Reticular chemistry for improving the activity of biocatalysts: Synthesis strategies and advanced characterization techniques

Abstract

Biocatalysis has become an indispensable tool for modern organic synthesis, both in academia and across pharmaceutical and chemical industries. In the past decade, new materials chemistry strategies have been employed to modulate and enhance the enzyme activity, uncovering the frontier of natural enzyme catalysis. In this review, we spotlight cutting-edge examples of reticular chemistry, including metal-organic frameworks, covalent-organic frameworks, and hydrogen-bonded organic frameworks to expand the scope of biocatalysts to achieve activities beyond the natural enzyme or conventional biocatalysts. Then, we discuss how modern advanced characterization techniques can assist in understanding the mechanisms of the enhanced catalytic performance at the nano-bio interface. These advances are anticipated to help researchers to create more useful strategies and use advanced characterization technologies to tackle the key issues as well as improve the biocatalysts performance so as to promote the research and application of biocatalytic reticular frameworks. • Synthesis strategies employing reticular chemistry to enhance biocatalysis are focused on • Advanced characterization techniques revealing enhanced biocatalytic mechanisms are spotlighted • Opportunities and challenges are proposed for designing advanced nanobiocatalysts Biocatalysis has become an indispensable tool for modern organic synthesis across many industries. New materials chemistry strategies have been employed to modulate and enhance enzyme activity, uncovering the frontier of natural enzyme catalysis. Recently, reticular chemistry has been emphasized in many crystalline open-framework materials, and these have been reported to successfully immobilize enzymes. Biocatalytic reticular frameworks have demonstrated superior stability compared with natural enzymes and conventional biocatalysts. However, three important factors could alter enzymatic activity upon immobilization: (1) substrate affinity, (2) availability of enzyme active sites, and (3) conformational change of enzyme. Herein, the role of reticular chemistry and advanced synthesis strategies for tuning biocatalytic activity beyond natural and conventional biocatalysts, as well as advanced characterization techniques for revealing enhanced biocatalytic mechanisms, are thoroughly summarized. We anticipate that the continued ingenuity of reticular chemistry development, as well as the growing power and complexity of protein engineering techniques, will provide boundless surprises in the field of biocatalysis. Biocatalysis has been developed as a powerful technology for chemical innovation both in academia and across many industries. Enzymes are customized biomacromolecules that can efficiently catalyze specific conversions under defined environmental constraints. Reticular chemistry can promote and refine bioreactivity of enzymes, which is crucial to facilitate their industrial application. The continued ingenuity of materials development, as well as the growing power and complexity of protein engineering techniques, is expected to provide boundless surprises in the field of biocatalysis.