. The
electrolyte solution was diluted sulfuric acid with or without aniline. The experiments were performed
at temperatures
ranging from 25 to 45oC and an electrochemical potential interval between – 0.5 ÷ 1.6 V. A white
green to blue color
(depending on the electrochemical potential) polyaniline film was deposited on the nickel electrode.
The main reactions
that take place on the electrode and the effect of the working conditions on these processes were
identified through cyclic
voltammetry.

1. Introduction
Polyaniline (PANI) is one of the most studied conductive polymers because of its exceptional
chemical, electrical and optical properties. It can be obtained through chemical and electrochemical
methods. Through electrochemical synthesis the polymer is obtained directly under the shape of thin
films deposited on electrodes (metallic or non-metallic), having an ordered structure, with a high
degree of crystallinity. The electrode thus obtained, possibly modified with appropriate structure
compounds has many applications. It can be used as a biosensor for biomolecular compounds batching.
One such compound is dopamine – a biogenic amine that acts as a neurotransmitter in the brain and is
involved in motricity control [1]. A reduction in dopamine concentration leads to muscle stiffening, a
decrease in movement speed and trembling while resting, symptoms that indicate a neurodegenerative
disease such as Parkinson’s disease or schizophrenia.

Electrochemical Deposition and Properties of

Polyaniline Films on Carbon and Precious Metal
Surfaces in Perchloric Acid/ Acetonitrile
1. INTRODUCTION
Pristine polyaniline (PANI) is a special kind of conducting electroactive organic polymer
which shows many interesting properties such as electrochemical redox behavior,
electrochromic [1] catalytic activities [2-4]. Polyaniline being environmental stable, the
conductivity easily controllable, many researchers reported on this conducting polymer
by interesting on the redox properties associated with the chain nitrogen atoms [5].
Polyaniline also economically continues to be attractive despite the discovery of
numerous polyaniline derivatives based on functionalized aniline [6-7]. The properties
and several applications of PANI obtained depend on synthesis parameters such as the
technique of electrosynthesis and the composition of the polymerization solution. Of
particular interest is the electropolymerization of this most readily available monomer
into conductive PANI films.
Electrochemical polymerization also called electropolymerisation using for this study is a
typical method generally used for the synthesis of PANI coating [8] because of its
simplicity and reproducibility. In general, this method consists of applying a potential to a
working electrode immersed in electrochemical cell containing an electrolyte solution
with the reference and counter electrodes. The monomer is thus electrochemically
oxidized given place to the polymerization to occur at the electrode surface with
deposition of the polymer film. The first step of the synthesis is the formation of C 6H5-
NH2+ cation radical via the transfer of an electron from a sp 3 orbital of nitrogen atom to
the electrode when oxidation occurred. During polymerization, the PANI chain
propagation starts with the formation of non-conducting PANI, leucoemeraldine
(oxidation state n = 1) complete reduction state and terminates with the formation of the
most conductive PANI form, the emeraldine (n = 0.5) oxidation state. In some cases,
when using this method, the intermediate process occurs, and it forms the pernigraniline
(n = 0) fully oxidized state [9]. This technique presents as advantages greater simplicity
and reproducibility, completed coverage of the active surface, greater control over film
thickness and perhaps provide a means for the entrapment of both the specific agent and a
suitable mediator. Moreover, electropolymerisation is a cheap technique and
polymerization media can be used repeatedly. For electrochemical methods,
potentiostatic, galvanostatic and potential sweep methods are usually used for
electropolymerisation of PANI and its derivatives. The commonly used working
electrodes are conducting substrates such as gold, carbon, platinum and indium-tin oxide
coated glass plates [10].
On the other hand, the low cost of the monomer and its easy synthesis in different
aqueous medium confer to polyanilines more advantages. The synthesis of PANI is
performed generally in aqueous acid solutions [11] and neutral aqueous media [12],
either chemically or electrochemically. But in the case of organic media, it was
considered that good quality of PANI films cannot be obtained. Indeed, in aqueous acids,
some acids such as hydrochloric acid, sulfuric acid [13], oxalic acid and nitric acid [14-
16], oxalic acid [8] have been used; In aquous salts, copper (II) nitrate, sodium sulfate,
sodium sulfate/sodium perchlorate, lithium perchlorate, sodium benzoate, and
propylene carbonate/lithium perchlorate [17-24] have been used; In organic acid
electrolytes, many electrolyte solution as tetramethylammonium trifluoromethane-
sulfonate/acetonitrile, periodic acid/tetraethylammonium
tetrafluoroborate/acetonitrile, trichloromethan, tetrabutylammonium tetrafluoroborate
/trifluoroacetic acid, tetrabuthylammonium perchlorate/acetonitrile and perchloric
acid/benzenesulfonic acids [25-27] have been used in the electrosynthesis of PANI; In
ionic liquids electrolytes the ionic solution such as 1-methyl-3-butylimidazolium
tetrafluoroborate [28-32] has been investigated; In addition, PANI has been
electrosynthesized in fluoride medium such as ammonium fluoride and hydrofluoric Acid
[33]. From these previous studies done on the synthesis of polyaniline in different
media, some of them have shown that the medium of the polymerization affects the
properties of the polyaniline. For example, the yield and electrical conductivity of
emeraldine salt-form PANI prepared in acid medium is increased by decreasing the ionic
strength of the acid [34].
Glucose Biosensor from Covalent
Immobilization of Chitosan-Coupled
Carbon
Nanotubes on Polyaniline-Modified
Gold
Electrode

