Project/Area Number |
07455322
|
Research Category |
Grant-in-Aid for Scientific Research (B)
|
Allocation Type | Single-year Grants |
Section | 一般 |
Research Field |
触媒・化学プロセス
|
Research Institution | KYOTO UNIVERSITY |
Principal Investigator |
FUNABIKI Takuzo Kyoto University, Faculty of Engineering, Assistant Professor, 工学研究科, 助教授 (70026061)
|
Co-Investigator(Kenkyū-buntansha) |
SUGIURA Yukio Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (40025698)
TAKANO Mikio Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (70068138)
TANAKA Tsunehiro Kyoto University, Graduated School of Engineering, Associate Professor, 工学研究科, 助手 (70201621)
|
Project Period (FY) |
1995 – 1996
|
Project Status |
Completed (Fiscal Year 1996)
|
Budget Amount *help |
¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1996: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1995: ¥4,900,000 (Direct Cost: ¥4,900,000)
|
Keywords | Nonheme Complex / Oxygenases / Monooxyenases / Dioxyenases / Catechol / Aromatic Ring Cleavage / Chlorocatechol / Development of Enzymatic Function / 不活性炭化水素 |
Research Abstract |
Catalytic oxygenation of nonactivated hydrocarbons by oxygenase-model nonheme iron complexes has been studied from the viewpoints of catalysis. Selective intradiol oxygenation of catechols by iron (III) complexes has been extensively studied. In this project the first example of catalytic oxygenation of chlorocatechols by model iron complexes has been achieved. This is very important result not only as the first model reaction for chlorocatechol dioxygenases, but also for the first step of development of decomposition of haloaromatics which are environmental pollutant. The model intermediate complexes, chlorocateholaoiron - (TPA) complexes have been isolated, and their structures were analyzed by XAFS.Another dioxygenase model reaction, i.e.lipoxygenase model reaction catalyzed by nonheme iron complexes, has been studied. Radical intermediates were detected by ESR,supporting the radical mechanism proposed in the enzymatic systems. Monooxygenase model reactions have also been studied, specially by using hydroquinones as electron and proton transfer reagents. In this project, selective ortho-hydroxylation of phenols by iron (III) complexes has been developed, as an model reaction for tyrosine hydroxylase. It is specific that substituents on hydroquinones play essential role for controlling reactivity.
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