Synthetic Metals 129 (2002) 303±308

Electrical conductivity response of polyaniline ®lms

to ethanol±water mixtures
L. Tarachiwina, P. Kiattibutra, L. Ruangchuaya, A. Sirivata,*, J. Schwankb
a
The Petroleum and Petrochemical College, Chulalongkorn University, Phya Thai Road Soi Chulalongkorn, Bangkok 10330, Thailand
b
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109-2136, USA
Received 8 May 2001; received in revised form 23 January 2002; accepted 6 May 2002

Abstract

Polyaniline emeraldine base was chemically synthesized and converted to polyaniline emeraldine salts through the protonation doping
process using HCl and CH3COOH as the acid dopants. The doped polyanilines were characterized by ultraviolet±visible (UV±VIS)
spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, TGA, GPC. The four-point probe technique was used to evaluate the effect of
dopant type and doping molar ratio on the speci®c conductivity. Weak acid doping, by CH3COOH, produces ®lms with the speci®c
conductivity which depends solely on the degree of protonation, or the number of charge carriers. On the other hand, stronger acid doping by
HCl can induce crystalline domains, a greater electron mobility and hence a greater speci®c conductivity value. The speci®c conductivity of
the HCl-doped and CH3COOH-doped polyaniline ®lms responds with positive increments upon exposed to water and ethanol. The interchain
H-transfer is suggested to be a common mechanism which increases electron mobility upon exposure to water and ethanol, whereas additional
protonation occurs only with the exposure to water. No evidence for ethanol molecules to interact chemically with the doped polyaniline ®lms
was found. The ®lm electrical conductivity sensitivity is inversely proportional to ethanol concentration, with a higher sensitivity to
concentration found in the ®lm doped with the acid with a lower pKa value.
# 2002 Published by Elsevier Science B.V.

Keywords: Polyaniline emeraldine salts; Protonic acid doping; Speci®c electrical conductivity; Exposures to water and ethanol

1. Introduction polarons resulting from an ``internal'' redox reaction. The

Polyaniline constitutes an important class of conductive
polymers known and it can be synthesized either by chemical
or electrochemical oxidative polymerizations [1,2]. In the
emeraldine base form, or the half-oxidized form, the number
of amine nitrogen atoms is equal to the number of imine
nitrogen atoms; therefore, emeraldine base is also called
poly(phenylene amine±imine) [1]. The structure of emeral-
dine base consists of two amine nitrogen atoms followed by
two imine nitrogen atoms. The imine nitrogen indeed con-
tributes a single p electron, with its lone pair lying within the
molecular plane. Emeraldine base can be doped through a
doping process called the protonation doping. Reaction of
polyaniline emeraldine base in aqueous HCl solution results
in a complete or partial protonation of the imine nitrogens to
give a protonated emeraldine hydrochloride salt [3]. The
protonated polyaniline is actually polysemiquinone radical
cation [1,4]; one resonance form consists of two separated
*
Corresponding author. Tel.: ‡66-2-218-4131; fax: ‡66-2-611-7221.
E-mail address: anuvat.s@chula.ac.th (A. Sirivat).
polarons are then separated into polaron lattice to minimize
the eletrostatic repulsion between positive charges [1]. The
overall structure is expected to have extensive spins and
charge delocalization, resulting in a half-®lled polaron con-
duction band and an increase in the electrical conductivity by
several orders of magnitude without any changes in the
number of electrons on the polyaniline backbone [3,4].
In recent applications of polyaniline, in its conductive
form of emeraldine salt, it has been used as a sensor material
in solution sensor applications. Polyaniline was used to
entrap enzyme glucose oxidase [5±11], used as a pH trans-
ducer [12], used as a chlorine biosensor [13], used as a
deposited ferrocene-modi®ed polyaniline ®lm to detect
hydrogen peroxide [14], used in fabricating a glucose
amperometric sensor [15], used in fabricating a urea bio-
sensor [16], and used as a sensor to detect aliphatic alcohol
vapors [17,18]. Recently, interactions with water [19±21]
and methanol [22] have been speci®cally investigated.
In the present work, we are interested in utilizing con-
ductive polymers, in particular doped polyaniline, in detect-
ing ethanol concentration in ethanol±water mixtures.

