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三氧化钨纳米结构促进酶的电子转移:在高选择性检测过氧化氢中的应用。

WO3 nanostructures facilitate electron transfer of enzyme: application to detection of H2O2 with high selectivity.

作者信息

Deng Zifeng, Gong Yichun, Luo Yongping, Tian Yang

机构信息

Department of Chemistry, Tongji University, Siping Road 1239, Shanghai 200092, PR China.

出版信息

Biosens Bioelectron. 2009 Apr 15;24(8):2465-9. doi: 10.1016/j.bios.2008.12.037. Epub 2009 Jan 6.

Abstract

The WO(3) nanoparticles film is first employed as a support matrix for confining cytochrome c (cyt. c), an excellent model for studying electron transfer between the redox enzymes and the electrode. The surface pK(a) of nanostructured WO(3) film is estimated to be approximately 2.74 using electrochemical method. The present WO(3) surface with negative charge at the neutral solution is very benefit for the adsorption of cyt. c with positive charge and facilitates electron transfer of cyt. c. As a result, direct and fast electron transfer of cyt. c is realized at the nanostructured WO(3) surface with the redox formal potential (E(0)') of -133.5+/-1.7 mV (n=4) versus Ag/AgCl and heterogeneous electron transfer rate constant of 5.57+/-0.54 s(-1). Experimental data indicate that cyt. c is stably confined onto the WO(3) nanoparticles film, possibly due to the electrostatic interaction between WO(3) nanostructures and cyt. c, and processes its enzymatic activity toward H(2)O(2). Based on these results, the third-generation biosensor for H(2)O(2) is developed with high selectivity, free from not only common anodic interferences like ascorbic acid, uric acid, 3,4-dihydroxyphenylacetic acid, and so on, but also cathodic interference-O(2). The remarkable analytical advantages, as well as the characteristic of WO(3) nanoparticles film such as biocompatibility, low-cost, and facile to miniature give a strong basis for continuous, on-line detection of H(2)O(2) under pathophysiological conditions.

摘要

三氧化钨(WO₃)纳米颗粒薄膜首次被用作限制细胞色素c(cyt. c)的支撑基质,细胞色素c是研究氧化还原酶与电极之间电子转移的优秀模型。采用电化学方法估计纳米结构WO₃薄膜的表面pK(a)约为2.74。在中性溶液中带负电荷的当前WO₃表面非常有利于带正电荷的细胞色素c的吸附,并促进细胞色素c的电子转移。结果,在纳米结构WO₃表面实现了细胞色素c的直接快速电子转移,相对于Ag/AgCl的氧化还原形式电位(E(0)')为 -133.5±1.7 mV(n = 4),异质电子转移速率常数为5.57±0.54 s⁻¹。实验数据表明,细胞色素c稳定地限制在WO₃纳米颗粒薄膜上,这可能是由于WO₃纳米结构与细胞色素c之间的静电相互作用,并且细胞色素c对过氧化氢具有酶活性。基于这些结果,开发了用于过氧化氢的第三代生物传感器,该传感器具有高选择性,不仅不受抗坏血酸、尿酸、3,4 - 二羟基苯乙酸等常见阳极干扰的影响,也不受阴极干扰——氧气的影响。显著的分析优势以及WO₃纳米颗粒薄膜的生物相容性、低成本和易于微型化等特性为在病理生理条件下连续在线检测过氧化氢提供了有力依据。

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