Limin Ma, Yadi Wang, Yaoyao Chen, Rui Han, Genqi Xu, Chunxia Ma, Dongxu Jiao, Huanhuan Xing, Dewen Wang, Xiurong Yang
ABSTRACT Laccases are widely utilized in biochemical sensing, food quality monitoring, and pollutant degradation due to their environmentally friendly nature. However, the development of non‐copper‐based laccase mimics remains limited, and their catalytic mechanisms and practical applications require further investigation. Herein, we incorporate non‐metallic boron (B) into manganese (Mn)‐based oxides (MBO), endowing the material with exceptional laccase‐like activity, free from interference typically induced by extraneous metal sites. Acting as an electron modulator, B increases the electron density of Mn active centers and lowers their average valence state (Mn n−δ ), thereby promoting O 2 reduction through a non‐radical pathway. This electronic regulation alters the catalytic mechanism and lowers the activation energy required for benzoquinone formation. As an efficient laccase mimic, MBO catalyzes the Michael addition between dopamine and resorcinol, yielding a dual‐signal product with measurable absorbance and fluorescence. By exploiting the specific coordination and inhibition of MBO by ergothioneine (EGT), a dual‐mode sensing detection and molecular logic operation (“AND”‐“INH”) system was constructed for EGT detection, which achieved high sensitivity, a low detection limit, and excellent operational stability. This work presents a novel strategy for enhancing the laccase‐like performance of Mn‐based nanozymes through non‐metallic doping and applying it to biochemical sensing with logical analysis.