Enzyme Catalysis in Non‐Native Environment with Unnatural Selectivity Using Polymeric Nanoreactors

Abstract

The utilization of enzymes for catalysis in organic solvents, while exhibiting selectivity to different substrates, is a big challenge. We report an amphiphilic random copolymer system that self‐assembles with enzymes in an organic solvent to form nanoreactors. These encapsulated enzymes are not denatured and they do preserve the catalytic activity. The cross‐linkable functional groups in the hydrophobic compartments of the polymers offer to control accessibility to the enzyme. This varied accessibility due to the polymer host, rather than the enzyme itself, endows the nanoreactor with an unnatural selectivity. The findings here highlight the significant potential of simple polymer‐based enzyme nanoreactors to execute selective organic reactions under non‐native conditions.

Facile Fabrication of 1-Methylimidazole/Cu Nanozyme with Enhanced Laccase Activity for Fast Degradation and Sensitive Detection of Phenol Compounds

“…Although natural enzymes are widely used, there are some shortcomings to be solved towards the practical applications, such as high cost of separation and purification, low thermal/salty stability, unsatisfied environmental tolerance and difficult recyclability [ 4 , 5 , 6 ]. In order to overcome these limitations of natural enzymes, researchers have developed several strategies including enzyme engineering, enzyme immobilization, enzyme nanoreactors and nanozymes with enzyme-like activities [ 7 , 8 , 9 , 10 ]. Enzyme engineering allows enzymes to achieve higher reaction rates and stability, but mutating protein sequences remains a complex task [ 11 ]; enzyme immobilization and enzyme nanoreactors improve enzyme stability and reusability, but may also lead to enzyme activity decrease [ 12 ].…”

Supramolecular Ionic Liquid Gels for Enzyme Entrapment

“…This is quite different from surface immobilization, which does not remove exposure to external environments. Biocatalysts have been entrapped within different gel environments, including hydrogels, , organogels, , aerogels, and ionic liquid silica gels . The method adopted in this study was entrapment within a supramolecular ionic liquid gel.…”

Solvent Remodeling in Single‐Chain Amphiphilic Heteropolymer Systems

“…Methacrylate-based random heteropolymers (RHPs) are one such system, which self-assembles into nano-scale particles containing single or few chains in water, and offers an exciting DOI: 10.1002/marc.202200142 avenue for protein stabilization and mimicry, nanofiltration, and other promising applications. [3][4][5][6][7] Behavior of methacrylate-based designs in water have been studied most in depth, as many of their applications occur in aqueous environments. [8,9] We previously studied a specific RHP design-space through molecular dynamics (MD) simulations and elucidated the resulting SCNP structure, dynamics, and driving forces to assembly in water.…”

“…Methacrylate‐based random heteropolymers (RHPs) are one such system, which self‐assembles into nano‐scale particles containing single or few chains in water, and offers an exciting avenue for protein stabilization and mimicry, nanofiltration, and other promising applications. [ 3–7 ] Behavior of methacrylate‐based designs in water have been studied most in depth, as many of their applications occur in aqueous environments. [ 8,9 ]…”