MOF‐Hosted Enzymes for Continuous Flow Catalysis in Aqueous and Organic Solvents

Abstract

Fully exploiting the potential of enzymes in cell‐free biocatalysis requires stabilization of the catalytically active proteins and their integration into efficient reactor systems. Although in recent years initial steps towards the immobilization of such biomolecules in metal–organic frameworks (MOFs) have been taken, these demonstrations have been limited to batch experiments and to aqueous conditions. Here we demonstrate a MOF‐based continuous flow enzyme reactor system, with high productivity and stability, which is also suitable for organic solvents. Under aqueous conditions, the stability of the enzyme was increased 30‐fold, and the space–time yield exceeded that obtained with other enzyme immobilization strategies by an order of magnitude. Importantly, the infiltration of the proteins into the MOF did not require additional functionalization, thus allowing for time‐ and cost‐efficient fabrication of the biocatalysts using label‐free enzymes.

Boosting Protein Encapsulation through Lewis-Acid-Mediated Metal–Organic Framework Mineralization: Toward Effective Intracellular Delivery

“…2 Metal−organic frameworks (MOFs) have been recently used as porous platforms for the entrapment and preservation of different bioentities. 3 Characterized by a hybrid nature, MOFs result in unique crystalline structures that offer great performances not only in gas storage/separation 4 but also in biotechnological 5 and health-related fields 6,7 due to their high cargo loading, biodegradability, and processability. 8 Most of these uses consider MOFs as small-molecule carriers; however, the encapsulation, transport, and release of biological macromolecules have gained an exceptional popularity in the last decade.…”

“…Metal–organic frameworks (MOFs) have been recently used as porous platforms for the entrapment and preservation of different bioentities . Characterized by a hybrid nature, MOFs result in unique crystalline structures that offer great performances not only in gas storage/separation but also in biotechnological and health-related fields , due to their high cargo loading, biodegradability, and processability …”

Confining enzymes in porous organic frameworks: from synthetic strategy and characterization to healthcare applications

“…Under aqueous conditions, the stability of the enzyme increased by 30-fold, and the space-time yield of the biocomposite outperformed that of other zeolite-, kaolin-, montmorillonite-and ion exchange-based immobilization strategies by an order of magnitude. 63 Considering the large dimensions of most enzymes (usually larger than 4 nm), it is still difficult to immobilize enzymes with dimensions larger than 3.1 nm NU-1000. Regarding this, a series of Zr-based MOFs, with interconnected hierarchical pores ranging from 3.3 to 6.7 nm, was carefully assembled by maintaining precise control of the torsional angles associated with the organic linkers.…”

“…Under aqueous conditions, the stability of the enzyme increased by 30-fold, and the space-time yield of the biocomposite outperformed that of other zeolite-, kaolin-, montmorillonite- and ion exchange-based immobilization strategies by an order of magnitude. 63…”

Strategies for Transferring Photobiocatalysis to Continuous Flow Exemplified by the Photodecarboxylation of Fatty Acids

“…28,29 Performance of light-dependent reactions in continuous flow, in particular in microchannels (ID < 1 mm), represents a convenient way of circumventing this issue. 28,29 Although the performance of biocatalytic transformations in continuous flow has been established, [30][31][32][33][34][35][36] examples of flow photobiocatalysis remain scarce and are not of synthetic applicability. 37 Examples include the generation of oxygen by a cyanobacterium for the oxidation of cyclohexene to cyclohexanol, 38 and the photochemical cofactor regeneration for the enzymatic reduction of CO2 to formate.…”