7th International Science, SocialSciences, Engineering and Energy Conference
24-26 November, 2015, Wangchan Riverview Hotel, Phitsanulok, Thailand
I-SEEC 2015
http//iseec2015.psru.ac.th
Electrochemical Fabrication of Functionalized Polypyrrole/
Graphene Oxide Composite Thin Film for
Biosensor Application
Arraya Kertyooa, Waridsara Ruangnoia, Jantamanee Kongpuaka,
Supriya Theanpana, Rapiphun Janmaneea,e1
a
Department of Chemistry, Faculty of Science and Technology, Pibulsongkram Rajabhat University, Phitsanuloke 65000,
THAILAND
e1
joyrapiphun@gmail.com
Abstract
The present work, describes electrochemical preparation of functionalized conducting polymer/graphene
oxide (GO) composite thin film for the detection of biomolecule. Polypyrrole/poly(pyrrole-3-carboxylic
acid)/graphene oxide (PPy/PP3C/GO) composite thin films were synthesized by electropolymerization on
an indium tin oxide (ITO) coated glass slide. The effect of experimental conditions such as concentration
and composition of precursor solution on the electrochemical behaviour of the composited material were
investigated. The PPy/PP3C/GO composite thin film under the optimized experimental conditions was
characterized by cyclic voltammetry (CV). In addition, the electrochemical behavior and doping/dedoping
properties of the obtained composite thin film in a neutral phosphate-buffered saline (PBS) solution were
also studied. It was found that the presented functionalized polypyrrole/graphene oxide composite thin
film showed good electroactivity property in neutral PBS solution and could be applied to the detection of
biomolecule. Therefore, it can be concluded that an electrochemically fabricated PPy/PP3C/GO
composite material is a promising candidate as smart material for the biosensor applications in the future.
Keywords: Graphene Oxide, Polypyrrole, Electropolymerization, Biosensor
1. Introduction
Conducting polymers (CPs) such as polythiophene, polyaniline, poly(phenylene vinylene) and
polypyrrole (PPy) and their derivatives have received considerable attention because of their unique
electrical optical, chemical and biochemical properties [1-5]. In recent years, CPs have potential
applications in various fields such as fuel cells, electrochromic displays, field effect transistors (FETs)
2
drug release system, affinity chromatography and biosensors [2, 6-10]. Nowadays, CPs and their
derivatives based biological sensor have been extensively investigated to detect the biomolecules for
example glucose, urea, enzyme, hormone, neurotransmitter, antibody and antigen [11-15]. Among these
CPs, polypyrrole (PPy) and their derivatives are especially promising materials used for chemical and
biochemical sensors due to their good electrical conductivity, environmental stability to air and water,
good biocompatibility, facile synthesis and versatility compared to many CPs [2, 16-17]. PPy films
usually are prepared electrochemically polymerization techniques because this synthetic procedure is
relatively straightforward, ability of controlling thickness, shape and morphology of CPs [5, 18-19].
It is well know that the nanomaterials have been extensively utilized in electrochemical biosensor due
to their conductivity, chemical stability, flexibility and low cost. Some nanomaterials, including
nanoparticles, carbon nanotubes (CNTs) and graphene (GR) have been successfully fabricated onto CPs in
the field of biosensor [20-25]. GR is a promising nanomaterial currently employed for the fabrication of
electrochemical biosensors duo to its unique properties including fast electron transportation, excellent
thermal conductivity, rich surface chemistry and good biocompatibility [20, 24]. Considering the
individual advantages of the CPs and nanomaterials, the CPs composite nanomaterial designed for
biosensor could benefit from the good conductivity, the enhanced binding ability by covalent
immobilization of CPs and the superior stability and conductivity of nanomaterial.
