A Study of Electron-Transfer Pathways in the Electron-Transfer Reactions of Metal Complexes and Hemoproteins

金属配合物与血红素蛋白电子转移反应中电子转移途径的研究

• 批准号: 03453049
• 负责人: TSUKAHARA Keiichi
• 金额: $ 4.42万
• 依托单位: Nara Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453049/
• 关键词: Electron-Transfer Reaction; Electron-Transfer Pathway; Hemoprotein; Chemically Modified Myoglobin; Zinc Myoglobin; Porphyrins; Photoinduced Electron-Transfer Reaction; Intramolecular Electron Transfer; Electron-Transfer Reaction; Electron-Transfer Pathway; Hemoprotein; Chemically Modified Myoglobin; Zinc Myoglobin; Porphyrins; Photoinduced Electron-Transfer Reaction; Intramolecular Electron Transfer

1) Role of the Heme Propionates in the Reduction of Metmyoglobin-It is suggested that the heme propionates have an important role in the reductions of metmyoglobins by using the dimethylester hemins and octaethylhemin which has no propionates in the heme.2) Redox Behavior of Viologen Attached Metmyoglobin-Metmyoglobin whose lysine residue was modified with viologen was newly prepared and reduced by dithionite ions faster than native metmyoglobin. It is suggested that the viologen attached to myoglobin is reduced, following the rapid intramolecular electron-transfer reaction from the viologen radical cation to the iron(III) center.3) Syntheses and Characterizations of a New Type of Viologen-Linked N-Alkylporphyrin and Its Zinc(II) Complex-New type of viologen-linked tetraphenylporphyrin and its zinc(II) complex containing an N-trimethylene bridge were synthesized and characterized by a two dimensional ^1H-NMR spectroscopy. The decay of the porphyrin-based fluorescence was fitted by two … More exponentials, suggesting the presence of two conformers with respect to the orientation of viologen.4) Photoinduced Electron-Transfer Reactions of Zinc and Magnesium Myoglobins-Both photoinduced electron-transfer and thermal backward electron-transfer reactions of zinc and magnesium myoglobins with cationic quenchers were bimolecular steps and the reaction rates were insensitive to the driving force of reactions, suggesting that the reactions are controlled by conformational changes of myoglobins. The intramolecular photoinduced electrontransfer was observed in a zinc myoglobin-hexacyanoferrate(III) complex, which forms by electrostatic interactions, and was inhibited in addition of poly-L-lysine by forming a stable complex of poly-L-lysine and hexacyanoferrate(III) ions.5) Syntheses and Characterizations of Optical Active Viologens-Optical acitive viologens (OAV^<2+>) were newly synthesized and characterized. The stereoselectivity was found for the formation of the charge-transfer complex of OAV^<2+> with an L-ascorbate ion and for the ion-pair formation between OAV^<2+> and poly-L-glutamate ion. Less

1）血红素丙酸酯在减少食血激蛋白中的作用，提示血红素丙酸属通过使用二甲基抑制蛋白和八甲基甲蛋白和八甲基甲蛋白在减少中具有重要作用。并用二硫代石离子降低的速度比天然甲状腺激素快。 It is suggested that the violen attached to myoglobin is reduced, following the rapid intramolecular electron-transfer reaction from the violen radical cation to the iron(III) center.3) Syntheses and Characterizations of a New Type of Violen-Linked N-Alkylporphyrin and Its Zinc(II) Complex-New type of violen-linked tetraphenylporphyrin and its zinc(II) complex containing an合成N-三甲基桥并以二维 ^1H-NMR光谱法进行了特征。基于卟啉的荧光的衰变由两个……更多的指数拟合，这表明存在两个构象相对于紫罗兰的方向。4）光诱导的电子转移反应锌和肌球蛋白镁和镁的光诱导电子转移和热向后电子反应的ZINC和热向后转移的反应，并具有ZINC的ZINC和热向后转移反应，并具有ZINCENS的固定反应量。双分子的步骤和反应速率对反应的驱动力不敏感，这表明反应是由肌红蛋白的构象变化控制的。在肌红蛋白 - 己糖酰二甲甲苯甲甲甲基甲酯（III）络合物中观察到分子内光诱导的电子转移，该复合物是通过静电相互作用形成的，除了形成多l-赖氨酸外，还通过形成稳定的l-赖氨酸和甲基苯胺和己氨酸和己糖甲甲苯甲酸酯（III）的aacivians和特征，以及抑制了多l-赖氨酸。 （OAV^<2+>）是新合成和表征的。发现了立体选择性，用于与L-抗坏血酸离子的OAV^<2+>的电荷转移复合物以及OAV^<2+>和聚-L-谷氨酸离子之间的离子对形成。较少的