Key Laboratory of Industrial Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, Jiangsu, China.
Key Laboratory of Industrial Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, Jiangsu, China.
Bioorg Chem. 2024 Jun;147:107418. doi: 10.1016/j.bioorg.2024.107418. Epub 2024 Apr 29.
A key approach in developing green chemistry involves converting solar energy into chemical energy of biomolecules through photocatalysis. Photocatalysis can facilitate the regeneration of nicotinamide cofactors during redox processes. Nicotinamide cofactor biomimetics (NCBs) are economical substitutes for natural cofactors. Here, photocatalytic regeneration of NADH and reduced NCBs (NCBs) using graphitic carbon nitride (g-CN) was developed. The process involves g-CN as the photocatalyst, Cp*Rh(bpy)HO as the electron mediator, and Triethanolamine as the electron donor, facilitating the reduction of NAD and various oxidative NCBs (NCBs) under light irradiation. Notably, the highest reduction yield of 48.32 % was achieved with BANA, outperforming the natural cofactor NAD. Electrochemical analysis reveals that the reduction efficiency and capacity of cofactors relies on their redox potentials. Additionally, a coupled photo-enzymatic catalysis system was explored for the reduction of 4-Ketoisophorone by Old Yellow Enzyme XenA. Among all the NCBs and NAD, the highest conversion ratio of over 99 % was obtained with BANA. After recycled for 8 times, g-CN maintained over 93.6 % catalytic efficiency. The photocatalytic cofactor regeneration showcases its outstanding performance with NAD as well as NCBs. This work significantly advances the development of photocatalytic cofactor regeneration for artificial cofactors and its potential application.
将太阳能转化为生物分子的化学能是开发绿色化学的关键方法之一，通过光催化来实现。光催化可以促进氧化还原过程中烟酰胺辅酶的再生。烟酰胺辅酶模拟物（NCB）是天然辅酶的经济替代品。在这里，开发了使用石墨相氮化碳（g-CN）光催化再生 NADH 和还原型 NCB（NCB）的方法。该过程涉及 g-CN 作为光催化剂、Cp*Rh(bpy)HO 作为电子介体和三乙醇胺作为电子供体，在光照下促进 NAD 和各种氧化型 NCB（NCB）的还原。值得注意的是，BANA 的还原产率最高达到 48.32%，优于天然辅酶 NAD。电化学分析表明，辅酶的还原效率和容量取决于其氧化还原电位。此外，还探索了用于 Old Yellow Enzyme XenA 还原 4-酮异佛尔酮的偶联光酶催化体系。在所有 NCB 和 NAD 中，BANA 的转化率最高，超过 99%。经过 8 次回收后，g-CN 保持了超过 93.6%的催化效率。该光催化辅酶再生展示了其与 NAD 以及 NCB 一起的出色性能。这项工作为人工辅酶的光催化辅酶再生及其潜在应用提供了重要进展。