Therefore, this study aims to fabricate the functionalized polypyrrle/graphene oxide composite material
for the detection of biomolecule in biosensor application. The fabrication and characterization of
polypyrrole/poly(pyrrole-3-carboxylic acid)/graphene oxide (PPy/PP3C/GO) composite thin film were
reported. Their electrochemical behavior and doping/dedoping properties were monitored by cyclic
voltammetry (CV) in a neutral phosphate-buffered saline (PBS) solution. It was found that the
electrochemical conducting polymer composite graphene oxide designed in this work is a promising
candidate as smart material for the biosensor applications in the future.
2. Materials and Methods
2.1. Chemicals and Materials
The pyrrole (Py) and pyrrole-3-carboxylic acid (P3C) were purchased from Sigma-Aldrich Co.
Graphene oxide (GO) was prepared by a modified Hummers method [26]. All other chemicals were
analytical grade with highest purity and used as received.
Electrochemical experiments were performed with a Digi-Ivy model DY2000 potentiostat with
conventional three-electrode cell. An indium tin oxide (ITO) coated glass slide was used as the working
electrode. Ag/AgCl electrode and a platinum wire were used as the reference and counter electrodes,
respectively.
2.2. Fabrication of PPy/PP3C/GO composite thin film
PPy/PP3C/GO composite material was fabricated on ITO substrate via electrochemical method. The
precursor solutions containing 0.2 g of GO in a monomer solution of α mM Py and β mM P3C with
constant 10 mM monomer concentration in 0.5 M H2SO4 solution, the simple notation of α:β Py/P3C,
such as 9:1 Py/P3C 5:5 Py/P3C, 1:9 Py/P3C etc., were used for fabricating the PPy/PP3C/GO thin films.
In this study, 0.5 M sulfuric acid was acted not only as electrolyte solution but also solvent in the
fabrication conditions.
For the electrochemical system, platinum wire, Ag/AgCl electrode and ITO were used as counter,
reference and working electrodes, respectively.
3
2.3. Characterization
The fabrication of PPy/PP3C/GO composite thin film was monitored by CV. The effect of experimental
conditions such as concentration and composition of precursor solution on the electrochemical behaviour
of the composited material were also investigated. In addition, the electrochemical behavior and
doping/dedoping properties of the obtained composite thin film under the optimized experimental
conditions in a neutral phosphate-buffered saline (PBS) solution pH 7.4 containing 10.0 mM
K3[Fe(CN)6]/K4[Fe(CN)6] (1:1 mixture as redox probe) ([Fe(CN) 6]3-/4-) were studied.
3. Results and discussion
3.1. Fabrication of an functionalized polypyrrole/graphene oxide composite thin film (PPy/PP3C/GO)
The electrochemical property during the electrochemical fabrication of PPy/PP3C/GO composite thin
film was monitored using an electrochemical measurement. Figure 1 shows the cyclic voltammograms of
5:5 PPy/PP3C copolymer composited with GO, the current in the anodic scan increased at about 0.6 V,
indicating the beginning of the formation of polymer film on ITO electrodes. The current slightly
decreased at about 0.3 V in the cathodic scan, which indicated the dedoping process of the deposited
copolymer films [11]. The electroactivity property of the PPy/PP3C/GO composite material was
compared with PPy. It was found that the oxidation potential of PPy/PP3C/GO thin film exhibited lower
than that of PPy. However, the effect of experimental conditions such as concentration and composition
of precursor solution on the electrochemical behaviour of the composited material were also investigated.
(a)
(b)
Figure 1. Cyclic voltammograms of the electrochemical fabrication of (a) PPy/PP3C/GO and (b) PPy
3.2. The effect of concentration and composition of precursor solution
Cyclic voltammograms of the PPy/PP3C/GO thin film fabricated on an ITO glass substrate with
various ratio of monomer concentration are shown in Figure 2. As shown in the cyclic voltammogram of
1:9, 5:5 and 9:1 of PPy/PP3C/GO composite thin film, the current of 5:5 PPy/PP3C/GO exhibited higher
current than that of other conditions due to the large amount of deposited film on the electrode. These
results indicate that the 5:5 PPy/PP3C/GO has lower oxidation potential which facilitates the fabrication
of functionalized polypyrrole composite GO as compared to other combinations [27]. Based on these
results, obtained material was employed to represent the properties of PPy/PP3C/GO.
