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生物电分析化学近期研究专辑(南京大学 夏兴华教授主编)

生物醌分子伏安响应的多电子转移辨析

  • 周浩 ,
  • 龙亿涛
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  • 华东理工大学结构可控先进功能材料及其制备教育部重点实验室,上海 200237

收稿日期: 2014-04-29

  修回日期: 2014-06-23

  网络出版日期: 2014-06-28

基金资助

国家杰出青年基金(No. 21125522)和上海高校特聘教授(东方学者,跟踪计划)资助

Resolve Mono-Electronic Process in the Voltammetric Behaviors of Multi-Redox Bis-Coenzyme Q0

  • ZHOU Hao ,
  • LONG Yi-Tao
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  • Key Laboratory of Advanced Material (ECUST), Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Received date: 2014-04-29

  Revised date: 2014-06-23

  Online published: 2014-06-28

摘要

电化学反应中,一个基元电子转移反应仅对应一个电子交换,实际上多电子转移反应也涉及对应数目的单电子转移步骤,分离、辨析每个电子基元反应的氧化还原峰电位十分重要. 本文以辅酶Q0(CoQ0)、亚甲基桥连双辅酶Q0(Bis-CoQ0)为模型,采用循环伏安和方波伏安技术研究其电化学特性,提出了一种应用于多电子转移体系、分析单个电子转移电位的方法. 实验表明,CoQ0经历两步单电子还原反应;Bis-CoQ0中两个醌单元发生强电子相互作用,电极过程为4电子多步转移. 对于表观上的4电子“三步”转移反应,拟用Lorentzian-Gaussian分峰拟合CoQ0和Bis-CoQ0体系方波伏安响应曲线,分别获取每个电子转移步骤的电位,进一步证明Bis-CoQ0经历四分步单电子转移反应,为热力学研究提供更多信息.

本文引用格式

周浩 , 龙亿涛 . 生物醌分子伏安响应的多电子转移辨析[J]. 电化学, 2014 , 20(6) : 533 -537 . DOI: 10.13208/j.electrochem.140432

Abstract

A widely held concept in electrochemistry is that truly elementary electron-transfer reactions always involve the exchange of one electron, therefore, an overall process involving a change of n electrons must involve n distinct electron-transfer steps. It is highly desirable to resolve multiple-step electron transfer reactions into each electron transfer step. The electrochemical behaviors of coenzyme Q0 and methylene-bridged Bis-coenzyme Q0 were investigated by cyclic voltammetry and square wave voltammetry in nonaqueous dichloromethane containing 0.15 mol·L-1 Bu4NClO4 as the supporting electrolyte. The redox reaction of coenzyme Q0 is well described as two chemically reversible one-electron reduction processes. Bis-coenzyme Q0 exhibits three redox waves in voltammetric experiment, as two bridged coenzyme Q0 units show strong intramolecular electron communication. Experimental data were curve fitted with a Gaussian and Lorentzian mixed product function after subtracting the Shirley background. Results show that four-electron reduction of Bis-coenzyme Q0 is preceded by stepwise pathways, defining as four successive, mono-electronic electron-transfer steps.
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