Construction of Supramolecular Nanostructures with High Catalytic Activity by Photoinduced Hierarchical Co‐Assembly

Inspired by natural enzymes, hierarchical catalytic supramolecular nanostructures were developed by the co-assembly of hemin and glucose oxidase (or Au NPs) with the photosensitive ferrocene-tyrosine (Fc-Y) molecule. Illuminated by white light, the Fc-Y molecules are polymerized and co-assemble with hemin into truncated polyhedrons. The Au NPs grew in situ at the surface of the co-assembled polyhedrons, achieving ordered supramolecular nanostructures. Because the Au NPs can serve as an artificial glucose oxidase and the hemin could act as a peroxidase mimic, the supramolecular hybrid nanostructures were used to mimic natural enzymes and catalyze the glucose conversion cascade reaction. The hybrid Au NPs@Fc-Y&hemin polyhedrons showed superior catalytic activity, good reusability, and maintained the catalytic activity over a wide temperature and pH range. The study demonstrates a feasible strategy to construct hierarchical co-assembled supramolecular nanostructures as multi-enzyme mimics, with potential applications in biocatalysis and biosensing.