0379-6779/02/$ ± see front matter # 2002 Published by Elsevier Science B.V.

PII: S 0 3 7 9 - 6 7 7 9 ( 0 2 ) 0 0 1 1 2 - 1
304 L. Tarachiwin et al. / Synthetic Metals 129 (2002) 303±308
Ethanol molecule is relatively small compared to other
aliphatic alcohols; it is used widely in foods and beverages
and possibly as a substitute for regular gasoline. The essen-
tial requirements for an effective sensor material are: (a)
sensitivity which includes the change in sensor speci®c
conductivity for a given concentration, the lowest detectable
concentration, and the highest saturated concentration; (b)
selectivity for a particular chemical species; and (c) tem-
poral response. We shall report our study on the effect of
dopant type and doping molar ratio on the sensitivity and
selectivity of the polyaniline electrical conductivity upon
exposed to ethanol±water mixtures. The effect on temporal
response shall be reported elsewhere.
2. Experimental
2.1. Materials
Aniline monomer (Merck) was puri®ed prior to use.
Ammonium peroxydisulphate ((NH4)2S2O8) (Merck) was
used as an oxidant. HCl (BDH Laboratory) and CH3COOH
(Lab-Scan) were used as received as acid dopants. N-
methyl-2-pyrrolidone (Lab-Scan) was used as the solvent
in preparing polyaniline solutions for the ultraviolet±visible
(UV±VIS) spectra and for ®lm casting. N-Methyl-2-pyrro-
lidone (Lab-Scan), HPLC grade, was used as the mobile
phase in gel permeation chromatography.
2.2. Synthesis of polyaniline emeraldine base
Polyaniline emeraldine base was synthesized according to
the method described earlier [23]. Aniline monomer was
puri®ed by distillation under reduced pressure at 50±60 8C.
A 0.05 mol of puri®ed aniline monomers was dissolved in
300 ml of 1 M HCl aqueous solution and cooled at 0±5 8C
in an ice bath. A 0.01 mol of (NH4)2S2O8 was dissolved in
100 ml of 1 M HCl aqueous solution, then it was slowly
added into the previous aniline solution and the mixture was
vigorously stirred for 2 h at 0±5 8C. The polyaniline hydro-
chloride, PAN/Cl , was ®ltrated and repeatedly washed with
750 ml of 1 M HCl aqueous solution, 750 ml of deionized
water, and 750 ml of 0.1 M NH4OH until the ®ltrate was
colorless. Polyaniline hydrochloride was treated in a 500 ml
of 0.1 M NH4OH solution, by stirring vigorously for a period
of 5 h and ®nally converted to emeraldine base. The product,
the polyaniline emeraldine base, was ®ltrated and washed
with 750 ml of 1 M NH4OH solution and deionized water
until the ®ltrate was neutral. Polyaniline emeraldine base
powder was dried in a vacuum oven at 40±50 8C for a period
of 3 days and then stored in a dessicator at room temperature
for later use.
2.3. Preparation of doped polyaniline emeraldine salt films
Four grams of polyaniline emeraldine base was dissolved
in 1000 ml of N-methyl-2-pyrrolidone and the solution was
stirred for 5 h at room temperature. Eight milliliters of the
solution was then mixed with an acid dopant of a known
concentration, and the mixture was stirred for 15±20 h at
room temperature. Two acids were used as the dopants: HCl
and CH3COOH with the corresponding pKa values of 6.10
and 4.76, respectively. A 0.5 ml of doped polyaniline solu-
tion was cast on a glass slide and the solvent was allowed to
evaporate in a vacuum oven for a period between 96 and
100 h at 40±50 8C. The casting process was repeated several
times and the typical ®lm thickness obtained was between 12
and 20 mm.
2.4. Characterizations of undoped and doped polyanilines
The ultraviolet±visible (UV±VIS) spectra of polyaniline
were obtained from a UV±VIS spectrometer (Perkin-Elmer,
model Lambda 10) in the wavelength range of 300±900 nm.
The light source was a deuterium lamp. N-methyl-2-pyrro-
lidone was used as the solvent to prepare the sample polyani-
line solutions at the concentration of 0.1 g/l.
The Fourier transform-infrared (FT-IR) spectra of poly-
aniline were obtained from a FT-IR spectrometer (Bruker,
model FRA 106/S) in the absorbance mode with 20 scans at
