Highly Selective Electrocatalytic 1,4‐NADH Regeneration Based on Host–Guest Recognition Mediated by Cucurbit[8]uril on NiO

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Abstract Efficient regeneration of nicotinamide adenine dinucleotide (NADH) cofactors, particularly 1,4‐NADH, is crucial for advancing oxidoreductase catalysis. Electrocatalysis provides a promising route 1,4‐NADH regeneration, but an expensive catalyst, typically rhodium organometallic complex, frequently required to guarantee the high selectivity significantly limiting its large‐scale application. Herein, inspired by catalytic pocket and enzyme–substrate interaction in nature, direct electrochemical was designed modification surface nickel oxide (NiO) with cucurbit[8]uril (CB[8]) (denoted as CB[8]–NiO). The host–guest between CB[8] NAD + proved, which similar principle substrate–enzyme‐specific recognition. acted , providing suitable cavity volume accommodate positively charged part . entered approached surface‐adsorbed hydrogen atoms on NiO reaction‐ready configuration achieve regioselective regeneration. Remarkably higher 97.8% CB[8]–NiO obtained at −0.47 V versus reversible electrode (RHE) than that bare (77.4%).

Язык: Английский

Highly Selective Electrocatalytic 1,4‐NADH Regeneration Based on Host–Guest Recognition Mediated by Cucurbit[8]uril on NiO

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Abstract Efficient regeneration of nicotinamide adenine dinucleotide (NADH) cofactors, particularly 1,4‐NADH, is crucial for advancing oxidoreductase catalysis. Electrocatalysis provides a promising route 1,4‐NADH regeneration, but an expensive catalyst, typically rhodium organometallic complex, frequently required to guarantee the high selectivity significantly limiting its large‐scale application. Herein, inspired by catalytic pocket and enzyme–substrate interaction in nature, direct electrochemical was designed modification surface nickel oxide (NiO) with cucurbit[8]uril (CB[8]) (denoted as CB[8]–NiO). The host–guest between CB[8] NAD + proved, which similar principle substrate–enzyme‐specific recognition. acted , providing suitable cavity volume accommodate positively charged part . entered approached surface‐adsorbed hydrogen atoms on NiO reaction‐ready configuration achieve regioselective regeneration. Remarkably higher 97.8% CB[8]–NiO obtained at −0.47 V versus reversible electrode (RHE) than that bare (77.4%).

Язык: Английский

Product Distribution of Steady–State and Pulsed Electrochemical Regeneration of 1,4‐NADH and Integration with Enzymatic Reaction

ChemistryOpen, Год журнала: 2024, Номер 13(8)

Опубликована: Апрель 12, 2024

Abstract The direct electrochemical reduction of nicotinamide adenine dinucleotide (NAD + ) results in various products, complicating the regeneration crucial 1,4‐NADH cofactor for enzymatic reactions. Previous research primarily focused on steady–state polarization to examine potential impacts product selectivity. However, this study explores influence dynamic conditions selectivity NAD products by comparing two profiles with steady‐state conditions. Our findings reveal that main including 1,4‐NADH, several dimers, and ADP‐ribose, remained consistent across all A minor by–product, 1,6‐NADH, was also identified. distribution varied depending experimental (steady state vs. dynamic) concentration , higher concentrations overpotentials promoting dimerization. optimal yield achieved under low overpotential concentrations. While enhanced at shorter reaction times, they resulted a significant amount unidentified products. Furthermore, assessed using pulsed enoate reductase (XenB) cyclohexenone reduction.

Язык: Английский