Summary of Molecular Methodology and Reaction Control of Oxygen Active Species

氧活性物质的分子方法学和反应控制综述

• 批准号: 11228204
• 负责人: FUKUZUMI Shunichi
• 金额: $ 6.4万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11228204/
• 关键词: Active Oxygen Complexes; Electron Transfer; SOD; Monooxygenase; Cytochrome; X-ray Crystal Structure; Metalloproteins; Hemerythrin; Oxygenation; 触媒化学; 物質・エネルギー変換; 反応制御法; エネルギー問題; 地球環境

The structures and reactivities of a variety of active oxygen-metal complexes have been revealed in relation with enzymatic oxidation reaction. A large number of information about metal-dioxygen reactivity has been accumulated, providing profound insight into the mechanism of O_2-binding and activation at metal reaction sites involved in many biological systems as well as in a variety of catalytic oxidation processes. In particular, reversible dioxygen binding (functional model of hemocyanim) has been accomplished using a series of dinucleating ligands. The present research project has provided valuable insight into the mechanisms of the four-electron reduction of oxygen as well as the four-electron oxidation of water. The initial objectives of the present research project have been well accomplished by the intensive cooperative research activities among seven research groups. The final results are summarized in the international symposium on the active oxygen-metal complexes held in january 2004, when the future prospect of the field of active oxygen-metal complexes has been discussed

与酶促氧化反应有关的各种活性氧基形复合物的结构和反应率已被揭示。有关金属二氧化节反应性的大量信息已积累，为在许多生物系统以及多种催化氧化过程中涉及的金属反应位点上的O_2结合和激活机理提供了深刻的见解。特别是，已经使用一系列的夹克配体来完成可逆的二氧化结合（血能扬烷的功能模型）。本研究项目为氧气减少的机制以及水的四电子氧化提供了宝贵的见解。七个研究小组之间的密集合作研究活动已经完成了本研究项目的最初目标。最终结果总结在2004年1月举行的活跃氧金属复合物的国际研讨会上，当时已经讨论了活跃氧基准配合物的未来前景

项目成果

Fukuzumi, S. et al.: "Effects of Hydrogen Bonding on Metal Ion-Promoted Intramolecular Electron Transfer and Photoinduced Electron Transfer in a Ferrocene-Quinone Dyad with a Rigid Amide Spacer"Journal of the American Chemical Society. 125・4. 1007-1013 (2

Fukuzumi, S. 等人：“氢键对具有刚性酰胺间隔基的二茂铁-醌二元组中金属离子促进的分子内电子转移和光诱导电子转移的影响”，美国化学会杂志 125・4。 1013（2

Fukuzumi, S. et al.: "C_<70> vs. C_<60> in zinc porphyrin-fullerene dyads : prolonged charge separation and ultrafast energy transfer from the second excited singlet state of porphyrin"Photochemical & Photobiological Sciences. (in press). (2003)

Fukuzumi, S. 等人：“锌卟啉-富勒烯二元组中的 C_<70> 与 C_<60>：延长的电荷分离和从卟啉第二激发单线态的超快能量转移”光化学

Fukuzumi, S. et al.: "Thermal intramolecular electron transfer in a ferrocene-naphthoquinone linked dyad promoted by metal ions"Angewandte Chemie, International Edition. 41・4. 620-622 (2002)

Fukuzumi, S. 等人：“金属离子促进的二茂铁-萘醌连接二元组中的热分子内电子转移”Angewandte Chemie，国际版 41・4 (2002)。

Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu(II)-Zn(II) Heterodinuclear and Cu(II)-Cu(II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)

Shunichi Fukuzumi 等人：“咪唑桥联 Cu(II)-Zn(II) 异双核和 Cu(II)-Cu(II) 同双核氢过氧配合物作为 Cu、Zn-SOD 反应中间模型的表征”Chem.Commun。・12.1051-1052（2000）

Fukuzumi, S.et al.: "Seconds Lasting Charge-Separated State Generated in Ferrocene-meso, meso-Linked Porphyrin Trimer-Fullerene Pentad with a High Quantum Yield"Chemistry--A European Journal. (In press). (2004)

Fukuzumi, S.et al.：“具有高量子产率的二茂铁-内消旋、内消旋连接的卟啉三聚体-富勒烯五联体中产生的持续电荷分离态”化学 - 欧洲期刊。