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高选择性辅因子 NADH 再生有机铱配合物用于高效化学-酶级联催化氢转移。

High Selectivity Cofactor NADH Regeneration Organic Iridium Complexes Used for High-Efficiency Chem-Enzyme Cascade Catalytic Hydrogen Transfer.

机构信息

Yantai Key Laboratory of Gold Catalysis and Engineering, Shandong Applied Research Center of Gold Nanotechnology, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China.

Research Center for Hydrogen Energy-Based Society, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan.

出版信息

Inorg Chem. 2023 Oct 30;62(43):17577-17582. doi: 10.1021/acs.inorgchem.3c02882. Epub 2023 Oct 16.

DOI:10.1021/acs.inorgchem.3c02882
PMID:37843583
Abstract

Our research demonstrated that novel pentamethylcyclopentadienyl (Cp*) iridium pyridine sulfonamide complex PySONPh-Ir () could highly specifically catalyze nicotinamide adenine dinucleotide (NAD) into the corresponding reducing cofactor NADH in cell growth media containing various biomolecules. The structures and catalytic mechanism of were studied by single-crystal X-ray, NMR, electrochemical, and kinetic methods, and the formation of iridium hydride species Ir-H was confirmed to be the plausible hydride-transfer intermediate of . Moreover, benefiting from its high hydrogen-transfer activity and selectivity for NADH regeneration, was used as an optimal metal catalyst to establish a chem-enzyme cascade catalytic hydrogen-transfer system, which realized the high-efficiency preparation of l-glutamic acid by combining with l-glutamate dehydrogenase (GLDH).

摘要

我们的研究表明,新型五甲基环戊二烯基(Cp*)铱吡啶磺酰胺配合物 PySONPh-Ir()可以在含有各种生物分子的细胞生长培养基中高度特异性地将烟酰胺腺嘌呤二核苷酸(NAD)催化成相应的还原辅酶 NADH。通过单晶 X 射线、NMR、电化学和动力学方法研究了的结构和催化机制,证实了铱氢化物物种 Ir-H 是合理的氢转移中间体。此外,由于其对 NADH 再生的高氢转移活性和选择性,被用作最佳金属催化剂来建立化学-酶级联氢转移催化体系,该体系通过与谷氨酸脱氢酶(GLDH)结合实现了高效制备 l-谷氨酸。

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