Conducting polymers have attracted much attention in the development of efficient amperometric
glucose biosensors (6-10). Their unique electroactive properties allow them to act as excellent substrates for
the immobilization of biomolecules and rapid transfer of electrons (11, 12). Among the various conducting
polymers, polyaniline (PANI) is particularly attractive (13, 14) owing to its high electrical conductivity, ease
of preparation and good environmental stability. In biosensor applications, PANI provides a suitable matrix
for the immobilization of biomolecules and can significantly improve signal amplification by acting as a
mediator for electron transfer in enzymatic reaction (15-18).
In the fabrication of biosensors, chitosan (CS) has been widely used for the immobilization of
various enzymes in

recent years (19-21). The unusual combination of its properties,

such as excellent membrane-forming ability, good
adhesion, high mechanical strength, good biocompatibility,
and susceptibility to chemical modification arising from the
presence of reactive amino and hydroxyl functional groups,
has promoted its application in biosensors (22, 23). However,
CS is nonconductive, which hampers electron transfer
in the biocatalytic process of enzymes (24). On the other
hand, functionalization of carbon nanotubes (CNTs) with
biomolecules is often a key step in their biological applications,
such as biosensing (25). Thus, CS is usually used in
combination with conducting polymers, CNTs, redox mediators
or metal nanoparticles in electrochemical biosensing
platforms (26, 27). Arising from the attractive electronic,
chemical and mechanical properties of CNTs, CS/CNTs
composites have been explored for the development of
electrochemical biosensors (27-29). It is desirable to covalently
couple CS with CNTs (CS-CNTs), because CNTs can
enhance the conductivity of CS while CS can improve the
hydrophilicity and biocompatibility of CNTs, resulting in
good dispersity and long-term stability of CS-CNTs in diluted
organic acids (30).
Glucose biosensor based on Au nanoparticles–conductive
polyaniline nanocomposite
Abstract
In this paper, we report a novel glucose biosensor based on composite of Au nanoparticles (NPs)–conductive
polyaniline (PANI) nanofibers.
Immobilized with glucose oxidase (GOx) and Nafion on the surface of nanocomposite, a sensitive and selective
biosensor for glucose was
successfully developed by electrochemical oxidation of H 2O2. The glucose biosensor shows a linear calibration
curve over the range from
1.0×10−6 to 8.0×10−4 mol/L, with a slope and detection limit (S/N = 3) of 2.3 mA/M and 5.0×10−7 M, respectively.
In addition, the glucose
biosensor system indicates excellent reproducibility (less than 5% R.S.D.) and good operational stability (over 2
weeks).
© 2005 Elsevier B.V. All rights reserved.

Since the first report of electrical conductivity in a conjugated

polymer in 1977, conductive polymers have attracted
much interest due to their combined properties of organic polymers
and electronic properties of semiconductors (Shirakawa
et al., 1977; Shenhar et al., 2005; Liu et al., 2004). Especially,
immobilization of enzymes into/onto various conductive polymers
has been extensively studied (Cosnier, 1999; Raffa et al.,
2003; Gerard et al., 2002; Forzani et al., 2004) because of their
unique characteristics. Nanoscaled forms of polyaniline (PANI)
have been successfully used to design sensors because their
high surface area allows for fast diffusion of target molecules
(Virji et al., 2004). PANI nanoparticles, doped with dodecylbenzenesulfonic
acid (DBSA), have been used to fabricate
H2O2 biosensor after immobilized with horseradish peroxidase
(HRP) (Morrin et al., 2005a,b). Negatively charged sulfonatefunctionalized
Au NPs are incorporated into PANI film or microrod
by electropolymerization and the composite has been used
as a matrix for the enhanced bioelectrocatalysis (Granot et al.,
2005).

