A series of dopant-type polyaniline-polyacrylic acid composite (PAn-PAA) films with porous structures were prepared and developed for an enzyme-free hydrogen peroxide (H2O2) sensor. The composite films were highly electroactive in a neutral environment as compared to polyaniline (PAn). In addition, the carboxyl group of the PAA was found to react with H2O2 to form peroxy acid groups, and the peroxy acid could further oxidize the imine structure of PAn to form N-oxides. The N-oxides reverted to their original form via electrochemical reduction and increased the reduction current. Based on this result, PAn-PAA was used to modify a gold electrode (PAn-PAA/Au) as a working electrode for the non-enzymatic detection of H2O2. The characteristics of the proposed sensors could be tuned by the PAA/PAn molar ratio. Blending PAA with PAn enhanced the surface area, electrocatalytic activity, and conductivity of these sensors. Under optimal conditions, the linear concentration range of the H2O2 sensor was 0.04 to 12 mM with a sensitivity of 417.5 μA/mM-cm2. This enzyme-free H2O2 sensor also exhibited a rapid response time, excellent stability, and high selectivity.
References
[1]
Yang, Y; Mu, S. Determination of hydrogen peroxide using amperometric sensor of polyaniline doped with ferrocenesulfonic acid. Biosens. Bioelectron 2005, 21, 74–78, doi:10.1016/j.bios.2004.08.049. 15967353
[2]
Chang, MCY; Pralle, A; Isacoff, EY; Chang, CJ. A selective, cell-permeable optical probe for hydrogen peroxide in living cells. J. Am. Chem. Soc 2004, 126, 15392–15393, doi:10.1021/ja0441716. 15563161
[3]
Ohshima, H; Tatemichi, M; Sawa, T. Chemical basis of inflammation-induced carcinogenesis. Arch. Biochem. Biophys 2003, 417, 3–11, doi:10.1016/S0003-9861(03)00283-2. 12921773
[4]
Wang, H; Park, SM. Polypyrrole-based optical probe for a hydrogen peroxide assay. Anal. Chem 2007, 79, 240–245, doi:10.1021/ac0608319. 17194146
[5]
Zayats, M; Baron, R; Popov, I; Willner, I. Biocatalytic growth of Au nanoparticles: From mechanistic aspects to biosensors design. Nano Lett 2005, 5, 21–25, doi:10.1021/nl048547p. 15792406
[6]
Endo, T; Yanagida, Y; Hatsuzawa, T. Quantitative determination of hydrogen peroxide using polymer coated Ag nanoparticles. Measurement 2008, 41, 1045–1053, doi:10.1016/j.measurement.2008.03.004.
[7]
Filippo, E; Serra, A; Manno, D. Poly (vinyl alcohol) capped silver nanoparticles as localized surface plasmon resonance-based hydrogen peroxide sensor. Sens. Actuat. B 2009, 138, 625–630, doi:10.1016/j.snb.2009.02.056.
[8]
Vasileva, P; Donkova, B; Karadjova, I; Dushkin, C. Synthesis of starch-stabilized silver nanoparticles and their application as a surface plasmon resonance-based sensor of hydrogen peroxide. Colloids Surf. A: Physicochem. Eng. Aspects 2011, 382, 203–210, doi:10.1016/j.colsurfa.2010.11.060.
[9]
Luo, Y; Liu, H; Rui, Q; Tian, Y. Detection of extracellular H2O2 released from human liver cancer cells based on TiO2 nanoneedles with enhanced electron transfer of cytochrome c. Anal. Chem 2009, 81, 3035–3041, doi:10.1021/ac802721x. 19290667
[10]
Li, X; Liu, Y; Zhu, A; Luo, Y; Deng, Z; Tian, Y. Real-time electrochemical monitoring of cellular H2O2 integrated with in situ selective cultivation of living cells based on dual functional protein microarrays at Au-TiO2 surfaces. Anal. Chem 2010, 82, 6512–6518, doi:10.1021/ac100807c. 20583800
Liu, A; Wei, M; Honma, I; Zhou, H. Direct electrochemistry of myoglobin in titanate nanotubes film. Anal. Chem 2005, 77, 8068–8074, doi:10.1021/ac051640t. 16351157
[13]
Dai, Z; Xu, X; Ju, H. Direct electrochemistry and electrocatalysis of myoglobin immobilized on a hexagonal mesoporous silica matrix. Anal. Biochem 2004, 332, 23–31, doi:10.1016/j.ab.2004.03.067. 15301945
Zhang, T; Yuan, R; Chai, Y; Li, W; Ling, S. A novel nonenzymatic hydrogen peroxide sensor based on a polypyrrole nanowire-copper nanocomposite modified gold electrode. Sensors 2008, 8, 5141–5152, doi:10.3390/s8085141.
[20]
Wang, Q; Yun, Y; Zheng, J. Nonenzymatic hydrogen peroxide sensor based on a polyaniline-single walled carbon nanotubes composite in a room temperature ionic liquid. Microchim. Acta 2009, 167, 153–157, doi:10.1007/s00604-009-0236-1.
