Deracemisation and stereoinversion by a nanoconfined bidirectional enzyme cascade: dual control by electrochemistry and selective metal ion activation.
Deracemisation and stereoinversion by a nanoconfined bidirectional enzyme cascade: dual control by electrochemistry and selective metal ion activation.
复制标题
DOI：
10.1039/d2cc03638j
复制
发表时间：
2022-10-18
影响因子：
4.9
通讯作者：
Megarity, Clare F.
中科院分区：
文献类型：
--
作者：
Cheng, Beichen;Heath, Rachel S.;Turner, Nicholas J.;Armstrong, Fraser A.;Megarity, Clare F.
“电化学叶”（e-Leaf）双向驱动和控制纳米限制的酶级联的独特能力，同时直接实时监测它们的速率作为电流，被用来在一个锅中使用单个电极实现仲醇的去外消旋和立体转化。两种具有相反对映体选择性的醇脱氢酶，来自嗜热厌氧乙醇菌（对S有选择性）和开菲尔乳杆菌（对R有选择性），通过偶联到由铁氧还蛋白NADP+还原酶催化的NADP+/NADPH的快速和准可逆的相互转化来双向驱动-所有酶都被共同包埋在纳米多孔氧化铟锡电极中。开菲尔乳杆菌酶的活性取决于非催化性Mg 2+的结合，允许其在氧化半循环后通过添加EDTA -S-选择性酶而关闭，具有紧密结合的Zn 2+，保持完全活性。因此，以前所未有的容易性以高产率实现外消旋体→ S或R → S转化。在多孔电极中纳米限制的酶被电化学驱动用于去消旋化和转化，并通过金属离子活化进行额外控制。
The unique ability of the ‘electrochemical leaf’ (e-Leaf) to drive and control nanoconfined enzyme cascades bidirectionally, while directly monitoring their rate in real-time as electrical current, is exploited to achieve deracemisation and stereoinversion of secondary alcohols using a single electrode in one pot. Two alcohol dehydrogenase enzymes with opposing enantioselectivities, from Thermoanaerobacter ethanolicus (selective for S) and Lactobacillus kefir (selective for R) are driven bidirectionally via coupling to the fast and quasi-reversible interconversion of NADP+/NADPH catalysed by ferredoxin NADP+ reductase – all enzymes being co-entrapped in a nanoporous indium tin oxide electrode. Activity of the Lactobacillus kefir enzyme depends on the binding of a non-catalytic Mg2+, allowing it to be switched off after an oxidative half-cycle, by adding EDTA – the S-selective enzyme, with a tightly-bound Zn2+, remaining fully active. Racemate → S or R → S conversions are thus achieved in high yield with unprecedented ease. Enzymes nanoconfined in a porous electrode are electrochemically driven for deracemisation and inversion with additional control by metal ion activation.
登录
查看更多内容
DOI：
10.1021/acs.jpclett.1c01517
发表时间：
2021-07-08
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
Herold RA;Reinbold R;Megarity CF;Abboud MI;Schofield CJ;Armstrong FA
通讯作者：
Armstrong FA
影响因子：
8.4
作者：
Siritanaratkul B;Megarity CF;Roberts TG;Samuels TOM;Winkler M;Warner JH;Happe T;Armstrong FA
通讯作者：
Armstrong FA
影响因子：
12.9
作者：
Megarity, Clare F.;Weald, Thomas R. I.;Heath, Rachel S.;Turner, Nicholas J.;Armstrong, Fraser A.
通讯作者：
Armstrong, Fraser A.
影响因子：
15
作者：
Voss, Constance V.;Gruber, Christian C.;Kroutil, Wolfgang
通讯作者：
Kroutil, Wolfgang
影响因子：
4.5
作者：
Megarity, Clare F.;Siritanaratkul, Bhavin;Armstrong, Fraser A.
通讯作者：
Armstrong, Fraser A.