In the present work, the nanocomposite of Au NPs and conducting

PANI nanofibers is used to immobilize glucose oxidase
(GOx) and a novel glucose biosensor is developed. Because of
the large specific surface area, excellent conductivity, and many
microgaps existing between the nanocomposite, GOx could be
easily immobilized with high loading and activity. In addition,
the small dimensions and the high surface-to-volume ratio of the

nanocomposite allow the rapid transmit electron and enhance

current response. Moreover, Au NPs are in electrical contact,
through the PANI nanofibers, with the glassy carbon, enabling
the nanocomposite structure to be used as an excellent matrix for
electrocatalysis and enzyme immobilization. Thus, the Au NPsconducting
PANI nanocomposite modified biosensor displays
high sensitivity and is potentially useful for glucose sensing in
vitro or in vivo.
Revising the kinetics of aniline
electropolymerization under controlled potential
conditions
INTRODUCTION
Since the discovery of electrically conducting polymers
more than 20 years ago these novel materials
are finding increasing use in various fields of science
and technology [1–3]. For diverse uses of these
materials, the deposition of conducting polymer layers
onto different surfaces is of primary interest.
Apart from polymer processing and chemical oxidative
deposition [4], electrochemical (anodic) polymerization
of the corresponding monomers is of great
importance in obtaining conducting and electroactive
coatings onto metal surface. Two basic techniques
are widely used in obtaining conducting polymer
coatings at metal or other conducting surfaces.
These are the potential cycling procedure and
electrolysis at a controlled electrode potential. In
both cases the electropolymerization starts at a high
positive electrode potential, where highly reactive
species such as radical cations are formed due to
electrochemical oxidation of monomer molecules.
The electropolymerization process is well known
for its autoaccelerating character which has been a
subject of a few investigations during the past decade.
For electropolymerization of aniline, Wei et al.
expressed the rate of polymer formation as a sum
of two terms by the following empirical equation
[5]:
R = k · [P] · [M] + k’ · [M], (1)
where R represents the rate of polymer formation,
k is an empirical rate constant for electropolymerization
at a polymer covered electrode, k’ is a rate
constant before polymer is formed on the electrode
(i.e. the rate constant for a bare electrode), [M] is
the monomer (aniline) concentration, and [P] is the
polymer (polyaniline) concentration at the electrode
surface.
Both empirical rate constants k and k’ depend
on many variables such as electrode potential, scan
rate and switching potential (for electropolymerization
by potential cycling), temperature, acidity of
the polymerization solution, etc. Therefore, albeit
the absolute values of these constants are of little

interest, the ratio of the constants reflects the autoaccelerating

character of the electropolymerization
process. In accordance with Eq. (1), autoacceleration
should proceed at k >> k’, i.e. when the rate
of electropolymerization at a surface covered with a
polymer layer exceeds greatly the rate at a bare
substrate surface. For a variety of experimental conditions
used, Wei et al. found the ratio k’/k = 1.8
· 10–4 [5]. This means that the rate for polymerization
of aniline at a polyaniline-coated electrode exceeds
the polymerization rate at a bare electrode
approximately by four orders of magnitude.
Somewhat later, Wu and Yang analyzed the kinetics
of electropolymerization of aniline and its derivatives,
o- and m-toluidines (o- and m-methylanilines)
at a RuO2 coated titanium electrode in 1.0 M
HCl solution within the frame of the same kinetic
model, and obtained the ratio k’/k to vary between
3.5 · 10–6 and 5.4 · 10–6 for these three monomers
[6]. At a thermally prepared platinum coated titanium
electrode, the ratio k’/k of 6.64 · 10–6 for aniline
and 3.23 · 10–6 and 3.15 · 10–6 for o- and mtoluidines,
respectively, were obtained in 1.0 M HCl
solution [7]. The same tendencies were observed for
autoaccelerating chemical polymerization of aniline
in aqueous acidic solutions as well. With the use of
ammonium persulfate as an oxidizing agent, the following
empirical kinetic equation was derived [8]:
where [AN], [APS], and [P] are the concentrations
of aniline monomer, ammonium peroxydisulfate, and
polyaniline, respectively.
In general, the ratio k’/k of 10–2–10–3 was obtained
[8] in accordance with the autoaccelerating character
of chemical oxidative polymerization.
On the other hand, it is well known that polyaniline
undergoes degradation processes in an acidic
solution at a high electrode potential [9]. With the
use of UV-Vis spectroelectrochemical techniques,
first order degradation rate constants ranging from
8.40 · 10–6 to 2.93 · 10–3 s–1 were determined for
polyaniline deposited at an ITO glass electrode, within
the potential window of 0.85 to 1.20 V vs. RHE
(i.e. 0.65 to 1.00 vs. the Ag / AgCl reference electrode),
respectively [10]. For polyaniline deposited
on a platinum electrode, first-order degradation rate
constants ranging from 2.87 · 10–5 to 3.11 · 10–3
s–1 were found for electrode potentials ranging from
0.3 to 0.9 V vs. Ag / AgCl [11]. Similar results were
obtained also for poly(styrene sulfonate) doped polyaniline
deposited at a platinum electrode [12]. The
upper limit of the degradation rate constant of ca.
3 · 10–3 s–1, obtained at a high electrode potential of
0.9 or 1.0 V vs. Ag / AgCl, corresponds to fast
degradation process of a polymer film with the halfperiod
of ca. 3 min. Therefore, since electropolymerization

