生物催化
化学
量子产额
辅因子
酮
产量(工程)
催化作用
铑
人工光合作用
光化学
光催化
光子上转换
酶
有机化学
材料科学
反应机理
离子
物理
量子力学
冶金
荧光
作者
Qiao Li,Jing Zhang,Yongjian Jiang,Bianqin Ma,Haomin Chen,Peng Gao,Pengfei Zhang,Anming Wang,Roger A. Sheldon
标识
DOI:10.1016/j.ijbiomac.2024.130612
摘要
Effective photolytic regeneration of the NAD(P)H cofactor in enzymatic reductions is an important and elusive goal in biocatalysis. It can, in principle, be achieved using a near-infrared light (NIR) driven artificial photosynthesis system employing H2O as the sacrificial reductant. To this end we utilized TiO2/reduced graphene quantum dots (r-GQDs), combined with a novel rhodium electron mediator, to continuously supply NADPH in situ for aldo-keto reductase (AKR) mediated asymmetric reductions under NIR irradiation. This upconversion system, in which the Ti-O-C bonds formed between r-GQDs and TiO2 enabled efficient interfacial charge transfer, was able to regenerate NADPH efficiently in 64 % yield in 105 min. Based on this, the pharmaceutical intermediate (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol was obtained, in 84 % yield and 99.98 % ee, by reduction of the corresponding ketone. The photo-enzymatic system is recyclable with a polymeric electron mediator, which maintained 66 % of its original catalytic efficiency and excellent enantioselectivity (99.9 % ee) after 6 cycles.
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