Biosensor based on horseradish peroxidase modified carbon nanotubes for determination of 2,4-dichlorophenol Original Paper First Online: 10 December 2007 Received: 26 May 2007 Accepted: 13 September 2007 DOI:
10.1007/s00604-007-0872-2 Cite this article as: Huang, S., Qu, Y., Li, R. et al. Microchim Acta (2008) 162: 261. doi:10.1007/s00604-007-0872-2 Abstract.
A novel and convenient strategy is presented for determination of 2,4-dichlorophenol (2,4-DCP). Horseradish peroxidase (HRP) was self-assembled on a multiwalled carbon nanotubues (MWNTs) modified glassy carbon (GC) electrode. In the presence of hydrogen peroxide (H
2O 2), 2,4-DCP can be oxidized at this enzyme electrode and the reduction current is proportional to the concentration of the 2,4-DCP. The method showed good linearly for 1.0 × 10 −6–1.0 × 10 −4 M 2,4-DCP with a detection limit of 3.8 × 10 −7 M under the optimal conditions. The peak current of the HRP-MWNTs-GC electrode decreased by about 15% over two weeks. The mechanism of the enzyme biosensor was also studied, and a kinetic equation was derived. The performance of the electrode was verified by determination of 2,4-DCP in environmental water. Keywords: 2,4-Dichlorophenol; carbon nanotubules; horseradish peroxidase; detection; kinetic equation
Correspondence: Shasheng Huang, Life and Environmental Science College, Shanghai Normal University, Shanghai 200234, P.R. China
References Ureta-Zañartu, M S, Bustos, P, Berríos, C, Diez, M C, Mora, M L, Gutiérrez, C 2002 Electrooxidation of 2,4-dichlorophenol and other polychlorinated phenols at a glassy carbon electrode Electrochimica Acta 47 2399 CrossRef Google Scholar Laurenti, E, Ghibaudi, E, Ardissone, S, Ferrari, R P 2003 Oxidation of 2,4-di chloro-phenol catalyzed by horseradish peroxidase: characterization of the reaction mechanism by UV-visible spectroscopy and mass spectrometry Inorg Biochem 95 171 CrossRef Google Scholar Kintz, P, Tracqui, A, Mangin, P 1992 Accidental death caused by the absorption of 2,4-dichlorophenol through the skin Arch Toxicol 66 298 CrossRef Google Scholar Liu, B, Wang, J P, Liu, M L, Zhu, H M 2004 Determination of 2,4-dichlorophenol with internal standard method by gas chromatography Spectroscopy Laboratory 21 576 Google Scholar Wagner, M, Nicell, J A 2002 Detoxification of phenolic solutions with horseradish peroxidase and hydrogen peroxide Wat Res 36 4041 CrossRef Google Scholar Roper, J C, Sarkar, J M, Dec, J, Bollag, J M 1995 Enhanced enzymatic removal of chlorophenols in the presence of co-substrates Wat Res War 29 2720 CrossRef Google Scholar Dec, J, Bollag, J M 1990 Detoxification of substituted phenols by oxidoreductive enzymes through polymerization reactions Arch Environ Contam Toxicol 19 543 CrossRef Google Scholar Xu, F, Bhandari, A 2003 Retention and extractability of phenol, cresol and dichlorophenol exposed to two surface soils in the presence of horseradish peroxidase enzyme Agric Food Chem 51 183 CrossRef Google Scholar Yang, S, Rudolf, S S W, Kong, R Y C 2002 Biodegradation and enzymatic responses in the marine diatom Skeletonema costatum upon exposure to 2,4-dichlorophenol Aquat Toxicol 59 191 Google Scholar
Akhtar S, Husain Q (2006) Potential applications of immobilized bitter gourd (Momordica charantia) peroxidase in the removal of phenols from polluted water. Chemosphere, article (in press)