4
(a)
(b)
(c)
(c)
Figure 2. Cyclic voltammograms of the electrochemical fabrication of PPy/PP3C/GO with various ratio of monomer
concentration of α:β Py/P3C at (a) 1:9 (b) 5:5 and (c) 1:9
The effect of GO on the electrochemical behaviour the PPy/PP3C/GO composite material was studied
by electrochemical measurement. Cyclic voltammogram of PPy/PP3C/GO and PPy/PP3C recorded in
0.2 M KCl containing 10.0 mM of [Fe(CN) 6]3-/4- at a scan rate of 20 mV/sec are shown in Figure 3. It can
be clearly seen that the cyclic voltammogram of PPy/PP3C thin film shows a well-defined reversible
redox behaviour attributed to highly electron transfer of [Fe(CN)6]3-/4- to the electrode. After the
attachment of PPy/PP3C/GO on the surface of the electrode, the redox current of PPy/PP3C/GO thin film
was higher than that of PPy/PP3C thin film due to excellent electrocatalytic property of the composite
5
material was higher than that for PPy/PP3C copolymer, this would improve the efficiency of the electrode
[28].
Figure 3. Cyclic voltammograms of PPy/PP3C/GO and PPy/PP3C in 0.2 M KCl containing 10.0 mM of [Fe(CN) 6]3-/4- at a scan
rate of 20 mV/sec
3.3. Electrochemical property of PPy/PP3C/GO composite thin film
The effect of varying scan rate on the electrochemical performance was studied in the work. Figure 4
shows the cyclic voltammogram of the PPy/PP3C/GO thin film deposited on an ITO glass substrate in
PBS solution pH 7.4 containing 10.0 mM [Fe(CN) 6]3-/4- at different scan rate of 5, 10, 20, 50 and 100
mV/sec. The anodic and cathodic current of the composite thin film increased with increasing the scan
rates, which indicates that the PPy/PP3C/GO can be electroactive in neutral PBS solution. These results
can be concluded that the functionalized polypyrrole composited graphene oxide showed good
electroactivity in neutral solution which may possess potential applications to study in various systems of
the biosensors.
Figure 4. Cyclic voltammograms of PPy/PP3C/GO composite thin film in PBS solution pH 7.4 containing 10.0 mM
[Fe(CN)6]3-/4- at different scan rate of 5, 10, 20, 50 and 100 mV/sec.
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4. Conclusion
The fabrication of functionalized polypyrrole/graphene oxide composite thin films were successfully
prepared by electrochemical method. The PPy/PP3C/GO composite thin film remarkably improve
electron transfer of the redox in aqueous solution to the electrode. Moreover, the CV measurement of
PPy/PP3C/GO showed good electroactivity property in neutral PBS solution, which would improve the
sensitivity of the electrode for the detection of biomolecule in biosensor application. Therefore, it can be
concluded that an electrochemically fabricated functionalized pyrrole/graphene oxide composite thin film
is a promising candidate as smart materials for the biosensors application in the future.
Acknowledgements
The authors gratefully acknowledge Department of Chemistry, Faculty of Science and Technology,
Pibulsongkram Rajabhat University and Research and Development Institute of Pibulsongkram Rajabhat
University, Thailand and National Research Council of Thailand (NRCT), Thailand for financial
support. We also would like to thank Kulwadee Pinwattana for assistance in electrochemistry
experiments.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
Singh, M., Kathuroju, P. K., & Jampana N. (2009). Sens. Actuators B, 143. 430.
Jiang, H., Zhang, A., Sun, Y., Ru, X., Ge, D., & Shi, W. (2012). Electrochim. Acta, 70, 278.
Vidal, J. C., Ruiz, E. G., & Castillo, J. R. (2003). Microchim. Acta, 143, 93.
Peng, H., Zhang, L., Soeller, C., & Travas-Sejdic, J. (2009). Biomaterials, 30, 2132.
