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测定 NADH/NAD+ 氧化还原偶联的标准还原电势和聚(副玫瑰苯胺)修饰碳电极对 NADH 的催化氧化。

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes.

机构信息

Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan.

出版信息

Bioelectrochemistry. 2011 Feb;80(2):121-7. doi: 10.1016/j.bioelechem.2010.07.001. Epub 2010 Jul 7.

Abstract

The electrochemical regeneration of NADH/NAD(+) redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be -0.365±0.002V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2M NaClO(4)/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2M H(2)SO(4) solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10(3)-10(4)M(-)(1)s(-1) depending on the preparation conditions of the PPS-modified electrodes.

摘要

使用聚(副玫瑰苯胺)(PPS)修饰碳电极研究了 NADH/NAD(+)氧化还原偶联物的电化学再生,以评估 NADH 氧化的形式电势和催化速率常数。PPS 修饰电极通过在不同电解质溶液中在不同碳基底(玻碳(GC)和基面热解石墨(BPPG))上电聚合副玫瑰苯胺制备。在 pH 7.0 时,形式电势估计为-0.365±0.002V 相对于 SHE。对于裸碳电极,发现与 GC 电极相比,BPPG 电极上 NADH 的氧化得到增强。对于 PPS 修饰电极,发现 PPS 修饰电极对 NADH 氧化的电催化作用在很大程度上取决于用于制备它们的碳基底和电解质溶液,即,在 0.2M NaClO(4)/乙腈溶液中制备的 PPS 修饰 BPPG 电极在磷酸盐缓冲溶液(pH 7.0)中表现出对 NADH 氧化的优异和持久的电催化性能,与裸 GC 电极和在 0.2M H(2)SO(4)溶液中制备的 PPS 修饰 GC 电极相比,过电势降低约 740 和 670mV。基于旋转圆盘伏安法的电化学催化反应的定量分析给出了电催化反应速率常数,其数量级为 10(3)-10(4)M(-)(1)s(-1),这取决于 PPS 修饰电极的制备条件。

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