9128 J. Phys. Chem.

C 2009, 113, 9128–9134

Self-Assembly of Poly(o-methoxyaniline) Hollow Microspheres

Lijuan Zhang,* Hui Peng, Jing Sui, Christian Soeller, Paul A. Kilmartin, and
Jadranka Travas-Sejdic*
Polymer Electronics Research Centre, Department of Chemistry, UniVersity of Auckland,
PriVate Bag 92019, Auckland, New Zealand
ReceiVed: January 11, 2009; ReVised Manuscript ReceiVed: March 11, 2009

Hollow microspheres of poly(o-methoxyaniline) (POMA) were prepared in a solution of p-toluenesulfonic

acid (p-TSA) using ammonium persulfate (APS) as oxidant. The morphology of the final polymers was
characterized by scanning electron microscopy and transmission electron microscopy techniques. The molecular
structure and electrical properties of the products were investigated using a range of spectroscopic methods.
The mechanism of nanostructure formation was studied in the light of the chemical nature of the starting
monomer and other synthesis conditions, such as the reaction temperature and time and the concentrations of
the oxidant and of the dopant molecule. It was established that the mechanism of microsphere formation is
based on polymer growth on preformed micelles, which could be seen in freeze-fracture experiments. The
presence of p-TSA led to microspheres with a very regular size distribution. The CH3O- group on the aniline
side chain also increased the electrocatalytic activity of nanostructured POMA films cast on a glassy carbon
electrode for ascorbic acid (AA) oxidation, in comparison with polyaniline nanotubes.

Introduction reaction time, molar ratio of oxidant to o-methoxyaniline

Research into conducting polymers has attracted a great deal
of attention because of promising applications of these materials
in novel polymer electronic devices on the basis of their unique
optical and electronic properties. Recent advances in nanoscience
and nanotechnology have opened up new research fields, both
at a fundamental and an applied level, focused around the
development of novel devices based on nanosized materials.1,2
Synthesis of conducting polymer nanostructures has been
recently reported, with nanotubes, nanowires, and nanospheres
all being formed under various synthesis conditions.3,4 Among
these nanostructures, hollow nanospheres have created much
interest because of their high specific surface area and low
effective density, with potential applications in sensors and
biosensors,5 catalysis, and drug delivery systems.6 Some of the
commonly investigated methods to prepare hollow conducting
polymer nanospheres involve the use of templates.7,8 These
techniques require removal of the template by dissolution,
evaporation, or thermolysis that often destroy the final morphol-
ogy of the hollow nanospheres. The self-assembly method has
the advantage of being simple and it avoids the need for template
dissolving postsynthesis.3,9-11 Polyaniline (PANI) is a conduct-
ing polymer that has gained considerable attention due to its
electrical, electrochemical, optical properties, and environmental
stability.12,13 Development of PANI nanostructures for novel
applications has been a focus of recent research.14-16 We have
prepared a range of PANI nanostructures using the self-assembly
process and demonstrated their use in biosensors and as
oxidative autocatalytic materials.3,6,17
In this paper, we investigate the effect of a methoxy
substituent on the aniline monomer on the morphology and
properties of the poly(o-methoxyaniline) (POMA) obtained via
a simple self-assembly process. The reaction temperature,
* To whom correspondence should be addressed. Tel.: +64 9 373
7599, ext. 85876. Fax: +64 9 3737422. E-mail: lijuan.zhang@auckland.ac.nz
(L.Z.); j.travas-sejdic@auckland.ac.nz (J.T.-S.).
10.1021/jp900267t CCC: $40.75  2009 American Chemical Society
Published on Web 05/05/2009
(OMA), and the molar ratio of p-TSA to monomer were also
studied in order to understand the effect of synthesis parameters
on the formation mechanism of POMA hollow microspheres.
Experimental Section
Materials. o-Methoxyaniline (OMA), p-toluenesulfonic acid
(p-TSA), and ammonium persulfate ((NH4)2S2O8, APS) were
obtained from Sigma-Aldrich Chemical Co. o-Methoxyaniline
was distilled under reduced pressure and stored in the dark under
nitrogen.
Polymerization. A 10 mL aliquot of 0.2 M OMA and a
certain molarity of p-TSA were prepared by dissolving the
reagents in deionized water with magnetic stirring at room
temperature for 30 min. Then the stirring was stopped, and the
solution was kept at 3 °C for 2 h followed by the addition of 5
mL of a precooled solution of 0.6 M APS, which, when added,
gave initial concentrations of o-methoxyaniline ) 0.133 M and
APS ) 0.2 M. The reaction was left to proceed for 12 h, and
the resulting POMA precipitate was washed with water,
methanol, and ether. Finally, the product was dried under
vacuum at room temperature for 24 h.
Characterization. POMA morphologies were investigated
using a Philips XL30S field emission scanning electron micro-
scope (SEM) and a Philips CM12 transmission electron
microscope (TEM). To understand the formation mechanism
of the hollow microspheres, the freeze-fracture technology was
used to investigate the morphology of solutions of o-methoxy-
aniline on its own and o-methoxyaniline combined with p-TSA.
The experimental procedure involved placing a drop of each
solution onto a thin copper sheet as a holder, followed by rapid
quenching in liquid nitrogen. The frozen sample was fractured
with a liquid nitrogen cooled knife using an EE-FED B freeze-
fracture-etching unit in a Balzers 301 vacuum evaporator.
Replicate fracture samples were obtained using unidirectional
shadowing at an angle of 45° with platinum-carbon and
Self-Assembly of POMA Hollow Microspheres J. Phys. Chem. C, Vol. 113, No. 21, 2009 9129

