Enhancing Biocatalysis: Metal–Organic Frameworks as Multifunctional Enzyme Hosts

ConspectusEnzymes are highly efficient and selective catalysts that operate under mild conditions, making them invaluable for various chemical transformations. However, their limitations, such as instability and high cost, call for advancements in enzyme immobilization and the development of suitable host materials. Metal-organic frameworks (MOFs), characterized by high porosity, crystallinity, and tunability, are promising candidates for enzyme encapsulation. Among these, zirconium-based MOFs (Zr-MOFs) stand out due to their exceptional structural diversity and chemical stability. The physical and chemical properties of Zr-MOFs can be tuned and characterized with atomic precision, and their interactions with enzymes can be analyzed through a range of techniques spanning from chemistry and materials science to biochemistry. This tunable platform provides opportunities to systematically investigate the impact of encapsulation on the stability and activity of enzymes in order to develop design rules for enzyme hosts.In this Account, we discuss experimentally validated concepts for designing MOF hosts based on their structural properties and enzyme encapsulation mechanisms. We present methods to enhance enzyme catalytic performance through encapsulation and strategies for creating multifunctional enzyme@MOF systems via host modifications. We start by highlighting the importance of host structural design that maximizes substrate diffusion and enzyme availability, with particular focus on MOFs containing hierarchical mesoporous structures such as those in the