the resolution of 4 cm 1 covering the wavenumber between
400 and 4000 cm 1. A deuterated triglycine sulfate detector
was used. Spectroscopy grade KBr (Carlo Erba) was used as
the binding material. Polyaniline samples were mixed with
dried KBr, ground and pelletized.
A thermal gravimetric analyzer (Dupont, model TGA
2950) was used to study thermal stability and to determine
the decomposition temperature of polyanilines synthesized
at a heating rate of 20 8C/min.
A gel permeation chromatography (Waters, 150C-Plus)
was used to determine the molecular weight of polyaniline
emeraldine base synthesized. We used an ultrastyragel
column at 85 8C with NMP (Lab-Scan, HPLC grade) as
the mobile phase, and known molecular weight polystyrenes
were used as the standards for the calibration curve. Elution
time was detected by a refractometer. Polyaniline emeral-
dine base powder was ®rst dissolved in NMP at the con-
centration of 0.6 wt.%, and the solution was ®ltered through
a 0.2 mm PTFE ®lter.
An X-ray diffractometer (Rigaku, model D/MAX-2000)
was used to obtain the diffraction patterns and the degree of
crystallinity. The measurements were carried out in the
continuous mode with a scan speed of 58/min covering
the angle 2y between 5 and 508. Cu Ka1 was used as the
X-ray source.
Custom made four-point probe and associated electrical
units [24] were used to measure speci®c conductivity of
polyaniline ®lms under atmospheric conditions or under the
exposures to water, ethanol or their mixtures. The four-point
probe built was of a rectangular array geometry. A current of
0.05 mA was applied between probes numbered 1 and 2 and
the resultant voltage was measured across the probes num-
bered 3 and 4; the direction between the probes numbered 1
 L. Tarachiwin et al. / Synthetic Metals 129 (2002) 303±308
and 2 is parallel to that of the probe numbered 3 and 4. The
speci®c conductivity was calculated from s ˆ 1=KVt, where
K is the geometric correction factor or the ratio of the probe
width (distance between probes numbered 1 and 3) divided
by the probe length (distance between probes numbered 1
and 2), V the measured voltage drop over the probe length,
and t the polyaniline ®lm thickness. In preliminary tests, the
current used was varied in order to verify that the voltage
drop was in the Ohmic regime. The geometric correction
factor K was calibrated and obtained from SiO2 sheets
of known resistance values. In the study of the effect of
exposures to water, ethanol and their mixtures, 2.0 ml
of prepared solution was pipetted and dropped onto a
polyaniline ®lm without allowing any contact with the four
probes. The ®lm and solution temperatures were maintained
at 25 8C before measurements were taken.
3. Results and discussion
3.1. Characterizations of polyaniline emeraldine base
and salts
We veri®ed that the undoped and doped polymers synthe-
sized were polyaniline emearaldine base and salts by inves-
tigating their UV±VIS spectra. At a low doping molar ratio
(Na/NEB) for HCl-doped polyaniline, two absorption bands
were observed: the bands at 325 and 625 nm. These two
absorption peaks corresponded to the p±p transition of the
benzenoid ring and the exciton absorption of the quinoid
ring, respectively [25]. These two absorption peaks were
also found in an undoped polyaniline emeraldine base
synthesized. At a higher doping molar ratio, two new
absorption peaks were identi®ed. The peak at 865 nm repre-
sented the polaron species, replacing the absorbance peak of
625 nm which disappeared completely. The shoulder peak at
420 nm represented the bipolaron species which were also
present, but in a smaller proportion relative to the polaron
species. For the other protonic acid used, CH3COOH, the
absorption bands in the UV±VIS spectra at 420 and 865 nm
appeared in all of the doped polyanilines, provided doping
molar ratio was suf®ciently large. Our UV±VIS spectra
results are consistent with those reported previously [4].
A FT-IR spectrum of the polyaniline emeraldine base was
