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

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)丙酸血红素在甲肌红蛋白还原中的作用——提示丙酸血红素利用血红素中不含丙酸的二甲基lester血红素和八乙基血红素，在甲肌红蛋白还原中起重要作用。2)紫素修饰的氧化还原行为：新制备的紫素修饰赖氨酸残基的红蛋白被二亚砜离子还原的速度比天然的红蛋白快。这表明，随着紫素自由基阳离子到铁（III）中心的快速分子内电子转移反应，附着在肌红蛋白上的紫素被减少。3)一种新型堇菜原连接的n-烷基卟啉及其锌（II）配合物的合成与表征——合成了一种新型堇菜原连接的四苯基卟啉及其含n-三亚甲基桥的锌（II）配合物，并用二维^1H-NMR对其进行了表征。卟啉基荧光的衰减被两个以上的指数所拟合，表明在紫外光的取向方面存在两个构象。4)锌、镁肌红蛋白的光诱导电子转移反应——锌、镁肌红蛋白在阳离子猝灭剂作用下的光诱导电子转移反应和热逆向电子转移反应均为双分子反应，反应速率对反应驱动力不敏感，表明反应受肌红蛋白构象变化控制。在肌红蛋白锌-六氰铁酸盐（III）配合物中观察到分子内光致电子转移，该配合物是通过静电相互作用形成的，并且通过形成稳定的聚l -赖氨酸和六氰铁酸盐（III）离子的配合物来抑制多聚l -赖氨酸。5)光学活性viologens的合成与表征——新合成并表征了光学活性viologens （OAV^<2+>）。发现OAV^<2+>与l -抗坏血酸离子形成电荷转移配合物，OAV^<2+>与聚l -谷氨酸离子形成离子对具有立体选择性。少

项目成果

Keiichi Tsukahara,Satoko Asami,Mihoko Okada,Takeshi Sakurai: "Kinetics and Mechanisms of Photoinduced Electron-Transfer Reaction of Zinc Myoglobin.Intracomplex vs Intermolecular Quenching Controlled by Conformational Change Associated with Charge and Ster

Keiichi Tsukahara、Satoko Asami、Mihoko Okada、Takeshi Sakurai：“锌肌红蛋白光诱导电子转移反应的动力学和机制。由与电荷和立体相关的构象变化控制的复合物内与分子间猝灭

Keiichi Tsukahara,Kazuyo Ishida: "Kinetics and Mechanism of Reduction of Metmyoglobin by Dithionite.Role of the Heme Propionates" Bull.Chem.Soc.Jpn.64. 2378-2382 (1991)

Keiichi Tsukahara、Kazuyo Ishida：“连二亚硫酸盐还原高铁肌红蛋白的动力学和机制。血红素丙酸盐的作用”Bull.Chem.Soc.Jpn.64。

Keiichi Tsukahara,Mihoko Okada: "Electron-Transfer Quenching and Thermal Backward Electron-Transfer Reactions of Zinc Myoglobin Controlled by Conformational Change" Chem.Lett.1543-1546 (1992)

Keiichi Tsukahara、Mihoko Okada：“构象变化控制的锌肌红蛋白的电子转移淬灭和热后向电子转移反应”Chem.Lett.1543-1546 (1992)

Keiichi Tsukahara: "ElectronーTransfer Reactions of Metal Complexes and Iron Proteins with Viologen Radicals" Trends in Inorganic Chemistry. 2. 17-32 (1991)

Keiichi Tsukahara：“金属络合物和铁蛋白与紫罗碱自由基的电子转移反应”无机化学趋势 2. 17-32 (1991)。

Keiichi Tsukahara: "Electron-Transfer Reactions of Metal Complexes and Iron Proteins with Viologen Radicals" Trends in Inorganic Chemistry. 2. 17-32 (1991)

Keiichi Tsukahara：“金属配合物和铁蛋白与紫罗碱自由基的电子转移反应”无机化学趋势。