Issue 83, 2022

Deracemisation and stereoinversion by a nanoconfined bidirectional enzyme cascade: dual control by electrochemistry and selective metal ion activation

Abstract

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 RS conversions are thus achieved in high yield with unprecedented ease.

Graphical abstract: Deracemisation and stereoinversion by a nanoconfined bidirectional enzyme cascade: dual control by electrochemistry and selective metal ion activation

Supplementary files

Article information

Article type
Communication
Submitted
30 Jun 2022
Accepted
22 Sep 2022
First published
30 Sep 2022
This article is Open Access
Creative Commons BY license

Chem. Commun., 2022,58, 11713-11716

Deracemisation and stereoinversion by a nanoconfined bidirectional enzyme cascade: dual control by electrochemistry and selective metal ion activation

B. Cheng, R. S. Heath, N. J. Turner, F. A. Armstrong and C. F. Megarity, Chem. Commun., 2022, 58, 11713 DOI: 10.1039/D2CC03638J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements