| Project/Area Number |
11640558
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | KANAZAWA UNIVERSITY |
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Principal Investigator |
SAKURAI Takeshi KANAZAWA UNIVERSITY FACLTY OF SCIENCE PROFESSOR, 理学部, 教授 (90116038)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1999: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Keywords | multicopper oxidase / laccase / bilirubin oxidase / trinuclear Cu cluster / dioxygen reduction / hydroxyl radical / stopped-flow / ESR / アスコルビン酸オキシダーゼ / パーオキサイド |
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| Research Abstract |
The reactions of the reduced laccase and bilirubin oxidase with dioxygen were studied using mainly absorption and EPR spectra at a cryogenic temperature and also using stopped flow spectroscopy and SQUID magnetic measurement. The hydroxyl or oxyl radical bound to the trinuclear Cu site was detected as a reaction intermediate, three-electron reduced form of dioxygen, . Decays of this radical species were highly pH dependent on pH, indicating that the process was gated by the protonation to be water finally. A peroxide intermediate corresponding to the three electron reduced form of dioxygen could not be detected because diffusion of dioxygen to the trinuclear Cu site was rate-determining step and the electron transfer from type 1 Cu to the putative peroxide intermediate was very rapid. However, the peroxide intermediate could be detected by reaction dioxygen to the CuCl-acted type 2 Cu-depleted laccase under a strict anaerobic condition. Based on the successful detection and characterization of the two reaction intermediates the general reaction mechanism how dioxygen is four-electron reduced by multicopper oxidases was proposed.
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