measured. There were ®ve important absorption bands pre-
sent. The band at 1590 cm 1 represented the CˆˆN stretch-
ing of the quinoid ring. The band at 1495 cm 1 indicated the
stretching of the benzenoid ring. The C±N stretching of the
benzenoid ring appeared as the 1299 cm 1 band. The band at
1163 cm 1 re¯ected the in-plane C±H bending motion of the
quinoid ring and the band at 827 cm 1 was identi®ed with
the out-of-plane bending of C±H bond in the aromatic ring.
The peaks identi®ed are consistent with previously pub-
lished data [26,27].
FT-IR spectra of the PANI/HCl ®lms of various molar
ratios were measured. There were ®ve new bands present:
305
1735, 1154, 1054, 1014, and 854 cm 1. The band at
1735 cm 1 represented the CˆˆO stretching of NMP mole-
cules in the polyaniline ®lms [23]. The band at 1154 cm 1,
appearing at high values of the molar ratio, indicated the
broken symmetry mode of the quinoid ring [28]. The bands
of 1054 and 1014 cm 1, not present in the FT-IR spectra at
the low value of Na/NEB but visible at high value of Na/NEB,
represented the substitutions of excess chloride ions onto
the meta-position and ortho-position, respectively [29].
The band at 854 cm 1, representing the out of plane
bending of the aromatic ring [27], resulted from the shift
of the band at 827 cm 1 of the emeraldine base due to the
change from the quinoid structure to the benzenoid struc-
ture upon doping. FT-IR spectra of the PANI/CH3COOH
®lms were also measured and the peaks were identical to
those of the undoped PANI ®lms because CH3COOH is a
weak acid and has less ef®ciency to protonate H‡ on the
polymer chain even at relatively high doping molar ratios
used.
Thermal gravimetric analysis thermogram of polyaniline
emeraldine base was recorded in N2 atmosphere showing a
two-step weight loss behavior. The ®rst step, with 1±2 wt.%
loss occurring at temperature around 70 8C, can be attributed
to the loss of water molecules [30]. The second step occurred
at 510 8C where the skeletal of emeraldine base decomposed
[31]. For both PANI/HCl and PANI/CH3COOH polyaniline
®lms, a three-step weight loss behavior was observed. The
®rst step, occurring between 50 and 100 8C, was due to loss
of water. The second step, at approximately 200 8C, origi-
nated from the evaporation of NMP solvent molecules. The
third step corresponded to the loss of acid dopants and the
decomposition of polyaniline backbone; the decomposition
temperatures found were 400 8C for PANI/HCl and 500 8C
for PANI/CH3COOH.
Finally, we determined the molecular weight of the
polyaniline emeraldine base synthesized by GPC. Two
samples from two separate syntheses but of identical pro-
cedure were used. The average Mw and Mn values found
were 89,000 and 21,000, respectively and the corresponding
polydispersity was 4.16.
3.2. Electrical conductivity
Subsequent studies on speci®c conductivity of all polyani-
line ®lms were carried out with the ®lms which had been
previously dried in a vacuum oven at 40±50 8C for a period
of 3 days to reduce water contents to be as low as 2±3 wt.%.
In all speci®c electrical conductivity measurements, tem-
perature was kept between 25 and 27 8C and the relative
open air humidity was between 65 and 70%.
Fig. 1a and b show speci®c conductivity of PANI/HCl and
PANI/CH3COOH ®lms of various doping molar ratios under
the exposures to air, water and pure ethanol. In air, the
speci®c conductivity of PANI/HCl ®lms rises and then
declines with the doping molar ratio, Na/NEB. On the other
hand, the speci®c conductivity of the PANI/CH3COOH ®lms
306 L. Tarachiwin et al. / Synthetic Metals 129 (2002) 303±308
Fig. 1. (a) The specific conductivity of PANI/HCl films vs. doping molar
ratio, Na/NEB, under the exposures to air, water, and pure ethanol. The
temperature was between 25 and 27 8C and the open air relative humidity
was between 65 and 70%. (b) The specific conductivity of PANI/
CH3COOH films vs. doping molar ratio, Na/NEB, under the exposures to
air, water, and pure ethanol. The temperature was between 25 and 27 8C
