Molecularly Imprinted Polyaniline-Coated Cu-Zeolitic Imidazolate Framework Nanoparticles: Uricase-Mimicking “Polynanozyme” Catalyzing Uric Acid Oxidation

One of the drawbacks of nanozyme catalytic functions rests in their moderate catalytic activities due to the lack of effective binding sites concentrating the reaction substrate at the nanozyme catalytic interface. Methods to concentrate the substrates at the catalytic interface are essential to improving nanozyme functions. The present study addresses this goal by designing uric acid (UA) molecular-imprinted polyaniline (PAn)-coated Cu-zeolitic imidazolate framework (Cu-ZIF) nanoparticles as superior nanozymes, "polynanozymes", catalyzing the H2O2 oxidation of UA to allantoin (peroxidase activity) or the aerobic, uricase mimicking, oxidation of UA to allantoin (oxidase activity). While bare Cu-ZIF nanoparticles reveal only peroxidase activity and the nonimprinted PAn-coated Cu-ZIF nanoparticles reveal inhibited peroxidase activity, the molecular-imprinted PAn-coated Cu-ZIF nanoparticles reveal a 6.1-fold enhanced peroxidase activity, attributed to the concentration of the UA substrate at the catalytic nanoparticle interface. Moreover, the catalytic aerobic oxidation of UA to allantoin by the imprinted PAn-coated Cu-ZIF nanoparticles is lacking in the bare particles, demonstrating the evolved catalytic functions in the molecularly imprinted polynanozymes. Mechanistic characterization of the system reveals that within the UA molecular imprinting process of the PAn coating, Cu+ reactive units are generated within the Cu-ZIF nanoparticles, and these provide reactive sites for generating O2-• as an intermediate agent guiding the oxidase activities of the nanoparticles. The study highlights the practical utility of molecular-imprinted polynanozymes in catalytic pathways lacking in the bare nanozymes, thus broadening the scope of nanozyme systems.