Enzyme-chiral nanozyme hybrid catalysts at active interfaces for cascade enantioselective catalysis driven by in-situ generated H2O2.

Abstract

Multi-enzyme systems often face rate-limiting mismatches between catalytic steps, as well as the inherent limitations of enzymes under harsh conditions in practical applications. Herein, we report a co-immobilization cascade system of a chiral nanozyme and glucose oxidase (GOD) for the enantioselective catalysis of chiral 3,4-dihydroxyphenylalanine (DOPA). In the design of hybrid catalysts, a bio-bimetallic-organic framework (Fe-Zn-Glu(Bzim)) serves as the chiral recognition center and the peroxidase (POD)-like nanozyme, enabling integrated enantioselective and oxidative functions. GOD is covalently immobilized onto the surface of the chiral Fe-Zn-Glu(Bzim) nanozyme to construct a bionic cascade catalyst of GOD@Fe-Zn-Glu(Bzim). In addition, nanozyme exhibits excellent temperature and solvent resistance. Experimental results demonstrate that the covalent immobilization of GOD onto the nanozyme surface can generate H2O2 in situ in aqueous solution, efficiently driving the cascade reaction to achieve enantioselective catalysis of chiral DOPA. Notably, GOD@Fe-Zn-Glu(Bzim) shows 2.15-fold higher activity than free GOD at identical protein loading. The hybrid catalyst provides a promising strategy for effectively integrating the enzymatic and nanozyme catalysis, with potential implications for interface-enabled cascade biocatalysis.