Guimard, N. K., Gomez, N., & Schmidt C. E. (2007). Prog. Polym. Sci., 32, 876.
Damos, F. S., Luz, R. C. S., & Kubota, L. T. (2006). Electrochim. Acta, 51, 1304.
Adhikari, B., & Majumdar, S. (2004). Prog. Polym. Sci., 29, 699.
Baba, A., Mannen, T., Ohdaira, Y., Shinbo, K., Kato, K., Kaneko, F., Fukuda, N., & Ushijima, H. (2010). Langmuir, 26,
18476.
Yang, Y., Kang, M., Fang, S., Wang, M., He, L., Zhao, J., Zhang, H., & Zhang, Z. (2015). Sens. Actuators B, 214. 63.
Yue, H. Y., Zhang, H., Chang, J., Gao, X., Huang, S., Yao, L. H., Lin, X. L., & Guo, E. J. (2015). Anal. Biochem., 488.
22.
Janmanee, R., Baba, A., Phanichphan, S., Sriwichai, S., Shinbo, K., Kato, K., & Kaneko, F. (2011). Jpn. J. of Appl.
Phys., 50, 01BK02-1.
Sriwichai, S., Baba, A., Phanichphant, S., Shinbo, K., Kato, K., & Kaneko, F. (2010). Sens. Actuators B, 147, 322.
Janmanee, R., Baba, A., Phanichphan, S., Sriwichai, S., Shinbo, K., Kato, K., & Kaneko F. (2012). ACS Appl. Mater.
Inter., 4, 4270.
Chu, Z., Liu, Y., Xu, Y., Shi, L., Peng, J., & Jin, W. (2015). Electrochim. Acta, 176, 162.
Soares, J. C., Brisolari, A., Rodrigues, V. C., Sanches, E. A., & Goncalves, D. (2015). React. Funct Polym., 172, 148.
Lin, M., Hu, X., Ma, Z., & Chen, L. (2012). Anal. Chim. Acta., 746, 63.
Palod, P. A., & Singh, V. (2015). Mater. Sci. Eng. C, 55, 420.
Ravichandran, R., Sundarrajan, S., Venugopla, V. R., Mukherjee, S., & Ramakrishna, S. (2010). J. R. Soc. Interface, 10,
1098.
German, N., Ramanavicius, A., Voronovic, J., & Ramanaviciene, A. (2012). Colloids Surf. A, 413, 224.
Hwa, K. Y., & Subramani, B. (2014). Biosens. Bioelectron., 62, 127.
7
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
Devasenathipathy, R., Mani, V., Chen, S. M., Huang, S. T., Huang, T. T., Lin, C. M., Hwa, K. Y., Chen, T. Y., & Chen,
B. J. (2015). Enzyme Microb. Tech., 78, 40.
Peng, H. P., Hu, Y., Deng, Y. N., Wang, P., Chen, W., Liu, A. L., Chen, Y. Z., & Lin, X. H. (2015). Sens. Actuators B,
207, 269.
Nia, P., Meng, W. P., Lorestani, F., Mahmoudian, M. R., & Alias, Y. (2015). Sens. Actuators B, 209, 100.
Xue, K., Zhou, S., Shi, H., Feng, X., Xin, H., & Song, W. (2014). Sens. Actuators B, 203, 412.
Bai, X., & Shiu, K. K. (2014). J. Electroanal. Chem., 720-721, 84.
Hummers, W. S., & Offeman , R. E. (1958). J. Am. Chem. Soc., 80, 1339.
Peng, H., Soeller, C., Vigar, N., Kilmartin, P. A., Cannell, M. B., Bowmaker, G. A., Cooney, R. P., & Travas-Sejdic, J.
(2005), Biosens. Bioelectron., 20, 1821.
Ruiyi, Li., Qianfang, X., Zaijun, Li., Xiulan, S., & Junkang, L. (2013). Biosens. Bioelectron., 44, 235.