electropolymerization
of aniline proceeds at a high electrode
potential reaching or exceeding 0.9 V, intense degradation
processes should proceed in parallel to
electropolymerization. Thus, the degradation of polyaniline
should influence considerably the observed
kinetics of the electropolymerization process.
The present work has been aimed to study the
net kinetics of aniline electropolymerization at a controlled
electrode potential with the use of electrochemical
and UV-Vis spectroelectrochemical techniques
Electrochemical Preparation and Sensor Properties of
Conducting Polyaniline Films
A polyaniline-glucose oxidase electrode was prepared by the electrochemical polymerization of aniline
on a Pt electrode that was already pre-adsorbed by the enzyme (glucose oxidase) at a potential of 1 V
vs: Ag/AgCl. Then, the amperometric responses of the enzyme electrode to the electroactive hydrogen
peroxide formed by the enzyme-catalyzed reaction of the substrate (glucose) with oxygen were measured
at a potential of 0.7 V in PBS solution.
The e_ects of electrochemical polymerization (i.e., concentrations of monomer and electrolyte, _lm
thickness) and amperometric measurement parameters (i.e. pH, temperature) on the amperometric
response characteristics to glucose of the resultant enzyme electrode were systematically investigated
and all these parameters were optimized.
The prepared polymeric sensor exhibited a fast steady-state amperometric response time (4-5 s), a
linear amperometric response up to 6 mM glucose through with poor stability. Also, it was found that
the sensor responded successfully to glucose injections in the presence of some interfering substances such
as ascorbic acid, oxalic acid, lactose, sucrose and urea.
Key words: Polyaniline, enzyme electrode, amperometric biosensor.

Introduction
In the construction of the amperometric biosensor, a number of immobilization techniques, such as
physical entrapment [1], chemical immobilization in an inert matrix [2], and covalent attachment to
electrode surfaces [3-5] have been used to immobilize the relevant enzyme. On the other hand,
conducting or non-conducting polymeric _lms prepared by the electrochemical polymerization of the
relevant monomer have been also succesfully used as enzyme immobilization media. Among these
polymeric _lms, polypyrrole [6-9], polyphenols [10,11], polyphenylenediamines [12,13], polyindoline
[14], polybenzidine [15] and poly(o-toluidine) [16] have been recently used to immobilize enzyme or
to prevent electroactive interference and fouling of the electrode surface.
In the amperometric glucose measurement, the enzymatic reaction between glucose and glucose
oxidase in the presence of O2 as the electron acceptor can be expressed by the following equations [17]:
The electroactive H2O2 produced as a result of the enymatic reaction is responsible for the observed
faradaic signal.
In this article we describe a method for the preparation of a polyaniline-glucose oxidase enzyme
electrode. The e_ects of experimental parameters (i.e., concentrations of monomer and electrolyte, _lm
thickness, pH and temperature) on the amperometric sensor characteristics of the resulting biosensor
were
investigated.

An amperometric biosensor for glucose detection from

glucose
oxidase immobilized in polyaniline – polyvinylsulfonate –
potassium
ferricyanide fi lm
Th e conducting
polymers are being widely used in biosensor applications
because they provide stable and porous matrix for
the immobilization of biocomponent, and they also facilitate
the electron transfer process. Th e widely used conducting
polymers for immobilization of enzyme are polyaniline,
polypyrrole, polythiophene, etc. (Bidan 1992, Gaikwad et al.
2005, Barlett and Cooper 1993, Shirale et al. 2005, Cosiner
1999, Colak et al. 2012, Arslan et al. 2012).
In this study, a novel amperometric glucose biosensor
with immobilization of glucose oxidase on electrochemically
polymerized polyaniline– polyvinylsulphonate– potassium
ferricyanide (Pani– Pvs– Fc) fi lms has been accomplished
via the entrapment technique. Potassium ferricyanide was
used as the mediator. Eff ects of the immobilization process
on kinetic parameters, storage and reuse capability of the
enzyme were investigated. Th e optimum working conditions
of biosensor with respect to the substrate concentrations,
the pH and temperature were investigated.

