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Cofactor‐Free, Direct Photoactivation of Enoate Reductases for the Asymmetric Reduction of C=C Bonds
Lee, Sahng Ha,Choi, Da Som,Pesic, Milja,Lee, Yang Woo,Paul, Caroline E.,Hollmann, Frank,Park, Chan Beum VCH Verlagsgesellschaft mbH 2017 Angewandte Chemie Vol.56 No.30
<P><B>Abstract</B></P><P>Enoate reductases from the family of old yellow enzymes (OYEs) can catalyze stereoselective <I>trans</I>‐hydrogenation of activated C=C bonds. Their application is limited by the necessity for a continuous supply of redox equivalents such as nicotinamide cofactors [NAD(P)H]. Visible light‐driven activation of OYEs through NAD(P)H‐free, direct transfer of photoexcited electrons from xanthene dyes to the prosthetic flavin moiety is reported. Spectroscopic and electrochemical analyses verified spontaneous association of rose bengal and its derivatives with OYEs. Illumination of a white light‐emitting‐diode triggered photoreduction of OYEs by xanthene dyes, which facilitated the enantioselective reduction of C=C bonds in the absence of NADH. The photoenzymatic conversion of 2‐methylcyclohexenone resulted in enantiopure (<I>ee</I>>99 %) (<I>R</I>)‐2‐methylcyclohexanone with conversion yields as high as 80–90 %. The turnover frequency was significantly affected by the substitution of halogen atoms in xanthene dyes.</P>
Electronic and spin states ofSrRuO3thin films: An x-ray magnetic circular dichroism study
Agrestini, S.,Hu, Z.,Kuo, C.-Y.,Haverkort, M. W.,Ko, K.-T.,Hollmann, N.,Liu, Q.,Pellegrin, E.,Valvidares, M.,Herrero-Martin, J.,Gargiani, P.,Gegenwart, P.,Schneider, M.,Esser, S.,Tanaka, A.,Komarek, A American Physical Society 2015 Physical review. B, Condensed matter and materials Vol.91 No.7