[21]
Malhotra, BD; Chaubey, A; Singh, SP. Prospects of conducting polymers in biosensors. Anal. Chim. Acta 2006, 578, 59–74, doi:10.1016/j.aca.2006.04.055. 17723695
Shan, D; Wang, S; He, Y; Xue, H. Amperometric glucose biosensor based on in situ electropolymerized polyaniline/poly(acrylonitrile-co-acrylic acid) composite film. Mater. Sci. Eng. C 2008, 28, 213–217, doi:10.1016/j.msec.2006.12.003.
[24]
Xu, Q; Zhu, J; Hu, X. Ordered mesoporous polyaniline film as a new matrix for enzyme immobilization and biosensor construction. Anal. Chim. Acta 2007, 597, 151–156, doi:10.1016/j.aca.2007.06.034. 17658325
[25]
Dhand, C; Singh, SP; Arya, SK; Datta, M; Malhotra, BD. Cholesterol biosensor based on electrophoretically deposited conducting polymer film derived from nano-structured polyaniline colloidal suspension. Anal. Chim. Acta 2007, 602, 244–251, doi:10.1016/j.aca.2007.09.028. 17933610
Luo, YC; Do, JS. Urea biosensor based on PANi(urease)-Nafion?/Au composite electrode. Biosens. Bioelectron 2004, 20, 15–23, doi:10.1016/j.bios.2003.11.028. 15142572
[28]
Yan, W; Feng, X; Chen, X; Hou, W; Zhu, JJ. A super highly sensitive glucose biosensor based on Au nanoparticles-AgCl@polyaniline hybrid material. Biosens. Bioelectron 2008, 23, 925–931, doi:10.1016/j.bios.2007.09.002. 18093821
[29]
Yue, J; Epstein, AJ. Synthesis of self-doped conducting polyaniline. J. Am. Chem. Soc 1990, 112, 2800–2801, doi:10.1021/ja00163a051.
[30]
Mu, S; Kan, J. The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of ferrocenesulfonic acid. Synth. Met 2002, 132, 29–33, doi:10.1016/S0379-6779(02)00209-6.
[31]
Zhang, L; Lian, J. Electrochemical synthesis of copolymer of aniline and o-aminophenol and its use to the electrocatalytic oxidation of ascorbic acid. J. Electroanal. Chem 2007, 611, 51–59, doi:10.1016/j.jelechem.2007.08.002.
[32]
Gupta, B; Prakash, R. Processible polyacid doped polyaniline composites: Application for charge storage devices. Mater. Sci. Eng. C 2009, 29, 1746–1751, doi:10.1016/j.msec.2009.01.025.
[33]
Ball, IJ; Huang, SC; Wolf, RA; Shimano, JY; Kaner, RB. Pervaporation studies with polyaniline membranes and blends. J. Membr. Sci 2000, 174, 161–176, doi:10.1016/S0376-7388(00)00387-2.
[34]
Raitman, OA; Katz, E; Bückmann, AF; Willner, I. Integration of polyaniline/poly(acrylic acid) films and redox enzymes on electrode supports: An in situ electrochemical/surface plasmon resonance study of the bioelectrocatalyzed oxidation of glucose or lactate in the integrated bioelectrocatalytic systems. J. Am. Chen. Soc 2002, 124, 6487–6496, doi:10.1021/ja012680r.
[35]
Huang, J; Kaner, RB. A general chemical route to polyaniline nanofibers. J. Am. Chem. Soc 2004, 126, 851–855, doi:10.1021/ja0371754. 14733560
Dan, A; Sengupta, PK. Synthesis and characterization of conducting poly(aniline-co-diaminodiphenylsulfone) copolymers. J. Appl. Polym. Sci 2003, 90, 2337–2347, doi:10.1002/app.12827.
[42]
Nakanishi, K; Solomon, PH. Infrared Absorption Spectroscopy; Holden Day: San Francisco, CA, USA, 1997.
[43]
Donnici, CL; Filho, DHM; Moreira, LLC; dos Reis, GT; Cordeiro, ES; de Oliveira, IMF; Carvalho, S; Paniago, EP. Synthesis of the novel 4,4′- and 6,6′-dihydroxamic-2,2′-bipyridines and improved routes to 4,4′- and 6,6′-substituted-2,2′-bipyridines and mono-N-oxide-2,2′-bipyridine. J. Braz. Chem. Soc 1998, 9, 455–460.
[44]
Hua, MY; Chen, SH; Tsai, RY; Lin, YC; Wang, L. A novel biosensing mechanism based on poly (N-butyl benzimidazole) modified gold electrode for the detection of hydrogen peroxide. Analytica Chimica Acta 2011, 693, 114–120, doi:10.1016/j.aca.2011.03.020. 21504818
[45]
Hua, MY; Chen, SH; Tsai, RY; Leu, YL; Liu, YC; Lai, JT. Synthesis and characterization of carboxylated polybenzimidazole and its use as a highly sensitive and selective enzyme-free H2O2 sensor. J. Mater. Chem 2011, 21, 7254–7262, doi:10.1039/c0jm04119j.
[46]
Chen, YS; Huang, JH; Chuang, CC. Glucose biosensor based on multiwalled carbon nanotubes grown directly on Si. Carbon 2009, 47, 3106–3112, doi:10.1016/j.carbon.2009.07.029.