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. Graphical Dual-enzymatic mimics : Based on photoinduced hierarchical co-assembly, diverse dual-enzymatic mimics, such as nanospheres, surface folded nanoparticles, and truncated polyhedrons, are constructed. The formed nanostructures exhibit superior catalytic activity towards cascade reactions, with potential applications in biocatalysis and biosensing.