Correlating Descriptors of Chiral Au Nanoparticles with Their Capability toward Electrochemical Sensing of Enantiomers

The electrochemical recognition of enantiomers by intrinsically chiral Au nanoparticles is strongly regulated by key chiral descriptors, namely the g-factor, surface geometry, and anisotropy. However, the explicit correlation between these structural parameters and their enantioselective sensing performance remains an unresolved challenge. Herein, we report the controllable synthesis of chiral Au nanoparticles with tailorable g-factors, surface geometry, and anisotropic structures, enabling quantitative elucidation of the structure-performance relationship in the electrochemical sensing of enantiomers. Using l/d-dihydroxyphenylalanine as the electrochemical probe, we systematically established the regulatory effects of chiral descriptors on molecular enantiomer recognition. Specifically, for nanoparticles with identical chiral geometry, the enantioselectivity exhibits a positive correlation with the g-factor magnitude. In contrast, when g-factor values are comparable, both geometrical characteristics and structural anisotropy become the dominant determinants of the sensing selectivity. These findings not only clarify the intrinsic correlation between the chiral descriptors of nanostructures and their enantiomeric electrochemical recognition capability but also provide a critical knowledge framework for the rational design of high-performance chiral nanostructures tailored for enantioselective sensing applications.