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

1)丙酸亚铁血红素在还原高铁肌红蛋白中的作用--这表明丙酸亚铁血红素在利用二甲酯高铁血红素和八乙基高铁血红素还原高铁肌红蛋白中起着重要作用。2)新制备了紫精修饰赖氨酸残基的紫精结合高铁肌红蛋白-高铁血红蛋白的氧化还原行为，其还原速度快于天然高铁肌红蛋白。3)新型紫精连接的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紫精连接的四苯基卟啉及其含N-三亚甲基桥联的锌(II)配合物，并用二维1H-核磁共振进行了表征。用两个…对卟啉类化合物的荧光衰减进行了拟合4)锌和镁肌红蛋白的光诱导电子转移反应-锌和镁肌红蛋白与阳离子猝灭剂的光诱导电子转移和热反向电子转移反应都是双分子步骤，反应速度对反应的驱动力不敏感，表明反应是由肌红蛋白的构象变化控制的。在锌肌红蛋白-六氰基铁酸盐(III)络合物中观察到了分子内的光诱导电子转移，该络合物是通过静电相互作用形成的，并在多L赖氨酸的作用下被抑制，形成稳定的聚L赖氨酸与六氰基铁酸根离子的络合物。发现了OAv^&lt；2+&gt；与L-抗坏血酸离子形成电荷转移络合物，以及OaV^&lt；2+&gt；与多聚L-谷氨酸离子形成离子对的立体选择性。较少

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