A Versatile Chemoenzymatic Nanoreactor that Mimics NAD(P)H Oxidase for the In Situ Regeneration of Cofactors

Abstract

Herein, we report a multifunctional chemoenzymatic nanoreactor (NanoNOx) for the glucosecontrolled regeneration of natural and artificial nicotinamide cofactors. NanoNOx are built of glucose oxidasepolymer hybrids that assemble in the presence of an organometallic catalyst: hemin. The design of the hybrid is optimized to increase the effectiveness and the directional channeling at low substrate concentration. Importantly, NanoNOx can be reutilized without affecting the catalytic properties, can show high stability in the presence of organic solvents, and can effectively oxidize assorted natural and artificial enzyme cofactors. Finally, the hybrid was successfully coupled with NADHdependent dehydrogenases in one-pot reactions, using a strategy based on the sequential injection of a fuel, namely, glucose. Hence, this study describes the first example of a hybrid chemoenzymatic nanomaterial able to efficiently mimic NOx enzymes in cooperative onepot cascade reactions.

Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths

“…[4][5][6] Until now, a wide variety of enzyme classes have been utilized, encompassing halogenases, oxidoreductases, and hydrolytic enzymes. [7][8][9][10][11][12] Nonetheless, the activation of oxidoreductases typically necessitates the use of crucial and costly enzymatic cofactors. Oxidoreductases, which belong to one of the most extensive enzyme groups, commonly utilize reduced forms of cofactors such as reduced nicotinamide adenine dinucleotide (NADH) to catalyze the reduction of specific substrates.…”

Enzyme‐Polymer Conjugates for Tuning, Enhancing, and Expanding Biocatalytic Activity

“…This material was based on a previous EPH system in which glucose oxidase (GOx) enzyme is encapsulated inside a peroxidase‐like polymeric nanogel (Figure 5B). [80] NanoNOx are heterogeneous chemoenzymatic hybrids that mimic the NADH‐oxidase (NOx) enzymes [74] . GOx enzyme, in presence of glucose, releases hydrogen peroxide, which is used immediately to oxidize assorted enzyme cofactors, that is, NADH, NADPH, BAH, by the iron porphyrin catalysts that are allocated within the polymeric shell of the hybrid.…”

“…[80] NanoNOx are heterogeneous chemoenzymatic hybrids that mimic the NADHoxidase (NOx) enzymes. [74] GOx enzyme, in presence of glucose, releases hydrogen peroxide, which is used immediately to oxidize assorted enzyme cofactors, that is, NADH, NADPH, BAH, by the iron porphyrin catalysts that are allocated within the polymeric shell of the hybrid. We demonstrated that this system can be used for in-situ cofactor regeneration in combination with an alcohol dehydrogenase (ADH) enzyme.…”

Enzymatic Electrosynthesis of Glycine from CO2 and NH3

“…However, to deal with energy supply issue in vitro, efficient reductive regeneration of NAD(P)H from NAD(P) + is needed. Recently, alternative methods including chemical, [14] photochemical, [15] and electrochemical [16] regeneration have been developed, providing easier downstream operation and improving catalytic yield as compared to enzymatic regeneration. [17] Inspired by the reductive glycine pathway, in this study we constructed an enzymatic electrocatalytic system for the one-pot synthesis of glycine, the smallest amino acid, by the simultaneous utilization of CO 2 and NH 3 .…”