1.5-2.0 nm of mean metal deposit. The replicas were washed

with distilled water and then examined under a Philips CM12
TEM.
The UV-visible absorption spectra of the products dissolved
in m-cresol were recorded from 300 to 1100 nm using a
Shimadzu UV1700 UV-visible spectrophotometer. Infrared
spectra were measured in the range of 400-4000 cm-1 on pellets
made with KBr by means of a Perkin-Elmer 1600 FTIR
spectrophotometer, taking 20 scans at a resolution of 4 cm-1.
X-ray diffraction patterns were taken with a Bruker AXS D8
Advance X-ray diffraction instrument using Cu KR radiation.
The cyclic voltammetry response of the material was deter-
mined using a CHI440 (CH Instruments) electrochemical
workstation. Each sample was first dispersed in ethanol and the
dispersion drop-cast onto a 3 mm diameter glassy carbon
electrode (BioAnalytical Systems) and allowed to dry at room
temperature to form a thin film. The electrochemistry was run
in 0.5 M HCl and in two different citrate/phosphate buffers (pH
3 and pH 6), which were also used to examine the effect of
added ascorbic acid solutions (at 0.01-2 mM), which were
made up immediately prior to use. All of the electrochemical
experiments were undertaken at room temperature, and the
solutions were purged with N2 for approximately 10 min, and
N2 was allowed to flow over the solutions during the measure-
ments to prevent O2 re-entering the cell. Cyclic voltammograms
were recorded at a scan rate of 50 mV s-1, using an Ag/AgCl
(+207 mV vs SHE) reference electrode and a Pt wire counter
electrode.

