Electron Transfer Properties and Control of Active Oxygen Species

电子转移性质和活性氧的控制

• 批准号: 11228205
• 负责人: FUKUZUMI Shunichi
• 金额: $ 36.48万
• 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 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11228205/
• 关键词: 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

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.

研究了各种超氧化物金属配合物的形成及其催化作用。超氧化物-金属离子配合物的电磁共振光谱的gzz值随金属离子类型的不同而有显著的变化。根据gzz值与自由自旋值的偏差，确定了π_g能级由于络合物的形成而产生的能量分裂值（ΔE）。ΔE值与金属离子在氧的电子转移还原反应中的催化活性有很好的相关性。超氧化物离子与金属离子之间的这种络合物的形成在超氧化物歧化酶的酶促功能、活性氧-铜络合物的形成以及O_2对锌卟啉-富勒烯连接分子的反向电子转移的新型催化作用中发挥了重要作用。以锰卟啉和树状大分子为催化剂也实现了包括水在内的底物的催化氧化，并通过对活性氧的检测和详细的动力学研究揭示了催化机理。利用二钴卟啉和适当的间隔剂，阐明了氧四电子还原成水的催化机理。

项目成果

Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)

Shunichi Fukuzumi 等：“通过光诱导电子转移将对二甲苯 100% 选择性氧化为对甲苯甲醛”Org.Lett. 2・23 (2000)。

Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J. Am. Chem. Soc.. 122・4. 563-570 (2000)

Shunichi Fukuzumi 等：“两种 (C_6H_5CH_2)_4C_<60> 异构体的电合成和结构表征”J. Am. Chem. 122・4。

Shunichi Fukuzumi et al.: "Photoalkylation of 1O-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J.Am.Chem.Soc.. 123・35. 8459-8467 (2001)

Shunichi Fukuzumi 等人：“通过溶剂极性控制的电荷转移型光致电子转移实现 1O-烷基吖啶鎓离子的光烷基化”J.Am.Chem.Soc.. 123・35 (2001)。

Fukuzumi, S.: "Metal Ion-Catalyzed Diels-Alder and Hydride Transfer Reactions. Catalysis of Metal Ions in the Electron-Transfer Step"J. Am. Chem. Soc.. 124(42). 12566-12573 (2003)

Fukuzumi, S.：“金属离子催化的狄尔斯-阿尔德和氢化物转移反应。电子转移步骤中金属离子的催化”J。

Fukuzumi, S. et al.: "Fluorescence Maxima of 1O-Methylacridone-Metal Ion Salt Complexes : A Convenient and Quantitative Measure of Lewis Acidity of Metal Ion Salts"Journal of the American Chemical Society. 124・35. 10270-10271 (2002)

Fukuzumi, S. 等人：“1O-甲基吖啶酮-金属离子盐复合物的荧光最大值：金属离子盐路易斯酸度的便捷定量测量”美国化学会杂志 124・35（2002 年）。 ）