Experimental section

Equipment and reagents

Preparation of Pt/Pani – Pvs electrode

Preparation of Pt/Pani – Pvs – Fc – GOx electrode

Amperometric biosensor measurements

Results and discussion

The eff ect of mediator

The eff ect of working potential

The eff ect of potassium ferricyanide concentration

on the response of the Pt/Pani – Pvs – Fc electrode
to glucose

The eff ect of pH on amperometric response

of biosensors

The eff ect of temperature on amperometric response

of biosensors

Substrate concentration and calibration curves

Operational stability and storage stability

Interference eff ect

Conclusions
Electrodeposition and Characterization of
Polyaniline Films
Abstract — This study describes the effects of deposition
potential and deposition time on the electrodeposition of
Polyaniline (PANi) films on indium tin oxide (ITO)-coated glass
substrate. It was found that the aniline with 0.5M in 1M H2SO4
started to polymerize on ITO substrate at + 0.70 V vs Ag/AgCl.
Chronoamperometry was used to deposit PANi on ITO-coated
glass at three different applied potentials (ie: +0.75V, +1.0V and
+1.5V) and three different deposition times (ie: 60s, 300s and
600s). The surface morphology of the PANi films was imaged by
field emission scanning electron microscopy (FESEM). The films
electrodeposited at different potential and different deposition
time exhibit different surface morphologies. At short deposition
time (60s) with constant potential of +0.75V, a thin two
dimensional (2D) PANi film was deposited on the ITO and
adhered strongly on the ITO surface. However, when the
deposition time was prolonged longer, the microgranular and
nanorod-shaped PANI particles started growing upward on the
first layer (thin compact film) and finally the uppermost layer
consisted of compact and dense nano-fibrillar PANi particles
with few small voids. Nevertheless, the top layer was not strongly
adhered on the adherent thin film. On the other hand, deposition
at high potential (+1.50V) for a short time also produced a thick
and dense PANi layer (dark blue in colour) was formed on the
ITO surface with the presence of few voids and crevices. The
electrodeposition of Polyaniline (PANi) at +1.50 V was 2.5 times
faster than at +1.0V and 23 times faster than at +0.75V. The thin
compact PANi film is a promising material to be used in
electrochromic windows due to its good adhesion, transparency
and electrochromism.

I. INTRODUCTION
Conducting polymers are organic electroactive
materials due to the presence of _-conjugated polymers. These
polymers present _-electron delocalization, arising from
conjugated double bonds in the polymer backbone [1]. Thus,
they can reversibly change colors upon electrochemical
doping and de-doping treatments on _-conjugated system. The
properties of conducting polymers are distinctly different
according to their structure, sizes and morphologies.
Research on the synthesis and characterization of
conducting polymers has attracted great attention for the last
two decades due to their wide range of promising applications.

Among the family of conducting polymers, polyaniline

(PANi) has been extensively studied because of its excellent
electrochemical and electrical properties and its potential
applications in various areas such as sensors [2,3], corrosion
protection [4], batteries [5,6], electronic devices [7,8],
electrochromic displays [9,10] etc. It has received increasing
attention as electrochromic materials because of its high color
contrast, multiple color possibilities (polyelectrochromic
material), rapid response times and ease of processing.

The film can be synthesized either chemically by adding

oxidants or electrochemically by applying potentials to the
targeted substrates. Chemical polymerization methods include
template-free method [11], soft-template method [12] and
hard-template method [13]. However, the remaining oxidants
from chemical polymerization method can contaminate the
PANi film and thus affecting the properties of the film. Also,
the use of templates is a tedious process which the removal of
the templates from PANi structure might destroy the film.
Hence, electrochemical deposition of polyaniline is a more
environmentally and desirable method as compared to
chemical method. The discharged solution from
electrochemical process can be easily treated because no toxic
oxidant or surfactant is needed in the process and the
polymerization solution can be used repeatedly [14]. Another
advantage of this method is that the desired polyaniline film
may be deposited onto substrate materials at the desired
quantity and thickness in one single step. The electrochemical
deposition of polyaniline is strongly dependent on various
factors such as temperature [15], pH [16], solvent and dopant
ions used [17,18] and nature of substrate [19].
Electrochemical polymerization of
anilinium
hydrochloride
Abstract: Electropolymerization of anilinium hydrochloride was
carried out on platinum plate electrode in a protic medium by cyclic
voltammetry. The effects on the electrodeposition of the sweep rate,
monomer concentration, pH of the medium and electrode nature are
discussed.