Results and Discussion

To find the optimal conditions for the formation of POMA
microspheres, the influence of reaction temperature and time
on the polymer morphology was examined. It was found that
the morphology and the yield of POMA microspheres were
strongly affected by the reaction temperature. As shown in
Figure 1A, when the reaction temperature was 3 °C, most of
the products showed spherical structures with an average
diameter of 1.3 ( 0.8 µm. The diameter of spherical structures
became larger (approximately 2.5 µm in diameter), and some
circular flakes were obtained when the reaction was carried out
at 20 °C (Figure 1B). When the reaction temperature was
increased to 40 °C, a large fraction of the product was in the
form of (semi)circular flakes with some larger (>5 µm) spheres
also present (Figure 1C). By contrast, the reaction time did not
have a great affect on the morphology of the POMA micro-
spheres. These results indicate that reaction kinetics plays a Figure 1. SEM images of POMA synthesized from a solution of 0.133
major role in the formation of the hollow microspheres. M o-methoxyaniline, 0.2 M p-TSA, and 0.2 M APS, obtained at
Figure 2 presents SEM images of POMA obtained from the different temperatures: (A) 3, (B) 20, and (C) 40 °C.
solutions with different molar ratios of APS to OMA. One can
see that a half-sphere morphology was obtained when the molar and pale center in the TEM images confirms the hollow
ratio of APS to o-methoxyaniline was 1:1 (Figure 2A), with a structures of POMA microspheres and indicates a shell diameter
half-sphere diameter of approximately 2 µm. The proportion of about 150 ( 10 nm.
of half-spherical forms decreased, and more complete micro- Figure 4 presents UV-visible spectra of the POMA hollow
spheres appeared when the molar ratio of APS to OMA was microspheres dissolved in m-cresol obtained for different molar
increased to 1.25:1 (Figure 2B). The microsphere morphology ratios of APS to OMA. The spectra of the first three products,
became dominant when the molar ratio of APS to OMA obtained at molar ratios of APS to OMA of 1:1, 1.25:1, and
increased further to 1.5:1 and 2:1 (Figure 2C,D). The diameter 1.5:1 (Figure 4A-C), are very similar. The peak centered at
of microspheres obtained at the APS to OMA molar ratio of 330 nm corresponds to the π-π* transition of the benzenoid
2:1 (about 1.1 µm) was smaller than that obtained for a 1.5:1 rings.18 The second peak centered at 420 nm is attributed to the
molar ratio (about 1.8 µm), and in many cases holes could be polaron-π* transition, and the last broad peak centered at 920
observed at some point on the spheres. To investigate whether nm, to delocalized polarons of the emeraldine salt form of the
the POMA microspheres were hollow, TEM images were taken. POMA polyaniline derivative.19-22 However, for POMA ob-
Figure 3 presents TEM images of POMA at an APS to OMA tained with an APS to o-methoxyaniline molar ratio of 2:1
molar ratio of 1.5:1. The sharp contrast between the dark edge (Figure 4D), the peak at 330 nm disappeared, while the peak at
9130 J. Phys. Chem. C, Vol. 113, No. 21, 2009
Figure 2. SEM images of POMA obtained from a solution of 0.133 M o-methoxyaniline and 0.2 M p-TSA, using different molar ratios of APS
to o-methoxyaniline: (A) 1:1, (B) 1.25:1, (C) 1.5:1, and (D) 2:1.
420 nm and the broad band centered at 920 nm decreased in
the intensity, and instead a small broad band centered at 580
nm appeared in the spectrum. The band at 580 nm has previously
been assigned to the pernigraniline form of the polymer23 and
may indicate the high level of oxidation of the POMA obtained
under conditions of high APS concentration. On the basis of
the above results, including both SEM images and UV-visible
spectra, it was concluded that a molar ratio of APS to OMA of
1.5:1 was the optimal ratio for the preparation of well-formed
and conducting POMA hollow microspheres.
Figure 5 shows SEM images of POMA obtained using
different molar ratios of p-TSA to OMA from no p-TSA present
to a 1:1 ratio. The microspheres were not uniform in shape and
size when there was no p-TSA present (Figure 5A), and the
size distribution of the microspheres was between 1.4 and 3.2
µm (inset in Figure 5A). As the molar ratio of p-TSA to OMA
was increased from 0.1:1 to 0.5:1 (Figure 5B-D), the micro-
spheres became more uniform in size, as seen by the narrower
size distributions (insets in Figure 5B-D). The proportion of
microspheres decreased significantly when the molar ratio of
p-TSA to OMA was increased to 0.8:1 (Figure 5E) and
disappeared completely when the molar ratio reached 1:1 (Figure
5F). We can conclude that, at a moderate concentration, p-TSA
can play an important role in producing a more even size
distribution of smaller POMA microspheres but, at higher
concentrations, can lead to destruction of the POMA micro-
sphere morphology.
On the basis of previous reports with polyaniline nanostruc-
tures,17,24-26 OMA droplets (formed due to the low solubility
of o-methoxyaniline in aqueous solutions) and micelles com-
posed of o-methoxyaniline and p-TSA are proposed as soft
templates for the formation of the POMA hollow microspheres.
When the hydrophilic APS oxidant is added, polymerization
would take place at the surface of the OMA droplets and/or at
the micelle/water interface. The polymerized POMA would
Zhang et al.
become larger hollow spheres by accretion and fusion as the
polymerization proceeds, and holes would readily form as OMA
monomer diffuses to the micelle/water interface and as water
and water-soluble compounds enter the interior of the expanding
microspheres.
To establish the existence of micelles in the reaction solution,
the freeze-fracture technique was used to characterize the
morphology of solutions containing OMA and OMA/p-TSA.
Parts A-C of Figure 6 show FF-TEM images of OMA/p-TSA
droplets for different molar ratios of p-TSA to OMA, namely,
