Rh-Functionalized Donor−π–Acceptor Covalent Organic Framework for Efficient Photocatalytic Nicotinamide Cofactor Regeneration

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(34), P. 12775 - 12785

Published: Aug. 12, 2024

A nicotinamide adenine dinucleotide phosphate (NADPH)-mediated photoenzyme-coupled catalytic system is an attractive and green strategy for chemical conversion. However, artificial photocatalytic NADPH regeneration with low activity selectivity has posed a challenge when it coupled enzyme catalysis. Therefore, we developed to prepare "all-in-one" photocatalyst (Rh-sp2c-COF) by immobilizing electron mediator ([Cp*Rh(bpy)(H2O)]2+) in covalent organic framework (COF) donor−π–acceptor structure efficient regeneration. The immobilized [Cp*Rh(bpy)(H2O)]2+ not only achieves specific of 1,4-NADPH but also improves the efficiency transfer utilization constructing intramolecular channels buffer tanks. In addition, expands range light absorption promotes effective carrier separation directional transfer. turnover frequency Rh-sp2c-COF reaches 2.17 mmol·gCOF–1·h–1, which 3.28, 1.99, 4.5 times higher than those sp2c-COF, sp2c-COF + free [Cp*Rh(bpy)(H2O)]2+, imine-COF, respectively. Finally, ene reductase asymmetric hydrogenation C═C. This work provides approach accurate predesign photocatalysts achieve conversion solar energy.

Language: Английский

---

The Role of Reticular Chemistry in Photoenzymatic Reaction

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(23), P. 11468 - 11489

Published: Jan. 1, 2024

Photoenzymatic catalysis faces challenges like low stability and recyclability. Reticular framework materials offer solutions by enabling enzyme protection reuse. This review highlights recent advances, design strategies, future directions.

Language: Английский

---

Cr³⁺-ZnGa₂O₄@Pt for Light-Triggered Dark Catalytic Regeneration of Nicotinamide Coenzymes without Other Electron Mediators

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(4), P. 5273 - 5282

Published: Jan. 17, 2023

Photocatalysts for regeneration of reduced nicotinamide adenine dinucleotide (NADH) usually work with continuous lighting and electron mediators, which causes impracticability under dark conditions, risk NADH reoxidation, complex separation. To solve these problems, we present a new catalyst tiny Pt nanoparticles photodeposited on chromium-doped zinc gallate (CZGO@Pt). Upon being light-triggered, the photogenerated electrons are stored in traps CZGO then gradually released transferred by to directly reduce NAD+ after stoppage illumination. Three modes compared demonstrate feasibility advantage this light-triggered catalysis. Within 4 h reaction, in-the-dark yield reaches 75.0% prelighting CZGO@5%Pt it 80.0% triethanolamine (TEOA). However, is only 53.5% CZGO@5%Pt, TEOA, NAD+. Consequently, catalytic not saves energy operates easily but also significantly elevates yield. It thus would secure wide interests applications places where no light or intermittent available.

Language: Английский

---

Formate‐Mediated Electroenzymatic Synthesis via Biological Cofactor NADH

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 22, 2024

Abstract Synthetic biohybrid systems by coupling artificial system with nature's machinery may offer a disruptive solution to address the global energy crisis. We developed versatile electroenzymatic pathway for continuous synthesis of valuable chemicals, facilitated formate‐driven NADH regeneration. Utilizing bismuth electrocatalyst, we achieved stable CO 2 reduction formate approximately 90 % Faraday efficiency at current density 150 mA cm −2 . The generated acts as mediator regenerate NADH, which is then coupled immobilized redox enzymes—alcohol dehydrogenase (ADH), L ‐lactate (LDH), and ‐glutamate (GDH)—to produce targeted chemicals significant rates exceptionally high turnover numbers (1.8×10 6 3.1×10 ). These achievements not only underscore but also its practical applicability in industrial settings. By leveraging situ formate, this innovative approach demonstrates potential integrating electrocatalysis enzymatic reactions sustainable efficient chemical production on scale.

Language: Английский

---

Electron-mediator-free efficient photocatalytic regeneration of coenzyme NAD(P)H via direct electron transfer using ultrathin Bi₂MoO₆ nanosheets

Green Chemistry, Journal Year: 2024, Volume and Issue: 27(3), P. 623 - 632

Published: Nov. 12, 2024

The direct electron transfer mechanism of single-layer Bi 2 MoO 6 ultrathin nanosheets promotes the efficient regeneration photocatalytic coenzyme NAD(P)H.

Language: Английский

---