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    Creating a suprazyme: integrating a molecular enzyme mimic with a nanozyme for enhanced catalysis

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    Enzyme mimics, due to their limited complexity, traditionally display low catalytic efficiency. Herein we present a strategy that enables the transformation of a slow-acting catalyst into a highly active one by creating a non-covalent suprastructure, termed “suprazyme”. We show that cucurbit[7]uril macrocycles, rudimentary molecular enzyme mimics, embedded within an anionic monolayer on the surface of gold nanoparticles, outperform individual cucurbit[7]urils as well as nanoparticles, which also exhibit catalytic enzyme-like activity and thus act as nanozymes, by over 50 times, showcasing a 1044-fold acceleration in a model oxime formation reaction. The superior performance of such a suprazyme is attributed to a synergistic interplay between the organic monolayer and macrocycles, which is accompanied by a decreased local polarity and pH that favors the acid-catalyzed condensation process. The proposed approach holds promise for developing diverse suprazymes, contingent upon achieving a complementary structure and mechanism of action between the molecular catalyst and nanoparticles.This research was funded by the National Science Centre of Poland (grant OPUS 18 no. 2019/35/B/ST4/01758). We acknowledge the CINECA award under the ISCRA initiative, for the availability of high-performance computing resources and support, along with the SISSA Computing Center (https://www.sissa.it)
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