Electron-Transfer Reactions of Chemically Modified Hemoproteins and Their Model Compounds
化学修饰血红素蛋白及其模型化合物的电子转移反应
基本信息
- 批准号:08454209
- 负责人:
- 金额:$ 4.8万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:1996
- 资助国家:日本
- 起止时间:1996 至 1997
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
1) Metmyoglobin modified with diethylenetriaminepentaacetic acid (metMbDTPA) binds Cu(II) and Co(II) to form metMb{Cu^<II>(dtpa)} and metMb{Co^<II>(dtpa)}, respectively. The latter was further oxidized by K_3[Fe(CN)_6] to form metMb{Co^<III>(dtpa)}. These compounds were characterized by an ESR and an atomic absorption spectro-scopies and a cyclic voltammetry. 2) The intra- and intermolecular electron-transfer reactions of one electron-reduced deoxyMb{Co^<III>(dtpa)} were investigated by spectrophotometrically. The intramolecular electron-transfer reaction depends on the attached site of DTPA.3) The heme iron of metMbDTPA was replaced by a Zn(II) ion and the excited singlet and triplet states of ZnMbDTPA were efficiently quenched by a bound Cu(II) ion. The excited triplet state of ZnMbDTPA was also quenched intramolecularly by the oxidized form of cytochrome c. 4) Viologen or quinoliniumlinked N-alkylporphyrin dyads were synthesized and characterized. The orientation and distance effects on the rates of the quenching and photo-induced electron-transfer reactions were investigated in acetonitrile and propylene glycol. Orthogonal orientation of viologen or quinolinium ion against the porphyrin plane decelerated the electron- and energy-transfer reaction rates. 5) The stereoselective electron-transfer reactions between hemoproteins and chiral viologen-radical cations were investigated. The (S,S) -isomers of chiral viologens preferentially reduced metmyoglobin and cytochrome c.
1)用二乙烯苯甲酸苯甲酸(METMBDTPA)修饰的Metmyoglobin结合Cu(II)和CO(II)形成MetMB {Cu^<ii>(dtpa)}和MetMB {CO^<ii>(dtpa)}。后者被K_3 [Fe(CN)_6]进一步氧化以形成MetMB {Co^<iii>(dtpa)}。这些化合物的特征是ESR和原子吸收光谱镜和环状伏安法。 2)通过分光光度法测量研究了一种电子还原脱氧{co^<iii>(dtpa)}的一个电子内部和分子间电子转移反应。分子内电子转移反应取决于DTPA的附着位点。3)METMBDTPA的血红素铁被Zn(II)离子代替,而激发的单线和ZnMBDTPA的三胞胎和三重态被有效淬andecent cu(ii)离子离子(II)离子离子(II)离子离子。 。 ZnMBDTPA的激发三重态也通过细胞色素c的氧化形式在分子内淬灭。 4)合成并表征了Viologen或quinolin-link的N-烷基孢子蛋白二元组。在乙腈和丙二醇中研究了对淬火和光诱导的电子转移反应速率的方向和距离影响。 Viologen或quinolinium离子针对卟啉平面的正交取向减速了电子和能量转移反应速率。 5)研究了血红蛋白和手性维多利亚激进阳离子之间的立体选择性电子转移反应。手性viologens的(s,s) - 异构体优先降低梅莫洛蛋白和细胞色素c。
项目成果
期刊论文数量(22)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
K.Tsukahara, C.Kimura, T.Sakurai: "Intracomplex quenching by copper (II) ion of excited singlet and triplet states of zinc myoglobin modified with diethylenetriaminepentaacetic acid" Chem.Lett.601-602 (1997)
K.Tsukahara、C.Kimura、T.Sakurai:“用二乙烯三胺五乙酸修饰的锌肌红蛋白的激发单线态和三线态铜 (II) 离子进行复合物内猝灭”Chem.Lett.601-602 (1997)
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K.Tsukahara,J.Kaneko,T.Miyaji,T.Hara,M.Kato,M.Kimura: "Stereoselective Iuminescence quenching in the complex of excited triplet state of Δ-tris(2,2′-bipyridine)ruthenium(II)with optically active viologens in an aqueous solution" Chem.Lett.(in press). (199
K. Tsukahara、J. Kaneko、T. Miyaji、T. Hara、M. Kato、M. Kimura:“Δ-三(2,2′-联吡啶)钌(II)激发三重态复合物中的立体选择性发光猝灭)在水溶液中具有光学活性的紫精”Chem.Lett.(印刷中)。(199
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K.Tsukahara,J.Kaneko,T.Miyaji,K.Abe: "Charge-transfer interaction between bipyridinium and naphthyl groups of optically active viologens in an aqueous solution" Tetrahedron Lett.37(17). 3149-3152 (1996)
K.Tsukahara、J.Kaneko、T.Miyaji、K.Abe:“水溶液中联吡啶鎓和光学活性紫精的萘基之间的电荷转移相互作用”Tetrahedron Lett.37(17)。
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K.Tsukahara, K.Abe, and M.Matsuoka: "Chiral recognition in disproportionation of monoradical cation of optically active bisviologen in an aqueous solution" Chem.Lett.941-942 (1997)
K.Tsukahara、K.Abe 和 M.Matsuoka:“水溶液中光学活性双紫精单自由基阳离子歧化中的手性识别”Chem.Lett.941-942 (1997)
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K.Tsukahara, J.Kaneko, T.Miyaji, and K.Abe: "Chargetransfer interaction between bipyridinium and naphthyl groups of optically active viologens in an aqueous solution" Tetrahedron Lett.37 (18). 3149-3152 (1996)
K.Tsukahara、J.Kaneko、T.Miyaji 和 K.Abe:“水溶液中光学活性紫精的联吡啶和萘基之间的电荷转移相互作用”Tetrahedron Lett.37 (18)。
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TSUKAHARA Keiichi其他文献
TSUKAHARA Keiichi的其他文献
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{{ truncateString('TSUKAHARA Keiichi', 18)}}的其他基金
PHOTOINDUCED ELECTRON TRANSFER OF METAL COMPLEXES AND CHEMICALLY MODIFIED METALLOPROTEINS
金属络合物和化学修饰金属蛋白的光诱导电子转移
- 批准号:
19550064 - 财政年份:2007
- 资助金额:
$ 4.8万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Cytochrome c Peroxidase-Like Activity of Chemically Modified Myoglobins
化学修饰肌红蛋白的细胞色素 c 过氧化物酶样活性
- 批准号:
10640546 - 财政年份:1998
- 资助金额:
$ 4.8万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
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 - 财政年份:1991
- 资助金额:
$ 4.8万 - 项目类别:
Grant-in-Aid for General Scientific Research (B)