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Shimakoshi, Hisashi,Nagami, Yoko,Hisaeda, Yoshio Korean Society of Photoscience 2015 Rapid communication in photoscience Vol.4 No.1
The debromination of phenethyl bromide by the $B_{12}-TiO_2$ hybrid catalyst under UV light irradiation was investigated. The catalytic efficiency was dependent on the type of $TiO_2$. The anatase form of $TiO_2$ was superior to the rutile form of $TiO_2$. The selectivity of the product was also dependent on the crystal structure of $TiO_2$, and the rutile form of $TiO_2$ showed a high selectivity for the formation of the coupling product, 2,3-diphenylbutane, when compared to that of the anatase form of $TiO_2$.
Tian, Hui,Shimakoshi, Hisashi,Park, Gyurim,Kim, Sinheui,You, Youngmin,Hisaeda, Yoshio The Royal Society of Chemistry 2018 Dalton transactions Vol.47 No.3
<P>A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(iii) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6) as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(ii)(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, <I>i.e.</I>, the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that the oxidative quenching of the photosensitizer dominated over the reductive quenching pathway.</P>