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

Abstract

Inspired by natural enzymes, hierarchical catalytic supramolecular nanostructuresw ere developed by the coassembly of hemin and glucose oxidase (or Au NPs) with the photosensitive ferrocene-tyrosine (Fc-Y) molecule. Illuminated by white light, the Fc-Y moleculesa re polymerized and co-assemblew ith hemin into truncated polyhedrons. The Au NPs grew in situ at the surface of the co-assembled polyhedrons, achieving ordered supramolecular nanostructures. Becauset he Au NPs can serve as an artificial glucose oxidase and the hemin could act as ap eroxidase mimic, the supra-molecular hybrid nanostructures were used to mimicn atural enzymes and catalyzet he glucosec onversionc ascade reaction. The hybrid Au NPs@Fc-Y&hemin polyhedrons showed superior catalytic activity,g ood reusability,a nd maintained the catalytic activity over aw ide temperaturea nd pH range. The study demonstrates af easible strategy to construct hierarchicalc o-assembled supramolecular nanostructures as multi-enzyme mimics,w ith potential applications in biocatalysis and biosensing.

Nanomaterials with Glucose Oxidase-Mimicking Activity for Biomedical Applications

“…Apart from the optimized dispersity and reaction kinetics, the nanocarrier-supported Au NPs have also been discovered with dual enzyme-like catalytic activities for realizing the biomimetic enzymatic cascade reaction [ 34 ]. By taking advantage of the GOD-like activity, the obtained MSN–Au NPs catalytically oxidize glucose to yield gluconic acid and H 2 O 2 in the physiological environment ( Figure 3 c) [ 35 ].…”

A covalent crosslinking strategy to construct a robust peptide-based artificial esterase

“…34,35 After photo-crosslinking, the CQO stretching band in the amide I region red-shifted to 1657 cm À1 , and the C-N stretching band in the amide III region red-shifted to 1170 cm À1 , indicating that strong hydrogen bonding was involved in the CL-YYHYY. 36 The free YYHYY displayed characteristic tyrosine peaks at 835 cm À1 (aromatic ring bending vibrations) and 723 cm À1 (the aromatic C-H bending vibration of the associated tyrosine). 37 After crosslinking, the peak at 723 cm À1 disappeared, indicating a new substitution occurred on the aromatic ring which affected the di-substituted state of the tyrosine side chain.…”

Improving the catalytic ability of a peptide-based artificial glycosidase through a tyrosine strategy

“…The phenolic side chains of Tyr can form a dityrosine bond under UV irradiation, which is favourable for stabilizing the supramolecular structure through the formation of intermolecular covalent bonds. 31,32 Herein, YA 2 Y-E 3 assemblies were explored to UV light for 48 h to fabricate CL-YA 2 Y-E 3 through the photocrosslinking of tyrosine residues. The hydrogel became light brown and generated aggregates gradually (Fig.…”