Amino-Induced Cleavage of Electron-Communicating S-Bridge to Unlock Mixed-Valence Copper for Potent Oxidase-like Catalysis and Selective Sensing

Abstract

Transition metal sites with mixed valence often coexisted in diverse catalysis, yet their precise roles remained elusive. Taking a thiadiazole-coordinated Cu nanozyme system for example, we developed ligand side-group engineering to modulate adjacent dicopper sites with different mixed Cu1+/Cu2+ states. Amino functionalization of ligand induced the cleavage of electron-communicating S-bridge connecting adjacent dicopper centers to precisely manipulate the ratio of mixed Cu1+/Cu2+ sites. Such a tailored mixed-valence composition accelerated the preferential and selective activation of O2 to O2•− through the synergistical mechanism of Cu2+-dominated adsorption of O2 and Cu1+-controlled electron transfer in the initial step of catalysis. This targeted pathway boosted the oxidase-mimicking activity of the mixed-valence nanozyme by nearly 85-fold compared to its counterpart with the adjacent S-bridged Cu centers. The outstanding oxidase-like activity, coupled with the unique affinity of mixed Cu1+/Cu2+ sites for phosphorus, further enabled highly selective and sensitive sensing of cytotoxic tris(2-carboxyethyl)phosphine with a 0.96 ppm detection limit via the complexation-dominated activity inhibition mechanism. This fundamental insight into mixed-valence synergy of metal sites provided a new perspective for designing efficient catalysts for various catalysis, sensing and beyond.

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Article information

Article type
Edge Article
Submitted
15 May 2025
Accepted
04 Jul 2025
First published
05 Jul 2025
This article is Open Access

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

Chem. Sci., 2025, Accepted Manuscript

Amino-Induced Cleavage of Electron-Communicating S-Bridge to Unlock Mixed-Valence Copper for Potent Oxidase-like Catalysis and Selective Sensing

B. Li, N. N. Xia, C. Huang, X. Hu and F. He, Chem. Sci., 2025, Accepted Manuscript , DOI: 10.1039/D5SC03521J

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