(A) no added p-TSA, (B) 0.5:1, and (C) 1:1. In the absence of
added p-TSA, the FF-TEM images revealed nanospheres of
different sizes (in the range from 50 to 200 nm; Figure 6A),
expected to be droplets of OMA. When a molar ratio of p-TSA
to OMA of 0.5:1 was used, more uniform nanospheres in the
range of 50-80 nm diameter (Figure 6B) were observed, which
may originate from p-TSA/OMA micelles, rather than OMA
droplets, since the solubility of o-methoxyaniline increases when
p-TSA is added. At the higher molar ratio of p-TSA to OMA
of 1:1, the morphology was less uniform and was composed of
nanospheres and various merged structures (Figure 6C). These
results are consistent with the SEM images given in Figure 5,
in that in the absence of p-TSA larger and less uniform POMA
microspheres were obtained; with moderate concentrations of
p-TSA (0.5:1 compared to OMA), very even and smaller POMA
microspheres form, while for higher p-TSA concentrations
(1:1) a more granular morphology was obtained without
microspheres.
Figure 7 shows the UV-vis spectra of POMA obtained from
the solutions of different molar ratios of p-TSA to OMA. The
first peak, corresponding to the π-π* transition of the benzenoid
rings, shifts from 310 nm (3.99 eV) to 330 nm (3.75 eV) with
an increase of the molar ratio of p-TSA to OMA from 0.1:1 to
1:1, suggesting longer conjugation length in the polymer when
the p-TSA ratio is increased. The intensity of the broad band at
Self-Assembly of POMA Hollow Microspheres
Figure 3. TEM images of POMA obtained at a molar ratio of APS to
o-methoxyaniline of 1.5:1 (A and B).
Figure 4. UV-vis spectra of POMA dissolved in m-cresol, obtained from
a solution of 0.133 M o-methoxyaniline and 0.2 M p-TSA using different
molar ratios of APS to o-methoxyaniline: (A) 1:1, (B) 1.25:1, (C) 1.5:1,
and (D) 2:1.
>800 nm, which is characteristic of charge carrying POMA,
increased, and the peak position shifted from 900 nm (1.38 eV)
to 920 nm (1.34 eV), with the increase in the molar ratio of
p-TSA to OMA, indicating an increased doping level when a
higher concentration of p-TSA was present.
J. Phys. Chem. C, Vol. 113, No. 21, 2009 9131
Figure 8 presents the FTIR spectra of the POMA obtained
for different molar ratios of p-TSA to OMA. Various bands
typical of POMA can be observed. The characteristic POMA
peaks at 1589 and 1505 cm-1 are attributed to the CdC
stretching of quinoid and benzenoid rings, respectively.27,28 It
needs to be noted that the relative intensity of the 1589-1505
cm-1 band decreased when the molar ratio of p-TSA to OMA
was increased from 0.1:1 to 0.8:1, accompanied by an increase
in the intensity of the peak at 1273 cm-1, ascribed to the C-N+
stretching vibration in the polaron structure, consistent with the
results of the UV-visible spectra (Figure 7).29,30 The low-
intensity peak at 1456 cm-1 is ascribed to the C-H bending of
the -OCH3 group,31 the bands at 1258 and 1024 cm-1 to the
C-O-C stretching of alkyl aryl ether linkage, and the band at
1210 cm-1 to the stretching of secondary aromatic amine.27,32
The bands at 2939 and 2838 cm-1 originate from C-H
stretching vibration in the methoxy (-OCH3) group in POMA
and the methyl (-CH3) group in p-TSA.23,33 The absorption of
aromatic C-H in-plane bending appears at 1127 cm-1 and the
out-of-plane deformation of C-H in the o-substituted benzene
ring at 952 and 810 cm-1.34
Figure 9 shows the XRD patterns of POMA obtained at
different molar ratios of p-TSA to OMA. Two broad peaks
centered at 2θ ) 13 and 26° were observed, which can be
ascribed to the periodicity parallel and perpendicular to the
polymer chains of POMA.35-37 The position of these peaks is
different from that of PANI (with two broad peaks centered at
2θ ) 19 and 25°), which may be caused by the presence of the
CH3O- groups attached on the polymer backbone.
The electrochemical characteristics of the POMA micro-
spheres were investigated by cyclic voltammetry. The POMA
microsphere sample obtained using a molar ratio of p-TSA to
OMA of 0.5:1 was dispersed in ethanol, and the solution was
dropped onto a glassy carbon electrode to form a thin film. The
sample was cycled in 0.1 M HCl at different scan rates, and
the resulting voltammograms are shown in Figure 10. The
electrochemical behavior of the POMA microspheres was
similar to that seen for POMA grown electrochemically on an
inert electrode, with up to three redox processes evident at the
lowest scan rate of 20 mV s-1, although not as well-defined as
with films grown electrochemically.18,38 The oxidation process
with a peak at approximately +260 mV is attributed to the
oxidation of the leucoemeraldine to the protonated emeraldine
form of POMA, and the broad peak at approximately +560
mV is generally assigned to oxidation from the protonated
emeraldine to the fully oxidized pernigraniline form.39-41 At
the higher scan rate of 120 mV s-1, the sets of POMA peaks
largely overlapped into a single set of redox peaks with an
oxidation peak seen at +420 mV.
Parts A and B of Figure 11 show the CVs of the POMA
hollow microsphere electrode in the presence of different
concentrations of ascorbic acid (AA) in pH 3 and pH 6 citrate/
phosphate buffer solutions at a scan rate of 50 mV s-1. In both
cases the conducting polymer acted as an effective redox
mediator for ascorbic acid oxidation, and the oxidation peak
current increased linearly with AA concentration in the range
of 0.1-2 mM; the correlation coefficients were 0.996 and 0.993
in the pH 3 and pH 6 buffer solutions, respectively (see the
figure insets). In this case the onset of ascorbic acid oxidation
occurred at a lower electrode potential for POMA compared to
a redox mediating electrode made up using polyaniline nano-
tubes cast on the glassy carbon electrode, and the peak current
using POMA (of 39 µA for 2 mM AA) was nearly twice as
large as in the PANI nanotube case (23 µA).42 This result
9132 J. Phys. Chem. C, Vol. 113, No. 21, 2009 Zhang et al.

