Biocatalytic Metal–Organic Frameworks: Prospects Beyond Bioprotective Porous Matrices

Abstract

Biocatalytic metal-organic framework (MOF) composites, synthesized by interfacing MOFs with biocatalytic components, possess the unprecedented synergetic properties that is hard to achieve by the conventional strategies, represents one of the next-generation composite materials for diverse biotechnological applications. Until now , research on the applications of biocatalytic MOFs is still in its preliminary stage, with a wide variety of studies being focusing on the bioprotection role of MOFs. However, their diversity of building units, molecular-scale tunability, modular synthetic routes, and more detailed understanding of the heterogeneous MOF-biointerface could even lead to completely new applications and potentials beyond our current imagination. The most recent rapid advanced progress in biocatalytic MOFs present ground-breaking applications in smart and tunable biocatalysis, precision nanomedicine, vaccine and gene delivery, biosensing and nano-biohybrids. Herein, the general and advanced synthesis strategies for improving the materials properties of biocatalytic MOFs, from tuning biocatalytic activity to framework stability to synergistic properties with other materials, are summarized. Then, the latest state-of-the-art applications of the biocatalytic MOF systems and recent advanced developments that are shaping this emerging field are surveyed. Finally, to define promising research directions, a critical evaluation and future prospects for the potential applications of biocatalytic MOFs are provided.

Multi‐enzyme Cascade Reactions in Metal‐organic Frameworks

“…Among which, the coupling of enzymes with metal-organic frameworks (MOFs) has attracted burgeoning interests in the last few years. [16][17][18][19][20][21][22][23] Constructed from organic linkers and metal ions or metalcontaining clusters, MOFs demonstrate many superior properties, such as well-defined pore aperture, tunable pore window, tailorable composition and structure, versatile functionality and high guest loading efficiency. [24,25] When introducing multi-enzyme in MOFs, MOFs enable the selective diffusion of substrates and intermediates to the reactive site, thus accelerating the multi-enzyme cascade reactions.…”

“…[54] In addition, with extraordinary chemical robustness and high enzyme encapsulation capacity of MOFs, the multi-enzyme@MOF systems allow new possibilities in artificial and hybrid cells design, enabling new potentials in cell manipulation and enzyme replacement therapy. [47,57] Although a series of review articles on the diversity of enzymatic cascades [1,[58][59][60][61][62] and their immobilization in macromolecular scaffolds have been published within the past few years, [9,18,21,22,31,[63][64][65][66][67][68][69] none has particularly focused on the immobilization strategies of multi-enzyme within MOFs and their cutting-edge applications. In this Personal Account, the most recent advances and challenges on multi-enzyme cascade reactions within MOFs, from the works by us and the work of others, are provided.…”

Metal–Organic Frameworks for Enzyme Immobilization: Beyond Host Matrix Materials

“…Therefore, those selected enzymes usually are relatively small biomolecules, and the dimensions are around 3–6 nm (e.g., myoglobin 2.1 × 3.5 × 4.4 nm, GFP 3.4 × 4.5 nm, Cyt c 2.6 × 3.2 × 3.3 nm, HRP 4.0 × 4.4 × 6.8 nm, GOx 6.0 × 5.2 × 7.7 nm, lysozyme 3.0 × 3.0 × 4.5 nm, lipase 3.0 × 3.2 × 6.6). 8 − 10 Notably, some large mesoporous MOFs would allow oversized enzymes to infiltrate through slightly smaller apertures, but with a partial unfolding process before entering pores, and it, in turn, increases the possibility of selecting those MOFs with slightly smaller pore dimensions. 20 In this approach, the design and synthesis of large mesoporous MOFs play the dominant role, especially regarding those MOFs with high water stability.…”

Biofriendly micro/nanomotors operating on biocatalysis: from natural to biological environments

“…In addition, less biofriendly fuel such as H 2 O 2 , needs to be kept at lower level or replaced by other more biofriendly fuels. Nevertheless, with the research of new nanomaterials that can protect enzymes even inside the body (Guo et al 2020;Liang and Liang 2020), enzymepowered MNMs are expected to open a new era in nanomedicine.…”