1. Introduction
A polymeric material that possesses the electronic, magnetic, electrical and
optical properties of a metal while retaining the processability and mechanical
properties usually associated with a conventional organic polymer is called a
conducting polymer.
It has been recognized that any organic polymer containing a conjugated π −
electron system can always have metallic conductivity upon addition of electrons or
holes by doping (chemically or electrochemically). Metallic conductivities have been
observed in a number of conjugated systems, for example, polyaniline, polypyrrole,
polythiophene and poly(p-phenylen). In addition to their use as electrical conductors,
conjugated polymers are becoming more and more important as functional materials
in other areas, such as optics (transparent/flexible electrodes and electrochromic
devices), nonlinear optics, microelectronics (light-emitting diodes and organic
transistors), microelectromechanical systems (sensors, rechargeable batteries, and
artificial muscles), electromagnetic devices (static charge dissipating and
electromagnetic shielding), and membranes for selective gas separation. Many of
these concepts are in various stages of development, and some commercial products
such as rechargeable lithium-polymer batteries have been marketed by Seiko, BASF,
and Allied Signal.
Polyaniline (PANI) is probably the oldest organic polymer ever synthesized
(in 1862) [1]. In the early work published in 1910s, it was described as existing in
four different oxidation states; each of them was an octomer. In 1967, Josefowicz et
al. [2] reported that the conductivity of polyaniline increases by several orders of
magnitude when doped in protonic acids with decreasing pH values. Tjey also
recognized that polyaniline could serve as an electrode material for rechargeable
batteries. Unfortunately, all these early studies were fraught with problems such as
uncertain composition and were lost in literature. In 1980 Diaz and Logan [3]
reactivated research on polyanilines and several other groups immediately followed
up during the following decades [4].
Although (PANI) can be prepared by chemical means, the most widely used
technique is electrochemical anodic oxidation. It presents several advantages, such as
absence of catalyst, direct grafting of the doped conducting polymer onto the
electrode surface, and easy control of the film thickness by integration of deposition

charge. Monomer oxidation must occur in a solvent system characterized by a

suitable potential window, and the species produced must react preferentially to form
the polymer. Relatively high monomer concentrations (typically 0.1M) in an acidic
medium are generally used, as well as inert electrodes.
Cyclic voltammetry (CV) is an excellent technique for the investigation of the
best operative conditions. During the first potential scan, the current maximum
corresponds to the monomer oxidation potential. Continuous cycling of the potential
over the peak develops the redox cycle of the growing electroactive PANI. Reversible
oxidation of the polymers (doping-dedoping process) occurs at potentials lower than
that of the corresponding monomer and, therefore, the process is put in evidence
during potential scan.
The mechanism generally accepted for the electropolymerization of aniline by
anodic coupling is shown in scheme 1.
This mechanism is repeated for every cycle of sweeping and it allows interpreting the
augmentation of the concentration of the oxidized specie of the quasi-reversible
couple ( ip increases).
The first step is the formation of an aniline radical cation. This radical aniline is
resonance stabilized as shown in step two of the mechanism. These radicals may then
combine in different ways to form polyaniline. Head-to-tail coupling or 1-, 4-
substitution is believed to predominate and produce p-aminodiphenyl amine in step
three of the mechanism.
We have to notice that the proposed mechanism is the precursor of another
one more complex which explains the polyaniline film formation.
In the present paper, we report electropolymerization from an electrolyte containing
anilinium hydrochloride monomer in an acidified medium. The polymer films have
been studied by cyclic voltammetry. In fact this method reveals qualitatively the
reversibility of electron transfer during the electropolymerization and also examines
the electroactivity of the polymer film because the oxidation and reduction can be
monitored in the form of a current-potential diagram.
Electrochemical Polymerization of Aniline
in Phosphoric Acid

ABSTRACT: The electrochemical synthesis of common conductive polymers such as

polyaniline in phosphoric acid is a little different from that in other acidic media such
as sulfuric acid. Electropolymerization in phosphoric acid is difficult, and this electrolyte
medium is not applicable for this purpose. However, it is possible to overcome
this problem by the addition of a small amount of sulfuric acid. In this case, the electropolymerization
process can be successfully performed when the phosphate ion is
doped. For instance, polyaniline films electrodeposited from an electrolyte solution of
phosphoric acid have good stabilities and useful morphologies. Interestingly, phosphate
doping results in the formation of nanostructures, whereas the polymer surface
is macroscopically smooth. In an appropriate ratio, a mixed electrolyte of H 3PO4 and
H2SO4 can be used for the electropolymerization of aniline; thus, H 2SO4 acts as a
required agent for successful polymer growth, and H3PO4 acts as a doping agent. In
this case, a small amount of sulfate is incorporated into the polymer matrix, which
does not participate in the electrochemical insertion/extraction process. VVC 2006 Wiley
Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3304–3311, 2006
Keywords: conducting polymers; morphology; nanoheterogeneity; nanostructure;
polyaniline

