Rearranging Spin Electrons by Axial-Ligand-Induced Orbital Splitting to Regulate Enzymatic Activity of Single-Atom Nanozyme with Destructive d−π Conjugation

• DOI: 10.1021/jacs.4c04322
• Publication Date: 2024-05-16T03:38:26Z
• Authors: Qi Zhao; Min Zhang; Yixuan Gao; Hongliang Dong; Lirong Zheng; Yutian Zhang; Jin Ouyang; Na Na

Most of the nanozymes have been obtained based on trial and error, for which application is usually compromised by enzymatic activity regulation due to a vague catalytic mechanism. Herein, hollow axial Mo–Pt single-atom nanozyme (H-MoN5@PtN4/C) constructed two-tier template capture strategy. The ligand can induce Mo 4d orbital splitting, leading rearrangement spin electrons (↑ ↑ → ↑↓) regulate activity. This creates catalase-like enhances oxidase-like catalyze cascade reactions (H2O2 O2 O2•–), overcome tumor hypoxia accumulate cytotoxic superoxide radicals (O2•–). Significantly, H-MoN5@PtN4/C displays destructive d−π conjugation between metal substrate attenuate restriction orbitals electrons. markedly improves performance (catalase-like activity) single atom peroxidase-like properties Pt atom. Furthermore, deplete overexpressed glutathione (GSH) through redox reaction, avoid consumption ROS (O2•– •OH). As result, limitations complex microenvironment (TME) tumor-specific therapy TME-activated