Regulating Second Coordination Shell of Ce Atom Site and Reshaping of Carrier Enable Single-Atom Nanozyme to Efficiently Express Oxidase-like Activity

• Published in: Nano letters Vol. 24; no. 26; pp. 8071 - 8079
• Main Authors: Sun, Qijun, Wu, Meng, Niu, Na, Chen, Ligang, Liu, Song, Yu, Jie, Wu, Xinzhao, Bai, Fu-Quan, Yang, Piaoping
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.07.2024
• Subjects: Butyrylcholinesterase - chemistry; Butyrylcholinesterase - metabolism; Cerium - chemistry; Indoles - chemistry; Oxidation-Reduction; Oxidoreductases - chemistry; Oxidoreductases - metabolism; Oxygen - chemistry; Polyethylene Glycols - chemistry; Polymers - chemistry; coordination environment; Ce single-atom nanozyme; carbon-based carrier; oxidase mimicking; density functional theory
• DOI: 10.1021/acs.nanolett.4c01846
• ISSN: 1530-6984; 1530-6992

Single-atom nanozymes (SANs) are considered to be ideal substitutes for natural enzymes due to their high atom utilization. This work reported a strategy to manipulate the second coordination shell of the Ce atom and reshape the carbon carrier to improve the oxidase-like activity of SANs. Internally, S atoms were symmetrically embedded into the second coordination layer to form a Ce–N4S2–C structure, which reduced the energy barrier for O2 reduction, promoted the electron transfer from the Ce atom to O atoms, and enhanced the interaction between the d orbital of the Ce atom and p orbital of O atoms. Externally, in situ polymerization of mussel-inspired polydopamine on the precursor helps capture metal sources and protects the 3D structure of the carrier during pyrolysis. On the other hand, polyethylene glycol (PEG) modulated the interface of the material to enhance water dispersion and mass transfer efficiency. As a proof of concept, the constructed PEG@P@Ce–N/S–C was applied to the multimodal assay of butyrylcholinesterase activity.