Figure 5. SEM images of POMA obtained from a solution of 0.133 M o-methoxyaniline and 0.2 M APS using different molar ratios of p-TSA
to o-methoxyaniline: (A) no p-TSA, (B) 0.1:1, (C) 0.3:1, (D) 0.5:1, (E) 0.8:1, and (F) 1:1.

indicates that the presence of -OCH3 group on POMA led to a
very effective lowering of the overpotential for the AA oxidation
process, either due to the specific electroactivity of POMA or
as a result of the morphology of the POMA microspheres.
Conclusions
We prepared POMA hollow microspheres in solutions
containing p-TSA using APS as the oxidant through a self-
assembly process. The POMA microspheres were characterized
by SEM, TEM, and a range of spectroscopic methods. The
spherical morphology was found to be highly dependent upon
the molar ratio of APS to OMA and the concentration of p-TSA
in the reaction solution. A moderate level of p-TSA (0.5-1
compared to the o-methoxyaniline monomer) led to small evenly
sized, micrometer sized spheres of POMA. The CH3O- group
attached to aniline played an important role in the formation of
POMA hollow microspheres, given that nanotubes were formed
under similar conditions when pure aniline was used. Moreover,
with a CH3O- group present on the conducting polymer the
electrocatalytic activity for ascorbic acid oxidation of POMA
Self-Assembly of POMA Hollow Microspheres J. Phys. Chem. C, Vol. 113, No. 21, 2009 9133

Figure 7. UV-vis spectra of POMA obtained from a solution of 0.133

M o-methoxyaniline and 0.2 M APS using different molar ratios of
p-TSA to o-methoxyaniline: (A) no p-TSA, (B) 0.3:1, (C) 0.5:1, and
(D) 0.8:1.