INTRODUCTION
The electrochemical synthesis of conductive polymers
is accompanied by the doping of counterions
into the polymer network. Because the material
properties of conductive polymers are mainly
affected by their doping states,1–12 it is of particular
importance to choose an appropriate medium
for electropolymerization to attain conductive
polymers of desirable properties for various
applications. One of the prototypes of conductive
polymers is polyaniline,13–27 which has a welldefined
electropolymerization process. Indeed, its
electrochemical polymerization serves as an excellent

excellent
model for the study of electropolymerization
processes.
Aniline can be easily oxidized in the presence
of various supporting electrolytes. However, it
should be taken into account that polyaniline
has good conductivity only at low pHs. Thus,
acidic media are appropriate candidates for the
electrochemical synthesis of polyaniline. In this
direction, various acids have been employed for
this purpose.22–27 Among the simple inorganic
acids, phosphoric acid is a common example, but
less attention has been paid to it for the purpose
of electropolymerization. To our knowledge,
there has been no direct report on the electropolymerization
of aniline from a solution of phosphoric
acid. This is due to the fact that electropolymerization
is difficult to be performed in a
medium of phosphoric acid in comparison with
other acidic media. This means that less atten-
tion has been paid to the doping of polyaniline
(and generally conductive polymers) by phosphate
ions. In this context, there are some reports on
the doping of conductive polymers with phosphate
esters.28–30 A few reports have also been
devoted to physical studies of polyaniline doped
with phosphate. These studies are due to the advantageous
properties of conductive polymers
doped with phosphate.31–34 However, it is difficult
to prepare stable films of conductive polymers via
electropolymerization, whereas electrochemical
polymerization is an efficient approach for the
synthesis of conductive polymers and, in some
cases, is the best method for synthesis. Thus, it is
of particular importance to incorporate phosphate
ions into the polymer matrix in the course of electrochemical
synthesis. In this work, we explain
that although electropolymerization from a phosphoric
acid electrolyte is not favorable, it is possible
to design a successful electropolymerization
process resulting in phosphate doping. In other
words, we report a practical approach for the
preparation of phosphate-doped polyaniline (and
generally conductive polymers) via a simple electropolymerization
process under the appropriate
conditions.
c-Fe2O3/Polyaniline-Mesna prepared by
doping/dedoping method
Composite materials are used in all kinds of engineering structures, medical prosthetic
devices, sensors and electromagnetic interference shields and so on. The c-Fe2O3/polyaniline-
Mesna (c-Fe2O3/PANI-Mesna) composite with conducting and superparamagnetic characters
is synthesised in an aqueous hydrochloric acid solution (0?2 mol L21) containing aniline, 1-
ethyl-3-methylimidazolium ethyl sulphate (EMIES) and c-iron sesquioxide (c-Fe2O3) by
using mesna as a dopant and ammonium persulfate [(NH 4)2S2O8] as an oxidant. Fourier
transform infrared spectra (FTIR), X-ray diffraction (XRD) and transmission electron
microscope (TEM) have been used to characterise the c-Fe2O3/PANI-Mesna composite and to
confirm that mesna is doped into c-Fe2O3/PANI chains. The cyclic voltammetry (CV) and
magnetisation studies show that c-Fe2O3/ PANI-Mesna composite has the
superparamagnetism (14 emu g21) and electrochemical activity at pH 4–8. The study provides
an academic foundation for developing some new material for immobilising drugs of
anticancer.

Since the 1980s, the conductive polymer has broken

the traditional concept that polymer was only nonconductor,
1 and it shows extensive application prospect
in many aspects such as electrochemical power source,2
drug3 and sensors.4,5 Polyaniline was synthesised
150 years ago, so it is the oldest one but is one of the
most useful conducting polymers due to its ease of
synthesis, environmental stability and unique acid/base
doping/dedoping and reversible redox mechanism.6 It
can be readily synthesised by either chemical oxidation
or electrochemical polymerisation of aniline under mild
conditions. As an important conducting polymer,7,8–10
PANI has been used in engineering structures, rechargeable
batteries, electrochromic display devices, modified
electrodes and electromagnetic interference shields and
so on.

polyaniline (PANI) is a conducting polymeric material

which can be synthesized either chemically or electrochemically. It has many
applications in various domains. PANI belongs to a group of conducting polymers
prepared by the electrochemical oxidation and simultaneous polymerization of
monomer that reacts at the anode of an electrochemical cell. The electrochemical
preparation and characterization of polyaniline are commonly used [10, 11].

Conducting polymers are of great interest to researchers

in many fields due to their outstanding properties and
numerous possible applications. Polyaniline is one of the
most important conducting polymers because of its high
conductivity, ease of preparation, good environmental
stability, and large variety of applications such as electrochromic
devices, secondary batteries, catalysis, and corrosion
protection coatings [1–4]. The electro-oxidation of
ascorbic acid on various electrodes has been a subject of
several studies. The electrode materials include platinum,
Electrochemical fabrication of polyaniline films containing
gold nanoparticles deposited on titanium electrode
for electro-oxidation of ascorbic acid
Abstract Polyaniline films prepared on titanium were
employed as substrate for the electrodeposition of gold.
The modified electrode was used as anode for the electrooxidation
of ascorbic acid. The electrochemical behavior
and electro-catalytic activity of Au/PAni/Ti electrode were
characterized by cyclic voltammetry. The morphology of
the polyaniline film and gold coating on PAni/Ti electrode
were characterized by scanning electron microscopy
(SEM) and energy-dispersive X-ray (EDX) techniques,
respectively. Results indicated that gold nanoparticles were
homogeneously dispersed on the surface of polyaniline
film. The electro-oxidation of ascorbic acid is found to
proceed more facile on Au/PAni/Ti electrode than on bare
gold electrode. The irreversible oxidation current of
ascorbic acid exhibits a linear dependence on the ascorbic
acid concentration in the range of 1–5 mM.

Introduction
Conducting polymers are of great interest to researchers
in many fields due to their outstanding properties and
numerous possible applications. Polyaniline is one of the
most important conducting polymers because of its high
conductivity, ease of preparation, good environmental
stability, and large variety of applications such as electrochromic
devices, secondary batteries, catalysis, and corrosion
protection coatings [1–4]. The electro-oxidation of
ascorbic acid on various electrodes has been a subject of
several studies. The electrode materials include platinum,

carbon paste electrodes, polypyrrole nanowire-modified

electrode, vanadium oxide polypropylene carbonate-modified
electrode, PEDOT-modified electrode, layer-by-layer
assembled multilayer films of redox polymers, polypyrrole
films containing ferrocyanide ions deposited onto
thermally pre-treated and untreated iron substrate, etc.,
[5–12]. In all these studies, the reaction has been studied
on the bare or the surface-modified noble metals as well
as glassy carbon. The noble metals and glassy carbon
showed good catalytic activity toward oxidation reactions.
Study of electro-oxidation of ascorbic acid on surfacemodified
non-noble electrodes such as titanium, lacking
electro-catalytic activity in their original state, is an
interesting field of research. Additionally, low cost as well
as ease of electrode assembly are favorable factors in
using non-noble metals. Because ascorbate sensors are
anticipated to have potential applications, it would be
beneficial to employ a suitable metal for electro-oxidation
of ascorbic acid. To the best of our knowledge, the
electro-oxidation of ascorbic acid on a polyaniline-coated
non-platinum metals is only reported in two articles in the
literature [13, 14]. Immobilization of the noble metal
nanoparticles in an active matrix may enhance the overall
reactivity of the catalytic metal centers. For example, our
previous studies on the electro-catalytic oxidation of
glycerol and evolution of chlorine on Pt/TiO2/Ti electrode
and electro-catalytic oxidation of glucose on Au/TiO2/Ti
electrode, has shown that the modification of electrode
surface by anodizing of titanium enhances the electrocatalytic
activity to a great extent [15–17]. To date, the
variety of researches has been focused on the using of
nanoparticles and nanocomposites in the electrochemistry
fields [18–21]. The aim of the present work was
to investigate the electro-oxidation of ascorbic acid on
gold nanoparticles dispersed in polyaniline matrices and

analyze the effect of their morphologies on the electrocatalytic

characteristics of this modified electrode. The
polyaniline films were obtained by applying cyclic voltammetry
scans on titanium substrates. Our criteria behind
selecting titanium as substrate for electrodeposition of
polyaniline are its good corrosion resistance and human
body biocompatibility. Gold nanoparticles dispersed on
the polyaniline films by cathodic electrodeposition. The
electro-oxidation of ascorbic acid on Au/PAni/Ti electrodes
was carried out using cyclic voltammetry and the
results are discussed on the basis of differences in their
surface area. The surface morphology and element analysis
of polyaniline films on titanium and gold coating on
polyaniline films were characterized by scanning electron
microscopy (SEM) and energy-dispersive X-ray spectroscopy
(EDX), respectively.