{"title":"On the fundamentals of quantum rate theory and the long-range electron transport in respiratory chains†","authors":"Paulo Roberto Bueno","doi":"10.1039/D3CS00662J","DOIUrl":null,"url":null,"abstract":"<p >It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has an entirely quantum rate basis that encompasses the electron-transfer rate theory as originally proposed by Rudolph A. Marcus whether statistical mechanics is appropriately taken into account. I have prepared a concise review of the quantum mechanical rate theory principles focused on its quantum electrodynamics character to demonstrate that it can reconcile the conflicting views established on attempting to use the super-exchange (supported on electron transfer) or ‘metallic-like’ (supported on conductance quantum) mechanisms separately to explain the highly efficient long-range electron transport observed in the respiratory processes of living cells. The unresolved issues related to long-range electron transport are clarified in light of the quantum rate theory with a discussion focused on <em>Geobacter sulfurreducens</em> films as a reference standard of the respiration chain. Theoretical analyses supported by experimental data suggest that the efficiency of respiration within a long-range electron transport path is intrinsically a quantum mechanical event that follows relativistic quantum electrodynamics principles as addressed by quantum rate theory.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4000,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Society Reviews","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/cs/d3cs00662j","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has an entirely quantum rate basis that encompasses the electron-transfer rate theory as originally proposed by Rudolph A. Marcus whether statistical mechanics is appropriately taken into account. I have prepared a concise review of the quantum mechanical rate theory principles focused on its quantum electrodynamics character to demonstrate that it can reconcile the conflicting views established on attempting to use the super-exchange (supported on electron transfer) or ‘metallic-like’ (supported on conductance quantum) mechanisms separately to explain the highly efficient long-range electron transport observed in the respiratory processes of living cells. The unresolved issues related to long-range electron transport are clarified in light of the quantum rate theory with a discussion focused on Geobacter sulfurreducens films as a reference standard of the respiration chain. Theoretical analyses supported by experimental data suggest that the efficiency of respiration within a long-range electron transport path is intrinsically a quantum mechanical event that follows relativistic quantum electrodynamics principles as addressed by quantum rate theory.
研究表明,电化学反应的电子转移速率常数和电导量子都与量子电容的概念相关。这两个独立概念之间的简单联系完全以量子速率为基础,包括鲁道夫-马库斯(Rudolph A. Marcus)最初提出的电子转移速率理论(无论是否适当考虑了统计力学)。我对量子力学速率理论原理进行了简明扼要的评述,重点关注其量子电动力学特性,以证明它可以调和试图分别使用超交换(以电子转移为基础)或 "类金属"(以电导量子为基础)机制来解释活细胞呼吸过程中观察到的高效长程电子传递所产生的相互冲突的观点。根据量子速率理论澄清了与长程电子传递有关的未决问题,并重点讨论了作为呼吸链参考标准的硫化酵母菌薄膜。实验数据支持的理论分析表明,长程电子传递路径中的呼吸效率本质上是一个量子力学事件,遵循量子速率理论所涉及的相对论量子电动力学原理。
期刊介绍:
Chemical Society Reviews is published by: Royal Society of Chemistry.
Focus: Review articles on topics of current interest in chemistry;
Predecessors: Quarterly Reviews, Chemical Society (1947–1971);
Current title: Since 1971;
Impact factor: 60.615 (2021);
Themed issues: Occasional themed issues on new and emerging areas of research in the chemical sciences