Figure 8. FTIR spectra of POMA obtained from a solution of 0.133

M o-methoxyaniline and 0.2 M APS using different molar ratios of
p-TSA to o-methoxyaniline: (A) no p-TSA, (B) 0.3:1, (C) 0.5:1, and
(D) 0.8:1.

Figure 6. FF-TEM images of a 0.133 M o-methoxyaniline emulsion

for different molar ratios of p-TSA to o-methoxyaniline: (A) no p-TSA,
(B) 0.5:1, and (C) 1:1.

films cast on a glassy carbon electrode increased compared with

a film cast from polyaniline nanotubes. The electrochemical
activity and hollow structure of the POMA micropsheres may
allow the use of these materials in electrochemical sensors for
biomedical applications and in drug delivery systems.

Acknowledgment. We gratefully acknowledge a University Figure 9. XRD scattering curve of POMA obtained from a solution
of Auckland Research Committee Grant (No. 3606261) and the of 0.133 M o-methoxyaniline and 0.2 M APS using different molar
New Zealand Foundation for Science and Technology (Contract ratios of p-TSA to o-methoxyaniline: (A) no p-TSA, (B) 0.3:1, and
No. UOAX0806). (C) 0.5:1.
9134 J. Phys. Chem. C, Vol. 113, No. 21, 2009
Figure 10. Cyclic voltammograms of POMA microspheres, obtained
from a solution of 0.133 M o-methoxyaniline, 0.2 M APS, and 0.2
M p-TSA, cast on a glassy carbon electrode, in 0.1 M HCl solution,
and cycled at scan rates of 20-120 mV s-1 (increasing in 20 mV
s-1 steps).
Figure 11. Cyclic voltammograms of POMA microspheres, obtained
from a solution of 0.133 M o-methoxyaniline, 0.2 M APS, and 0.2 M
p-TSA, and cast on a glassy carbon electrode, in the presence of ascorbic
acid at concentrations 0, 0.01, 0.05, 0.1, 0.2, 0.5, 1, and 2 M, in a (A)
pH 3 and (B) pH 6 citrate/phosphate buffer solution at a scan rate of
50 mV s-1.
Zhang et al.
References and Notes
(1) Martin, C. R. Chem. Mater. 1996, 8, 1739.
(2) Martin, C. R. Science 1994, 266, 1961.
(3) Zhang, L.; Peng, H.; Hsu, C. F.; Kilmartin, P. A.; Travas-Sejdic,
J. Nanotechnology 2007, 18, 115607/1.
(4) Trchova, M.; Sedenkova, I.; Konyushenko, E. N.; Stejskal, J.;
Holler, P.; Ciric-Marjanovic, G. J. Phys. Chem. B 2006, 110, 9461.
(5) Virji, S.; Huang, J.; Kaner, R. B.; Weiller, B. H. Nano Lett. 2004,
4, 491.
(6) Zhang, L.; Peng, H.; Kilmartin, P. A.; Soeller, C.; Travas-Sejdic,
J. Electroanalysis 2007, 19, 870.
(7) Caruso, F. Chem.sEur. J. 2000, 6, 413.
(8) Donath, E.; Moya, S.; Neu, B.; Sukhorukov, G. B.; Georgieva, R.;
Voigt, A.; Baumler, H.; Kiesewetter, H.; Mohwald, H. Chem.sEur. J. 2002,
8, 5481.
(9) Konyushenko, E. N.; Stejskal, J.; Sedenkova, I.; Trchova, M.;
Sapurina, I.; Cieslar, M.; Prokes, J. Polym. Int. 2006, 55, 31.
(10) Huang, K.; Wan, M. Synth. Met. 2003, 135-136, 173.
(11) Kovtyukhova, N. I.; Gorchinskiy, A. D.; Waraksa, C. Mater.
Sci.Eng., B 2000, 69-70, 424.