Wang, C C, Lee, C M, Kuan, C H 2000 Removal of 2,4-dichlorophenol by suspended and immobilized Bacillus insolitus Chemosphere 41 447 CrossRef Google Scholar Ruedas Rama, M J, Ruiz Medina, A, Molina Di’az, A 2003 A simple and straightforward procedure for monitoring phenol compounds in waters by using UV solid phase transduction integrated in a continuous flow system Microchim Acta 141 143 CrossRef Google Scholar Marko-Varga, G, Emnéus, J, Gorton, L 1995 Development of enzyme-based amperometric sensors for the determination of phenolic compounds Trends Anal Chem 14 319 Google Scholar Lindgren, A, Emnéus, J, Ruzgas, T, Gorton, L, Marko-Varga, G 1997 Amperometric detection of phenols using peroxidase-modified graphite electrodes Anal Chim Act 347 51 CrossRef Google Scholar Rosatto, S S, Kubota, L T, Neto, G O 1999 Biosensor for phenol based on the direct electron transfer blocking of peroxidase immobilising on silica-titanium Anal Chim Acta 390 65 CrossRef Google Scholar Rosatto, S S, Sotomayor, P T, Kubota, L T, Gushikem, Y 2002 SiO 2/Nb 2O 5 sol–gel as a support for HRP immobilization inbiosensor preparation for phenol detection Electrochimica Acta 47 4451 CrossRef Google Scholar Riu, J, Maroto, A, Rius, F X 2006 Nanosensors in environmental analysis Talanta 69 288 CrossRef Google Scholar Wang, J, Abdel-Nasser, K, Jan, M R 2004 Carbon-nanotube-modified electrodes for amplified enzyme-based electrical detection of DNA hybridization Biosens Bioelectron 20 995 CrossRef Google Scholar Joshi, P P, Merchant, S A, Wang, Y, Schmidtke, D W 2005 Amperometric biosensors based on redox polymer-carbon nanotube-enzyme composites Anal Chem 77 3183 CrossRef Google Scholar Davis, J J, Green, M L H, Hill, H A O, Leung, Y C, Sadler, P J, Sloan, J, Xaviers, A V, Tsang, S C 1998 The immobilisation of proteins in carbon nanotubes Inorganica Chimica Acta 272 261 CrossRef Google Scholar Liu, G D, Lin, Y H 2006 Biosensor based on self-assembling acetylcholinesterase on carbon nanotubes for flow injection/amperometric detection of organophosphate pesticides and nerve agents Anal Chem 78 835 CrossRef Google Scholar Liu, G D, Riechers, S L, Mellen, M C, Lin, Y H 2005 Sensitive electrochemical detection of enzymatically generated thiocholine at carbon nanotube modified glassy carbon electrode Electrochem Commun 7 1163 CrossRef Google Scholar Cai, C X, Chen, J 2004 Direct electron transfer of redox proteins and enzymes promoted by carbon nanotube Electrochemistry 10 159 Google Scholar Yu, X, Chattopadhyay, D, Galeska, I, Papadimitrakopoulos, F, Rusling, J F 2003 Peroxidase activity of enzymes bound to the ends of single-wall carbon nanotube forest electrodes Electrochem Commun 5 408 CrossRef Google Scholar Qian, L, Yang, X 2006 Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor amperometric hydrogen peroxide biosensor Talanta 68 721 CrossRef Google Scholar Yan, Y M, Zheng, W, Zhang, M, Wang, L, Su, L, Mao, L 2005 Bioelectrochemically functional nanohybrids through co-assembling of proteins and surfactants onto carbon nanotubes: facilitated electron transfer of assembled proteins with enhanced faradic response Langmuir 21 6560 CrossRef Google Scholar Zhao, G C, Zhang, L, Wei, X W, Yang, Z S 2003 Myoglobin on multi-walled carbon nanotubes modified electrode: direct electrochemistry and electrocatalysis Electrochem Commun 5 825 CrossRef Google Scholar Chattopadhyay, K, Mazumdar, S 2000 Direct electrochemistry of heme proteins: effect of electrode surface modification by neutral surfactants Bioelectrochemistry 53 17 CrossRef Google Scholar Ruzgas, T, Emnéus, J, Gorton, L, Marko-Varga, G 1995 The development of a peroxidase biosensor for monitoring phenol and related aromatic compounds Analytica Chimca Acta 311 245 CrossRef Google Scholar Ruzgas, T, Gorton, L, Emnéus, J, Marko-Varga, G 1995 Kinetic models of horseradish peroxidase action on a graphite electrode Electroanal Chem 391 41 CrossRef Google Scholar Tang, L, Zeng, G M, Huang, G H, Shen, G L, Niu, C G 2004 Kinetic study on the inhibition and catalysis of horseradish peroxidase biosensor china Biotechnol 24 70 Google Scholar Chen, S G, Zhou, R Q 2001Enzymology Fudan University Press ShangHai 163 Google Scholar