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The redox property of the ultrasmall coinage nanoclusters (with several to tens of Au/Ag atoms) has elucidated the electron-transfer capacity of nanoclusters, and has been successfully utilized in a variety of redox conversions (such as from CO2 to CO). Nevertheless, their biological applications are mainly restricted by the scarcity of atomically precise, water-soluble metal nanoclusters, and the limited application (mainly on the decomposition of H2O2 in these days). Herein, mercaptosuccinic acid (MSA) protected ultrasmall alloy AuAg nanoclusters were prepared, and the main product was determined [Au3Ag5(MSA)3] by electrospray ionization mass spectrometry (ESI-MS). The clusters can not only mediate the decomposition of H2O2 to generate hydroxyl radicals, but is also able to mediate the reduction of nicotinamide adenine dinucleotide (NAD) to its reduced form of NADH. This is the first time that the atomically precise metal nanoclusters were used to mediate the coenzyme reduction. The preliminary mechanistic insights imply the reaction to be driven by the hydrogen bonding between the carboxylic groups (on the surface of MSA) and the amino N–H bonds (on NAD). In this context, the presence of the carboxylic groups, the sub-nanometer size regime (~ 1 nm), and the synergistic effect of the Au-Ag clusters are pre-requisite to the NAD reduction.


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Nicotinamide adenine dinucleotide (NAD+) reduction enabled by an atomically precise Au-Ag alloy nanocluster

Show Author's information Ling Chen1,2Yonglei Du1Ying Lv1Daoqing Fan1Junfei Wu1Lingbao Wu1Mengting Cui1Haizhu Yu1,2 ( )Manzhou Zhu1( )
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, China
Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230601, China

Abstract

The redox property of the ultrasmall coinage nanoclusters (with several to tens of Au/Ag atoms) has elucidated the electron-transfer capacity of nanoclusters, and has been successfully utilized in a variety of redox conversions (such as from CO2 to CO). Nevertheless, their biological applications are mainly restricted by the scarcity of atomically precise, water-soluble metal nanoclusters, and the limited application (mainly on the decomposition of H2O2 in these days). Herein, mercaptosuccinic acid (MSA) protected ultrasmall alloy AuAg nanoclusters were prepared, and the main product was determined [Au3Ag5(MSA)3] by electrospray ionization mass spectrometry (ESI-MS). The clusters can not only mediate the decomposition of H2O2 to generate hydroxyl radicals, but is also able to mediate the reduction of nicotinamide adenine dinucleotide (NAD) to its reduced form of NADH. This is the first time that the atomically precise metal nanoclusters were used to mediate the coenzyme reduction. The preliminary mechanistic insights imply the reaction to be driven by the hydrogen bonding between the carboxylic groups (on the surface of MSA) and the amino N–H bonds (on NAD). In this context, the presence of the carboxylic groups, the sub-nanometer size regime (~ 1 nm), and the synergistic effect of the Au-Ag clusters are pre-requisite to the NAD reduction.

Keywords: synergistic effect, redox-activity, alloy AuAg nanocluster, size-effect, nicotinamide adenine dinucleotide (NAD) reduction

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Publication history
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Acknowledgements

Publication history

Received: 19 November 2022
Revised: 13 December 2022
Accepted: 16 December 2022
Published: 16 February 2023
Issue date: May 2023

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© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We acknowledge financial support from National Science Foundation of Anhui Province (No. 2108085J08), the University Synergy Innovation Program of Anhui Province (No. GXXT-2021-023), and the technical support of high-performance computing platform of Anhui University.

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