Issue 45, 2022

Electrocatalytic NAD+ reduction via hydrogen atom-coupled electron transfer

Abstract

Nicotinamide adenine dinucleotide cofactor (NAD(P)H) is regarded as an important energy carrier and charge transfer mediator. Enzyme-catalyzed NADPH production in natural photosynthesis proceeds via a hydride transfer mechanism. Selective and effective regeneration of NAD(P)H from its oxidized form by artificial catalysts remains challenging due to the formation of byproducts. Herein, electrocatalytic NADH regeneration and the reaction mechanism on metal and carbon electrodes are studied. We find that the selectivity of bioactive 1,4-NADH is relatively high on Cu, Fe, and Co electrodes without forming commonly reported NAD2 byproducts. In contrast, more NAD2 side product is formed with the carbon electrode. ADP-ribose is confirmed to be a side product caused by the fragmentation reaction of NAD+. Based on H/D isotope effects and electron paramagnetic resonance analysis, it is proposed that the formation of NADH on these metal electrodes proceeds via a hydrogen atom-coupled electron transfer (HadCET) mechanism, in contrast to the direct electron-transfer and NAD˙ radical pathway on carbon electrodes, which leads to more by-product, NAD2. This work sheds light on the mechanism of electrocatalytic NADH regeneration, which is different from biocatalysis.

Graphical abstract: Electrocatalytic NAD+ reduction via hydrogen atom-coupled electron transfer

Supplementary files

Article information

Article type
Edge Article
Submitted
14 5月 2022
Accepted
24 10月 2022
First published
24 10月 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 13361-13367

Electrocatalytic NAD+ reduction via hydrogen atom-coupled electron transfer

F. Liu, C. Ding, S. Tian, S. Lu, C. Feng, D. Tu, Y. Liu, W. Wang and C. Li, Chem. Sci., 2022, 13, 13361 DOI: 10.1039/D2SC02691K

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.

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