and the open air relative humidity was between 65 and 70%.
gradually increases toward a constant value of about 0.01 S/cm
when Na/NEB is large.
The rise and decline in speci®c conductivity of PANI/HCl
®lms re¯ect the similar behavior observed in crystallinity. At
low doping molar ratios, the X-ray pattern consists only of a
broad band at 2y 258, characteristic of an amorphous
region [32]. At the doping molar ratio of 98, the X-ray
pattern contains several distinct peaks, suggesting some
crystalline domains present. The characteristic peak at 2y
11.08, d-spacing 8.04 A Ê , represents the average distance
between the polymer chains. The larger peak at 2y 14.68,
d-spacing 5.94 A Ê , corresponds to the distance between N
and the Cl counterions. These two X-ray peaks identi®ed are
consistent with those in a previously published result [32]
where they found d-spacings of 9.57 and 5.94 A Ê , respec-
tively. Other characteristic peaks of 2y 21.4, 26.0, 27.5,
28.8 30.5, 32.7, and 39.18 which appeared are similar to
those found previously [32]. At the doping molar ratios of
980 and 9800, the X-ray patterns show only broad bands at
2y 258.
For the PANI/CH3COOH ®lms, we found no evidence for
crystalline domains from their X-ray diffraction patterns.
Only a broad band at 2y 258 appeared, characteristic of
an X-ray diffraction pattern of an amorphous region [32].
The gradual increase in speci®c conductivity of PANI/
CH3COOH ®lms can be mainly attributed to higher doping
levels or larger numbers of charge carriers available. We
note that HCl is a relatively stronger acid whose pKa value is
6.10, whereas CH3COOH is a weaker acid with its pKa
value of 4.76 [33]. HCl with a lower pKa value has a higher
ef®ciency to donate H‡; polaron and bipolaron states can be
formed at very low acid/emeraldine base molar ratios and
induce crystallinity observed.
When PANI/HCl and PANI/CH3COOH ®lms were
exposed to water and pure ethanol at temperature between
25 and 27 8C, their speci®c conductivity increased. The
increments in speci®c conductivity upon exposure to water
were larger than those found when exposed to ethanol for
both PANI/HCl and PANI/CH3COOH ®lms, and at all
doping molar ratios investigated. This is equivalent to a
negative change in ®lm resistance observed under an expo-
sure to ethanol vapor [18].
The mechanism for the increase in speci®c conductivity
under the water exposure can be given in terms of the
interchain H‡-transfer [4] where water molecules act as
carriers to transfer H‡ from one chain to another. The inter-
chain H‡-transfer results in (a) the protonation on some
quinoid segments in which electrons can delocalize more
effectively along the chain, and (b) an increase in the inter-
chain charge mobility, and hence the increase in the speci®c
electrical conductivity observed. The same interchain H‡-
transfer mechanism can be applied to the ®lms exposed to
ethanol. However, the smaller increase in speci®c conductivity
observed under the exposure to ethanol can be partially
attributed to the larger size of ethanol molecules which have
a lower molecular diffusivity and therefore a lower interchain
electron mobility. The difference in electrical conductivity
response may also re¯ect the differences in solvatochromic
parameters between water and ethanol: ethanol has larger
polarizability and dispersion interactions, whereas dipolar
interactions are nearly the same [17]. A higher H-bond basicity
of water is the main factor here. Water molecule has a higher
ability to cause the H‡ transfer and hence induce a higher ionic
conductivity. A recent model of a variable size metallic island,
based on the increased size of the metallic islands in the
presence of water, has also been proposed [20,21].
The interaction between water and ethanol molecules
with PANI/HCl was investigated by means of FT-IR spectro-
scopy. Fig. 2 shows three FT-IR spectra of the polyaniline
 L. Tarachiwin et al. / Synthetic Metals 129 (2002) 303±308 307

