Spatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation

• Published in: Nature communications Vol. 15; no. 1; pp. 2239 - 13
• Main Authors: Wang, Ying, Paidi, Vinod K., Wang, Weizhen, Wang, Yong, Jia, Guangri, Yan, Tingyu, Cui, Xiaoqiang, Cai, Songhua, Zhao, Jingxiang, Lee, Kug-Seung, Lee, Lawrence Yoon Suk, Wong, Kwok-Yin
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 12.03.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/133; 140/146; 147/137; 147/3; 639/301/54/989; 639/638/77/887; 639/638/92/603; Biomimetics; Configurations; Cytochrome; Cytochrome P450; Cytochrome-c oxidase; Cytochromes P450; Drug interaction; Drug interactions; Drug metabolism; Electron transfer; Enzymes; Humanities and Social Sciences; multidisciplinary; Physics; Science; Science (multidisciplinary); Substrate preferences; Substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-46528-w

The precise design of single-atom nanozymes (SAzymes) and understanding of their biocatalytic mechanisms hold great promise for developing ideal bio-enzyme substitutes. While considerable efforts have been directed towards mimicking partial bio-inspired structures, the integration of heterogeneous SAzymes configurations and homogeneous enzyme-like mechanism remains an enormous challenge. Here, we show a spatial engineering strategy to fabricate dual-sites SAzymes with atomic Fe active center and adjacent Cu sites. Compared to planar Fe–Cu dual-atomic sites, vertically stacked Fe–Cu geometry in FePc@2D-Cu–N–C possesses highly optimized scaffolds, favorable substrate affinity, and fast electron transfer. These characteristics of FePc@2D-Cu–N–C SAzyme induces biomimetic O 2 activation through homogenous enzymatic pathway, resembling functional and mechanistic similarity to natural cytochrome c oxidase. Furthermore, it presents an appealing alternative of cytochrome P450 3A4 for drug metabolism and drug–drug interaction. These findings are expected to deepen the fundamental understanding of atomic-level design in next-generation bio-inspired nanozymes. Integrating heterogeneous single atom nanozyme (SAzyme) configurations and homogeneous enzyme-like mechanism is promising for optimizing SAzymes but elusive. Here the authors address this issue by developing a spatial engineering strategy to fabricate dual-sites SAzymes incorporating single atom Fe active centers (Fe–N 4 ) and Cu atomic sites (Cu–N 4 ) in a vertically stacked Fe–N 4 and Cu–N 4 geometry.