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.

研究了多种超氧化物-金属络合物的形成和催化功能，超氧化物-金属离子络合物的ESR光谱的gzz值根据金属离子的类型而变化很大。从自由自旋值可以确定由于络合物形成而产生的 π_g 能级的能量分裂值 (ΔE)。ΔE 值与电子中金属离子的催化反应性密切相关超氧离子与金属离子之间的这种络合物形成已被证明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在反向电子转移中的新型催化作用中发挥重要作用。使用锰卟啉和树枝状大分子作为催化剂和催化机制也实现了包括水在内的底物的催化氧化。基于活性氧的检测和详细的动力学研究，使用具有适当间隔基的二钴卟啉也阐明了氧四电子还原成水的催化机制。

项目成果

Fukuzumi, S. et al.: "Hydrogen-bonding dynamics in photoinduced electron transfer in a ferrocene-quinone linked dyad with a rigid amide spacer"Journal of the American Chemical Society. 124・24. 6794-6795 (2002)

Fukuzumi, S. 等人：“具有刚性酰胺间隔基的二茂铁-醌连接二元体中光致电子转移的氢键动力学”，美国化学会杂志 124・24（2002 年）。

Fukuzumi, S. et al.: "Effects of magnesium ion on kinetic stability and spin distribution of phenoxyl radical derived from a vitamin E analogue : mechanistic insight into antioxidative hydrogen-transfer reaction of vitamin E"Journal of the Chemical Societ

Fukuzumi, S. 等人：“镁离子对维生素 E 类似物衍生的苯氧基自由基的动力学稳定性和自旋分布的影响：维生素 E 抗氧化氢转移反应的机理洞察”化学会杂志

Ogo, S.et al.: "Isolation and Crystal Structure of Water-Soluble Iridium Hydride. Robust and Highly Active Catalyst for Acid-Catalyzed Transfer Hydrogenations of Carbonyl Compounds in Acidic Media"Journal of the American Chemical Society. 125(in press). (

Ogo, S.等人：“水溶性氢化铱的分离和晶体结构。酸性介质中羰基化合物酸催化转移氢化的鲁棒且高活性催化剂”美国化学会杂志。

Ogo, S.et al.: "Structural and Spectroscopic Features of a cis (Hydroxo)-Fe^<III>-(Carboxylato) Configuration as an Active Site Model for Lipoxygenases"Inorganic Chemistry. 41・21. 5513-5520 (2002)

Ogo, S. 等人：“作为脂氧合酶活性位点模型的顺式（羟基）-Fe^<III>-（羧基）构型的结构和光谱特征”无机化学 41・21（2002 年）。 ）

Shunichi Fukuzumi et al.: "Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer"Spectrochim. Acta Part A. 57. 2229-2244 (2001)

Shunichi Fukuzumi 等人：“通过马库斯电子转移理论分析紧凑型卟啉-富勒烯二元体的电荷转移发射”Spectrochim。