Fig. 2. The FT-IR spectra of PANI/HCl films (Na =NEB ˆ 98): (a) without
exposures to water and ethanol; (b) after exposure to water; (c) after
exposure to pure ethanol.

®lms under the exposures to air, water and ethanol respec-

tively. The ®lms exposed to water and ethanol were allowed
to dry at room temperature before sample preparations and
measurements were taken. All three FT-IR spectra were
nearly the same except that two peaks are now more visible
in the water-exposed ®lm. The more pronounced peaks are at
1493 and 1317 cm 1, representing the stretching mode of N-
benzenoid±N segment, and the stretching modes of quinoid±
benzenoid±quinoid segment/quinoid±benzenoid±benzenoid
segment/benzenoid±benzenoid±quinoid segment [34],
respectively. These two absorption bands indicate that some
quinoid segments may have been protonated and more
benzenoid segments were present. The absorption peak at
1153 cm 1, which represents the broken symmetry mode of
quinoid structure, also increased because of a greater degree
of protonation. For the PANI/HCl ®lm exposed to ethanol,
no new peak occurred in the FT-IR spectrum shown. Simi-
larly, the FT-IR spectrum of PANI/CH3COOH ®lm exposed
to ethanol showed the absorption bands identical to those of Fig. 3. (a) The specific conductivity of PANI/HCl films (Na =NEB ˆ 98)
a ®lm without an exposure. This suggests that ethanol vs. ethanol concentration. The temperature was between 25 and 27 8C, and
molecules do not permanently change with the polyaniline the open air relative humidity was between 65 and 70%. (b) The specific
emeraldine salt. conductivity of PANI/CH3COOH films (Na =NEB ˆ 5900) vs. ethanol
concentration. The temperature was between 25 and 27 8C, and the open
air relative humidity was between 65 and 70%.
3.3. Effect of ethanol concentration

Fig. 3a and 3b show speci®c conductivity versus ethanol
concentration of PANI/HCl and PANI/CH3COOH ®lms at
25 8C. The doping molar ratios, Na/NEB, were 98 and 5900
corresponding to their maximum speci®c electrical conduc-
tivity attainable in air, respectively. There are three response
regimes depending upon ethanol concentration. At low
ethanol concentrations, speci®c electrical conductivity
was independent of ethanol concentration, indicating that
no measurable physical or chemical adsorption taking place.
The minimum detectable concentration can be de®ned as the
concentration required for a polyaniline ®lm to become
sensitive to the presence of ethanol. They were 1.7 and
2.8 M for the PANI/HCl and PANI/CH3COOH ®lms, respec-
tively. At intermediate ethanol concentrations, speci®c elec-
trical conductivity was inversely proportional to ethanol
concentration with sensitivity equal to 1:91  10 3 and
1:1  10 4 S/(cm M) for the PANI/HCl and PANI/
CH3COOH ®lms, respectively. The last regime corresponds
to the concentration range in which speci®c conductivity
was independent of ethanol concentration; polyaniline ®lms
were saturated with ethanol molecules. The saturated con-
centrations were 8.3 M and 10.2 M for the PANI/HCl and
PANI/CH3COOH ®lms, respectively. The large difference in
concentration dependence observed for the PANI/HCl ®lm,
by an order of magnitude, can be attributed to the Cl anions
present and the greater degree of crystallinity induced.
308 L. Tarachiwin et al. / Synthetic Metals 129 (2002) 303±308
4. Conclusion
We have studied the effect of dopant type and concentra-
tion on speci®c conductivity of polyaniline ®lms under
atmospheric conditions and under exposures to water and
ethanol. PANI/HCl ®lms fabricated contained some crystal-
line domains causing a greater speci®c conductivity than
that of PANI/CH3COOH ®lms for the same doping molar
ratio; HCl is a relatively stronger acid with a greater
ef®ciency to protonate the emeraldine base. The speci®c
electrical conductivity of the PANI/HCl and PANI/
CH3COOH ®lms increases upon the exposures to ethanol
and water, with greater increments occurring with water at
all doping molar ratios studied. Interchain H‡-transfer is
suggested to be a common mechanism that induces ionic
electron mobility, whereas an additional protonation occurs
along the polymer chain upon the exposure to water. Ethanol
molecules do not permanently interact with the PANI/HCl
studied, only ionic conduction occurs. The speci®c conduc-
tivity of the PANI/HCl and PANI/CH3COOH ®lms studied is
inversely proportional to ethanol concentration. The sensi-
tivity to ethanol concentration can be varied by at least an
order of magnitude by changing the type of the acid dopant
used; a stronger acid induces higher crystallinity and gives a
polyaniline ®lm which has a greater ethanol concentration
sensitivity.
Acknowledgements
L.R. and A.S. would like to acknowledge the ®nancial
support from the Rajadapisek Fund of Chulalongkorn Uni-
versity, the RGJ grant from TRF, no. PHD/4/2541, and the
BGJ award from TRF, no. BGJ/5/2543. The authors are
grateful of the laboratory assistance provided from P. Saeng-
sawang, J. Amornlertratanatada, and C.P.O. Poon Arjpru.
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