| Project/Area Number |
11228205
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Osaka University |
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Principal Investigator |
FUKUZUMI Shunichi Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (40144430)
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| Co-Investigator(Kenkyū-buntansha) |
SUENOBU Tomoyoshi Osaka University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (90271030)
OGO Seiji Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (60290904)
今堀 博 大阪大学, 大学院・工学研究科, 助教授 (90243261)
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| Project Period (FY) |
1999 – 2002
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥57,000,000 (Direct Cost: ¥57,000,000)
Fiscal Year 2002: ¥13,500,000 (Direct Cost: ¥13,500,000)
Fiscal Year 2001: ¥12,200,000 (Direct Cost: ¥12,200,000)
Fiscal Year 2000: ¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 1999: ¥24,900,000 (Direct Cost: ¥24,900,000)
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| Keywords | Active Oxygen Complexes / Electron Transfer / SOD / Monooxygenase / Cytochrome / X-ray Crystal Structure / Metalloproteins / Hemerythrin / ルイス酸 / SOD / 金属酸素錯体活性種 / 電子移動触媒作用 / スカンジウムイオン / スーパーオキシド不均一化酵素 / SOD触媒サイクル / 人工光合成モデル / ESR / 反応機構 / ルイス酸触媒反応 / 核磁気共鳴 |
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| Research Abstract |
Formation of a variety of superoxide-metal complexes and the catalytic function have been investigated. The gzz-values of ESR spectra of superoxide-metal ion complexes vary significantly depending on the type of metal ions. From the deviation of the gzz-value from the free spin value are determined the energy splitting values (ΔE) of π_g levels due to the complex formation.The ΔE values are correlated well with the catalytic reactivities of metal ions in the electron transfer reduction of oxygen. Such a complex formation between superoxide ion and metal ions has been shown to play an essential role in the enzymatic function of superoxide dismutase, formation of active oxygen-opper complexes, and the novel catalytic effect of O_2 in back electron transfer of zinc porphyrin-fullerene linked molecules. The catalytic oxygenation of substrates including water has also been achieved using manganese porphyrins and dendrimers as catalysts and the catalytic mechanisms have been revealed based on the detection of active oxygen species and detailed kinetic studies. The catalytic mechanism of four-electron reduction of oxygen to water has also been elucidated using dicobalt porphyrins with an appropriate spacer.
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