A Hybrid VOx Incorporated Hexacyanoferrate Nanostructured Hydrogel as a Multienzyme Mimetic via Cascade Reactions

Inspired by the cascade reactions occurring in micro-organelles of living systems, we have developed a hybrid hydrogel, a nanozyme that mimics three key enzymes including peroxidase, superoxide dismutase, and catalase. The organic/inorganic nanostructured hydrogel constituting VOx incorporated hexacyanoferrate Berlin green analogue complex (VOxBG) is prepared by a simple one-step hydrothermal process, and its composition, structure, and properties are thoroughly investigated. Polyvinylpyrrolidone, a low-cost and biocompatible polymer, was utilized as a scaffold to increase the surface area and dispersion of the highly active catalytic centers of the nanozyme. Compared to the widely used horseradish peroxidase in enzyme-linked immunosorbent assay, our VOxBG analogue hydrogel displays an excellent affinity toward the chromogenic substrate that is used in these peroxidase-based assays. This higher affinity makes it a competent nanozyme for detection and oxidation of biomolecules, including glucose, in a cascade-like system which can be further used for hydrogel photolithography. The VOxBG analogue hydrogel also holds a good ability for the rapid and efficient oxidative degradation of environmentally unfriendly recalcitrant substrates under light irradiation. Detailed mechanistic studies of this multifaceted material suggest that different complex catalytic processes and routes are involved in these photo-Fenton and Fenton reactions that are responsible for the generation as well as consumption of reactive oxygen species, which are effectively activated by a multienzyme mimetic of the VOxBG analogue hydrogel.