Designed Synthesis of Compartmented Bienzyme Biocatalysts Based on Core–Shell Zeolitic Imidazole Framework Nanostructures

Abstract

For complex cascade biocatalysis, multienzyme compartmentalization helps to optimize substrate transport channels and promote the orderly and tunable progress of step reactions. Herein, a simple and general synthesis strategy is proposed for the construction of a multienzyme biocatalyst by compartmentalizing glucose oxidase and horseradish peroxidase (GOx and HRP) within core–shell zeolite imidazole frameworks (ZIF)‐8@ZIF‐8 nanostructures. Owing to the combined effects of biomimetic mineralization and the fine regulation of the ZIF‐8 growth process, the uniform shell encloses the seed (core) surface by epitaxial growth, and the bienzyme system is accurately localized in a controlled manner. The versatility of this strategy is also reflected in ZIF‐67. Meanwhile, with the ability to covalently bind divalent metal ions, lithocholic acid (LCA) is used as a competitive ligand to improve the pore structure of the ZIF from a single micropore to a hierarchical micro/mesopore network, which greatly increases mass transfer efficiency. Furthermore, the multienzyme cascade reaction is exemplified by the oxidation of o‐phenylenediamine (OPD). The findings show that the bienzyme assembly strategy significantly affects the biocatalytic efficiency mainly by influencing the utilization efficiency of the intermediate (Hydrogen peroxide, H2O2) between the step reactions. This study sheds new light on facile synthetic routes to constructing in vitro multienzyme biocatalysts.

Construction of a hollow MOF with high sedimentation performance and co-immobilization of multiple-enzymes for preparing rare ginsenoside CK

“…5b), corresponding to –N–H derived from the amino acids of enzymes. 45,51 The result shows that the enzymes were successfully immobilized. The Cu 2p spectrum (Fig.…”

Spatially Patterned, Porous Protein Crystals as Multifunctional Materials

“…GOx and HRP are model enzymes that have been utilized to demonstrate cooperative, cascade reactions. 5,86,87 Specifically, GOx catalyzes the O 2 -mediated oxidation of glucose into D-glucono-δ-lactone and produces H 2 O 2 , which HRP can utilize to oxidize small molecules such as Amplex Red to produce resorufin (Figure 6b).…”

“…Upon confirming that ΔC HuHF@ C157 HuHF PIX showed the same reversible expansion/contraction behavior as was observed with pure HuHF PIX (Figure S12), we set out to generate a spatially patterned, dual-enzyme system consisting of glucose oxidase (GOx; dimensions: 5.2 × 5.0 × 7.7 nm 3 ) and horseradish peroxidase (HRP; dimensions: 3.5 × 3.8 × 5.4 nm 3 ) (Figure a). GOx and HRP are model enzymes that have been utilized to demonstrate cooperative, cascade reactions. ,, Specifically, GOx catalyzes the O 2 -mediated oxidation of glucose into d -glucono-δ-lactone and produces H 2 O 2 , which HRP can utilize to oxidize small molecules such as Amplex Red to produce resorufin (Figure b).…”

Hollow Hierarchical Porous and Antihydrolytic Spherical Zeolitic Imidazolate Frameworks for Enzyme Encapsulation and Biocatalysis

“…32 However, if some of the Zn atoms were partially uncoordinated, they acted as Lewis's acid sites, having a tendency to react with adsorbates such as H 2 O and CO 2 present in the environment. 33 The hydroxyl (O−H) group and the hydrogen ion (H + ) can be created when H 2 O is adsorbed through a process known as dissociation. The Zn−O bond can be produced through the O−H group hydroxylating the Zn sites.…”

“…As the enzyme proteins immobilized, there was a significant increase in the peak areas of N−H, and the abnormal increase of N−Zn peak is caused by the interaction between the side chain group NH 2 in the protein molecules and unsaturated ligand zinc atoms. 33 Furthermore, a discernible drop in the C−N peak region is a result of the imidazole ring dissociation. The reduction in the number of organic linkers contributes to the formation of amorphous MOFs, which generally significantly increases the activity of the enzymes encapsulated in the MOFs.…”