氧化还原酶电催化反应研究进展  

Advances of bioelectrocatalysis by oxidoreductases

作　　者：王世珍[1] 刘凯泷 詹东平[1] Shizhen Wang;Kailong Liu;Dongping Zhan(College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

机构地区：[1]厦门大学化学化工学院,遛门361005

出　　处：《科学通报》2021年第10期1240-1249,共10页Chinese Science Bulletin

基　　金：国家自然科学基金(21776233,22078273);福建省自然科学基金(2018J01013);中央高校基本科研业务费专项(20720200038,20720170033)资助。

摘　　要：由于选择性好、效率高、无副产物和绿色环保等优点,生物电催化合成反应备受关注.氧化还原酶分子内部及其与电极界面间的电子传递效率,决定了生物电化学合成的效率.本文对近年来酶电催化的相关研究进行总结,聚焦氧化还原酶分子内的电子传递机制,阐述氧化还原酶共进化电子传递网络改造、分子开关设计、导电模块组装等酶分子内电子传递的调控策略;同时,以优化酶分子与电极界面间的电子传递为导向,通过蛋白质工程获得新型高效氧化还原酶,构建酶电催化还原反应器,实现高效生物电催化还原制备手性化合物,推动绿色生物制造发展.Bioelectrocatalysis attracts much attention with the advantages of high selectivity, high efficiency, no byproduct and environmental friendliness. Electrification of industrial biotechnology is challenging for the different operating conditions and catalysts of electrochemical and biochemical reactions. In this review, we present the state-of-the-art information on enzymatic electrosynthesis for the production of fine chemicals.Multidisciplinary strategies of electrode surface modification and enzyme immobilization have been integrated in electrocatalytic devices with various applications in biosensors and bioelectrocatalysis. However, the efficiency of bioelectrosynthesis is determined by the intramolecular electron transfer rate, and interfacial electron transfer rate between the oxidoreductases and electrode. This review aims to summarize recent progresses on the mechanism studies of intramolecular electron transferof redox proteins, including tunneling, hopping, proton-coupled electron transfer, etc. Modular origin of electron transfer chain was also discussed from the perspective of the evolution of spatial adjacency network.Novel and efficient oxidoreductases with enhanced intramolecular and interfacial electron transfer rate can be obtained by protein engineering. The strategies for facilitating intramolecular electron transfer are addressed, which includes the regulation of co-evolved electron transfer network, the designs of molecular switch and the assembly of conductive modules. Oxidoreductases are engineered to improve their biocatalytic performance by using the tools of molecular evolution, modeling, structure prediction, and mutation. Co-evolved molecular switches controll proton-coupled electron transfer and regulate electron transfer inside the multi-center redox proteins. Assembly of surface-binding conductive peptides to oxidoreductases facilitates electricity-driven catalysis. Moreover, the modifications of oxidoreductases allow their predictable immobilization on functionalized electrode surfa

关 键 词：氧化还原酶 生物电催化 辅酶再生 分子开关 共进化 电子传递 

分 类 号：Q814[生物学—生物工程]