(12) MacDiarmid, A. G. Angew. Chem., Int. Ed. 2001, 40, 2581.
(13) Pauliukaite, R.; Brett, C. M. A.; Monkman, A. P. Electrochim. Acta
2004, 50, 159.
(14) He, Y. Appl. Surf. Sci. 2006, 252, 2115.
(15) Zhang, L.; Long, Y.; Chen, Z.; Wan, M. AdV. Funct. Mater. 2004,
14, 693.
(16) Huang, K.; Wan, M. Chem. Mater. 2002, 14, 3486.
(17) Zhang, L.; Peng, H.; Zujovic, Z. D.; Kilmartin, P. A.; Travas-Sejdic,
J. Macromol. Chem. Phys. 2007, 208, 1210.
(18) Goncalves, D.; dos Santos, D. S., Jr.; Mattoso, L. H. C.; Karasz,
F. E.; Akcelrud, L.; Faria, R. M. Synth. Met. 1997, 90, 5.
(19) Ribeiro Paulo, A.; Steitz, R.; Lopis Irina, E.; Haas, H.; Souza Nara,
C.; Oliveira Osvaldo, N., Jr.; Raposo, M. J. Nanosci. Nanotechnol. 2006,
6, 1396.
(20) Raposo, M.; Mattoso, L. H. C.; Oliveira, O. N., Jr. Thin Solid Films
1998, 327-329, 739.
(21) Gupta, M. C.; Warhadpande, S. V.; Umare, S. S. Indian J. Chem.,
Sect. A: Inorg., Bio-inorg., Phys., Theor. Anal. Chem. 1993, 32A, 298.
(22) Xia, Y.; Wiesinger, J. M.; MacDiarmid, A. G.; Epstein, A. J. Chem.
Mater. 1995, 7, 443.
(23) Kulkarni, M. V.; Viswanath, A. K. Sens. Actuators, B 2005, 107,
791.
(24) Zhang, L.; Wan, M.; Wei, Y. Macromol. Rapid Commun. 2006,
27, 366.
(25) Han, J.; Song, G.; Guo, R. Chem. Mater. 2007, 19, 973.
(26) Han, J.; Song, G.; Guo, R. AdV. Mater. (Weinheim, Ger.) 2006,
18, 3140.
(27) Jamal, R.; Abdiryim, T.; Ding, Y.; Nurulla, I. J. Polym. Res. 2008,
15, 75.
(28) Gruger, A.; Novak, A.; Regis, A.; Colomban, P. J. Mol. Struct.
1994, 328, 153.
(29) Sapurina, I.; Mokeev, M.; Lavrentev, V.; Zgonnik, V.; Trchova,
M.; Hlavata, D.; Stejskal, J. Eur. Polym. J. 2000, 36, 2321.
(30) Gospodinova, N.; Terlemezyan, L. Prog. Polym. Sci. 1998, 23,
1443.
(31) Hasik, M.; Wenda, E.; Paluszkiewicz, C.; Bernasik, A.; Camra, J.
Synth. Met. 2004, 143, 341.
(32) Macinnes, D., Jr.; Funt, B. L. Synth. Met. 1988, 25, 235.
(33) Patil, S.; Mahajan, J. R.; More, M. A.; Patil, P. P. Mater. Chem.
Phys. 1999, 58, 31.
(34) Tan, Y.; Bai, F.; Wang, D.; Peng, Q.; Wang, X.; Li, Y. Chem.
Mater. 2007, 19, 5773.
(35) Gupta, M. C.; Umare, S. S. Macromolecules 1992, 25, 138.
(36) Mattoso, L. H. C.; Bulhoes, L. O. S. Synth. Met. 1992, 52, 171.
(37) Moon, Y. B.; Cao, Y.; Smith, P.; Heeger, A. J. Polym. Commun.
1989, 30, 196.
(38) Kilmartin, P. A.; Wright, G. A. Synth. Met. 1999, 104, 145.
(39) Bernard, M. C.; Hugot-Le Goff, A.; Arkoub, H.; Saidani, B.
Electrochim. Acta 2007, 52, 5030.
(40) Patil, S.; More, M. A.; Patil, P. P. J. Appl. Polym. Sci. 1999, 74,
3009.
(41) Pistoia, G.; Montesperelli, G.; Nunziante, P. J. Mol. Electron. 1990,
6, 89.
(42) Zhang, L.; Peng, H.; Kilmartin, P. A.; Soeller, C.; Travas-Sejdic,
J. Macromolecules 2008, 41, 7671.
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