Fabricating dicopper centers in nanozymes offered a promising route to mimic catecholase-like catalysis. However, some dicopper centers often suffered from symmetric configurations, which was prone to weaken the O-O bond polarization, thereby limiting O2 activation. This resulted in the unsatisfied intrinsic activities of nanozymes, thus hindering their potential sensing applications. Here, we reported a CO-like nanozyme (DTD-Cu) engineered with proximal and asymmetrically coordinated dicopper centers via a N/S-rich ligand. The unique asymmetric N4Cu-CuN4S configuration facilitated the preferential O2 adsorption/activation and the O-O bond polarization as well as subsequent 4-electron reduction to H2O via a H2O2 intermediate, thus endowing DTD-Cu with dramatically enhanced intrinsic activity, as evidenced by orders-of-magnitude improvements in Km and Kcat/Km over most reported CO-like nanozymes and artificial enzymes. Capitalizing on this superior activity, we achieved highly selective and sensitive detection of the cytotoxic tris(2-carboxyethyl)phosphine (TCEP) with a detection limit of 98.6 ppb via a synergistic dual-inhibition mechanism involving both TCEP-induced reduction of the oxidized substrate/ROS and direct TCEP-dominated chelation to the Cu sites.

This article is Open Access

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