San José State University, Department of Chemistry, One Washington Square, San José, CA, 95192-0101, USA.
San José State University, Department of Chemistry, One Washington Square, San José, CA, 95192-0101, USA.
Arch Biochem Biophys. 2019 Sep 15;672:108077. doi: 10.1016/j.abb.2019.108077. Epub 2019 Aug 16.
The light-driven hybrid P450 enzyme approach utilizing the photochemical properties of a covalently attached Ru(II)-diimine photosensitizer was extended to the archaeal Sulfolobus acidocaldarius CYP119 enzyme leading to high photocatalytic activity in the hydroxylation of the chromogenic substrate, 11-nitrophenoxyundecanoic acid. The determined k was greater than those reported with various natural redox partners. In addition, the sacrificial electron donor, diethyldithiocarbamate, used in the photocatalytic reaction is shown to play a dual role. It acts as an efficient quencher of the Ru(II) excited state leading to a highly reducing species necessary to inject electrons into the heme. It is also known for its antioxidant properties and is shown herein to be a useful probe to determine coupling efficiency in the light-driven hybrid enzymes.
利用共价连接的 Ru(II)-二亚胺光感受器的光化学性质的光驱动杂合 P450 酶方法被扩展到古细菌 Sulfolobus acidocaldarius CYP119 酶，导致在生色底物 11-硝基苯氧基十一烷酸的羟化中具有高的光催化活性。确定的 k 大于用各种天然氧化还原伴侣报道的 k。此外，在光催化反应中使用的牺牲电子供体二乙二硫代氨基甲酸盐被证明具有双重作用。它充当 Ru(II)激发态的有效猝灭剂，导致将电子注入血红素所需的高度还原物种。它也因其抗氧化性能而闻名，并在此处显示为确定光驱动杂合酶中的偶联效率的有用探针。
