Covalent organic frameworks as emerging host platforms for enzyme immobilization and robust biocatalysis - A review

In recent years, the synthesis and application of green and sustainable products have become global ecological and societal issues. Based on the principles of green chemistry, the application of different biocatalysts not only produce target products and decreases side effects but also enhances the selectivity and activity. Enzyme-based biocatalysts are very interesting due to their high catalytic performance, eco-friendly reaction systems, and selectivity. Immobilization is demonstrated as a favorable approach to improve the stability and recyclability of enzymes. Among different supports, porous and crystalline materials, covalent organic frameworks (COFs), represent an interesting class of support matrices for the immobilization of different enzymes. Owing to tunable physicochemical characteristics, a high degree of crystallinity, large specific surface area, superior adsorption capacity, pre-designable structure and marked stability, COFs might consider as perfect host materials for improving the desirable properties of enzymes, such as poor stability, low operational range, lack of repeatability, and products/by-products inhibition for large-scale applications. The enzyme-incorporated COFs have emerged as one of the hopeful ways to constitute tailor-made biocatalytic systems, which can be employed in an array of reactions. Highly porous nature of many COFs led to increased process output in contrast to other micro/nanoparticles. The enzymes can be integrated into COFs through different techniques, including physical adsorption and direct covalent attachment between the enzyme molecules and COFs or through a cross-linking agent. Herein, we discuss and highlight the synthesis methods, properties, and functionalization of COFs and the recent literature for the application of these materials in enzymes immobilization. Main approaches for immobilization of enzymes into COFs and the catalytic applications of these materials are also presented. This study offers new avenues to address the limitations of traditional enzyme immobilization supports as well as delivers new possibilities to construct smart biocatalytic systems for diverse biotechnological applications.