Abstract

Enzymes, as natural catalysts with remarkable catalytic activity and high region-selectivities, hold great promise in industrial catalysis. However, applications of enzymatic transformation are hampered by the fragility of enzymes in harsh conditions. Recently, metal–organic frameworks (MOFs), due to their high stability and available structural properties, have emerged as a promising platform for enzyme immobilization. Synthetic strategies of enzyme-MOF composites mainly including surface immobilization, covalent linkage, pore entrapment and in situ synthesis. Compared with free enzymes, most immobilized enzymes exhibit enhanced resistance against solvents and high temperatures. Besides, MOFs serving as matrixes for enzyme immobilization show extraordinary superiority in many aspects compared with other supporting materials. The advantages of using MOFs to support enzymes are discussed. To obtain a high enzyme loading capacity and to reduce the diffusion resistance of reactants and products during the reaction, the mesoporous MOFs have been designed and constructed. This review also covers the applications of enzyme-MOF composites in bio-sensing and detection, bio-catalysis, and cancer therapy, which is concerned with interdisciplinary nano-chemistry, material science and medical chemistry. Finally, some perspectives on reservation or enhancement of bio-catalytic activity of enzyme-MOF composites and the future of enzyme immobilization strategies are discussed.

Highlights

  • Enzymes are undisputedly one of most significant macromolecular biological catalysts, which are widely used in fields such as fine chemicals and drug synthesis, sensing, energy and food processing

  • Metal-organic frameworks have emerged as the comprehensive platform for enzyme immobilization or the synthesis of other hybrid materials since the crystalline structure, pore volume, physical and chemical properties of metal–organic frameworks (MOFs) can be modulated owing to an extensive choice of possible organic linkers and inorganic building units

  • Metal-organic frameworks are emerging as viable host matrixes for enzyme immobilization

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Summary

INTRODUCTION

Enzymes are undisputedly one of most significant macromolecular biological catalysts, which are widely used in fields such as fine chemicals and drug synthesis, sensing, energy and food processing. Mild operating conditions are the key for in situ enzyme-MOFs synthesis where enzymes and MOF precursors (metal ions and organic ligands) are mixed with the most common aqueous solution This method allows for the nucleation and growth of MOF simultaneously, and the size of the gust molecule can be larger than the pore size of MOFs, resulting in enzyme embedded MOF crystals (Figure 1A). The varying degree of activity loss was observed for GOx-CuBDC and GOx&CuBDC composites (Figure 4C) Though these preliminary researches are promising, the encapsulation of enzyme into MOFs by this in situ approach largely relies on the synthetic conditions, which should be simple and biocompatible. MP-11 was immobilized in all these MBS matrixes through van der Waals interaction between the MP-11 and TABLE 1 | Examples of preparation and application of the enzyme-MOF composites

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