Supramolecular Polyaniline-Metal Ion as Chiral Nanozymes for Enantioselective Catalysis

Understanding origin of asymmetric information encoded on chiral nanozymes is important in mediating enantioselective catalysis. Herein, the supramolecular chiral nanozymes constructed from P/M-polyaniline (P/M-PANI) nanotwists and metal ions (M²⁺ , M = Cu, Ni, Co, and Zn) are designed through thioglycolic acid (TA) without chiral molecules to show the regulated catalytic efficiency and enantioselectivity. With combination of chiral environment from supramolecular scaffolds and catalytic center from metal ions, the P-PANI-TA-M²⁺ as nanozymes show preference to 3,4-dihydroxy-S-phenylalanine (S-DOPA) oxidation while the M-PANI-TA-M²⁺ show better selectivity to R-DOPA oxidation. Among them, though the Cu²⁺ doped supramolecular nanotwists show the highest catalytic efficiency, the Co²⁺ doped ones with moderate catalytic efficiency can exhibit the best enantioselectivity with select factor as high as 2.07. The molecular dynamic (MD) simulation clarifies the mechanism of enantioselective catalysis caused by the differential kinetics with S/R-DOPA enantiomers adsorbed on chiral PANI surface and free in solution. This work systematically studies the synergistic effect between the chiral supramolecular nanostructures assembled by achiral species and metal ions as peroxidase-like catalytic centers to regulate the enantioselectivity, providing deep understanding of the origin of asymmetric catalysis and serving as strong foundation to guide the design of nanozymes with high enantioselectivity.