Integrating Enzymes with Reticular Frameworks To Govern Biocatalysis.

Integrating enzymes with reticular frameworks offers promising avenues for access to functionally tailorable biocatalysis. This Minireview explores recent advances in enzyme-reticular framework hybrid biocomposites, focusing on the utilization of porous reticular frameworks, including metal-organic frameworks, covalent-organic frameworks, and hydrogen-bonded organic frameworks, to regulate the reactivity of an enzyme encapsulated inside mainly by pore infiltration and in situ encapsulation strategies. We highlight how pore engineering and host-guest interfacial interactions within reticular frameworks create tailored microenvironments that substantially impact the mass transfer and enzyme conformation, leading to biocatalytic rate enhancement, or imparting enzymes with non-native biocatalytic functions, including substrate selectivity and new activity. Additionally, the feasibility of leveraging the photothermal effect of a framework to optimize the local reaction temperature and photoelectric effect to elicit diverse photoenzyme-coupled reactions is also summarized in detail, which can expand the functional repertoire of biocatalytic transformations under light irradiation. This Minireview underscores the potential of reticular frameworks as tunable and reliable platforms to govern biocatalysis, offering pathways for engineering sustainable, efficient, and selective biocatalytic reactors in pharmaceutical, environmental, and energy-related applications.