Studies on Chemical Functions of Novel Redox Coenzymes

新型氧化还原辅酶化学功能的研究

• 批准号: 08458177
• 负责人: ITOH Shinobu
• 金额: $ 4.67万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (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: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08458177/
• 关键词: Coenzyme; Pyrroloquinolinequione; Tryptophan Tryptophylquinone; Alcohol Dehydrogenase; Amino Dehydrogenase; Galactose Oxidase; Redox Reaction; Model Study; 補酵素モデル; 反応機構; キノプロテイン; オルトキノン; PQQ; TTQ; モデル銅錯体; 銅錯体

In this research project, the physicochemical properties and chemical functions of novel redox coenzymes such as PQQ (pyrroloquinolinequinone) of bacterial alcohol and glucose dehydrogenases, TTQ (tryptophan tryptophylquinone) of bacterial amine dehydrogenases, and Tyr-Cys (a dimer of tyrosine and cysteine) of galactose oxidase have been explored. Followings are the summary of the results.PQQ Project・Model studies on quinoprotein methanol dehydrogenase has been carried out to find that the oxidation of methanol by calcium complex of coenzyme PQQ proceeds via addition-elimination mechanism. The catalytic role of calcium ion on the methanol oxidation has been also explored.・Catalysis by calcium ion on the reoxidation of reduced PQQ by molecular oxygen has been investigated.・Electrochemical behavior of coenzyme PQQ in aprotic organic media has been explored.・Photochemical oxidation of benzyl alcohols by the triplet excited state of coenzyme PQQ has been explored.・Photochemical redox react … More ions of coenzyme PQQ and related o-quinones have been investigated in detail.・Novel addition-cyclization reaction of nitroalkane anions with o-quinone derivatives has been found to proceed via electron transfer in the charge-transfer complexes.・TTQ Project・Model studies of TTQ-containing amine dehydrogenases has been performed to clarify the amine oxidation mechanism by TTQ coenzyme.・Electrostatic environment of the TTQ cofactor in methylamine dehydrogenase has been investigated by using TTQ model compounds.・Synthesis, physicochemical properties, and amine-oxidation reaction ofindolequinone derivatives as model compounds of novel organic cofactor TTQ of amine dehydrogenases have been investigated.Try-Cys Project・Active site models for galactose oxidase have been developed in order to shed light on the electronic effect of the thioether group in the novel organic cofactor.・Active site models for galactose oxidase have been developed in order to study the physicochemical properties and reactivities of copper (II) complex of the phenoxyl radical species of the novel organic cofactor. Less

本研究对细菌乙醇和葡萄糖脱氢酶的吡咯喹诺酮(PQQ)、细菌胺脱氢酶的色氨酸色氨酸(TTQ)和半乳糖氧化酶的酪氨酸和半胱氨酸二聚体(Tyr-Cys)等新型氧化还原辅酶的物理化学性质和化学功能进行了研究。PQQ项目·对藜麦蛋白甲醇脱氢酶进行了模型研究，发现辅酶PQQ的钙络合物氧化甲醇是通过加成-消除机理进行的。探讨了钙离子对甲醇氧化的催化作用。·研究了钙离子对分子氧二次氧化还原PQQ的催化作用。·研究了辅酶PQQ在非质子有机介质中的电化学行为。·探索了辅酶PQQ的三重态激发态对苯甲醇的光化学氧化作用。·光化学氧化还原反应…对更多的辅酶PQQ离子和相关邻苯二酚进行了详细的研究。·发现硝基烷基阴离子与邻苯二酚衍生物的新型加成-环化反应是通过电荷转移络合物中的电子转移进行的。·TTQ计划·对含TTQ的胺脱氢酶进行了模型研究，以阐明TTQ辅酶对胺的氧化机理。·用TTQ模型化合物研究了甲胺脱氢酶中TTQ辅因子的静电环境。·研究了新型胺脱氢酶有机辅因子TTQ的合成、物化性质和胺氧化反应。Try-Cys计划·建立了半乳糖氧化酶的活性中心模型，以揭示新型有机辅因子中硫醚基团的电子效应。·为了研究新型有机辅因子酚氧基自由基铜(II)络合物的物理化学性质和反应活性，建立了半乳糖氧化酶的活性中心模型。较少

项目成果

Shinobu Itoh et al.: "Electrostatic Environment of the Tryptophylquinone Cofactor in Methylamine Dehydro- genase. Evidence from Resonance Raman Spectroscopy of Model Compounds." Biochemistry. 35・15. 4713-4720 (1996)

Shinobu Itoh 等人：“甲胺脱氢酶中色氨酸醌辅因子的静电环境。模型化合物共振拉曼光谱的证据”35・15（1996）。

Pierre.Moenne-Locoz, Nobuhumi Nakamura, Shinobu Itoh, Shunichi Fukuzumi, Antonius C.F.Gorren, Johannis A.Duine, and Joann Sanders-Loehr: "Electrostatic Environment of the Tryptophylquinone Cofactor in Methylamine Dehydroganase. Evidence from Resonance Ram

Pierre.Moenne-Locoz、Nobuhumi Nakamura、Shinobu Itoh、Shunichi Fukuzumi、Antonius C.F.Gorren、Johannis A.Duine 和 Joann Sanders-Loehr：“甲胺脱氢酶中色氨酸醌辅因子的静电环境。来自共振拉姆的证据

Shinobu Itoh et al.: "Addition-Cyclization Reaction of Nitoroalkane Anions with 0-Quinone Derivatives via Electron Transfer in the C-T Complexes" J.Chem.Soc.,Perkin Trans.2. (7). 1429-1433 (1996)

Shinobu Itoh 等人：“硝基烷阴离子与 0-醌衍生物通过 C-T 配合物中的电子转移进行加成环化反应”J.Chem.Soc.，Perkin Trans.2。

Shinobu Itoh, Takashi Komori, Yutaka Chiba, Akito Ishida, Setsuo Takamuku, and Shunichi Fukuzumi: "The Photochemical Oxidation of Benzyl Alcohols by the Triplet Excited State of Coenzyme Pyrroloquinolinequinone." Chem.Commun.(4). 465-466 (1996)

Shinobu Itoh、Takashi Komori、Yutaka Chiba、Akito Ishida、Setsuo Takamuku 和 Shunichi Fukuzumi：“辅酶吡咯并喹啉醌的三重激发态对苯甲醇的光化学氧化。”

Shinobu Itoh, Naoki Takada, Shigenobu Haranou, Takeya Ando, Mitsuo Komatsu, Yoshiki Ohshiro, and Shunichi Fukuzumi: "Model Studies of TTQ-Containing Amine Dehydrogenases." J.Org.Chem.61 (25). 8967-6974 (1996)

Shinobu Itoh、Naoki Takada、Shigenobu Haranou、Takeya Ando、Mitsuo Komatsu、Yoshiki Ohshiro 和 Shunichi Fukuzumi：“含 TTQ 的胺脱氢酶的模型研究”。