Interfacial Electron Transfer of Metalloproteins -Design of Functional Electrode Surfaces and Its Application in Bioelectrochemistry-

金属蛋白的界面电子转移-功能电极表面的设计及其在生物电化学中的应用-

• 批准号: 06045042
• 负责人: TANIGUCHI Isao
• 金额: $ 3.9万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06045042/
• 关键词: Metalloprotein; Interfacial electron transfer; Single crystal; Functional electrode; Spectroelectrochemical technique; Biocatalytic reaction; Circular dichroism; Digital simulation; 界面電子移勤; 分光電気化学; 再構成ミオグロビン; アミノ酸変異分子; 電解電子移動; 生物電気化学; ダイナミクス

In the present study, electron transfer reactions of metalloproteins at functional electrodes have been examined to understand biofunctions of metalloproteins and to develop various bioelectrochemical reactions.1. Interfacial electron transfer reactions of metalloproteins and their bioelectrochemical applications :(1) Functional electrodes for rapid electron transfer of metalloproteins have been developed. (2) At the highly hydrophilic indium oxide electrode, some artificially modified myoglobin molecules have been studied. (3) For cytochrome c, clear effect of the structure of the modifier adsorbed onto gold single crystal surfaces on the electrochemical responses was observed. (4) Amino acid residues of ferredoxin have clearly shown to have their own distinguished roles for biological functions, such as controlling the redox potential and the complex formation with enzymes.2. Dynamics of structural change of metalloproteins :(1) Stopped-flow circular dichroism (CD) spectroelectrochem … More ical techniques has been developed. (2) Both cytochrome c and ferredoxin changed their structures by steps during electron transfer, and (3) some kinetic data of structural changes were obtained. (4) A fine structural change as a function of temperature was suggested for ferredoxin.3. Application of ferredoxin electrochemistry to develop artificial photosynthetic reactions :(1) Electrochemically reduced ferredoxin was applicable as an electron transfer mediator to develop new bioelectrocatalytic reactions as in nature. For example, L-malic acid was obtained with carbon dioxide fixation in the presence of ferredoxin-NADP^+-reductase and malic enzyme. L-glutamic acid was also obtained from oxoglutaric acid with by introducing of ammonia, and (2) their reactions were analyzed by using a digital simulation technique.4. Semi-artificially designed metalloproteins :(1) New biological functions have been found using semi-artificially reconstituted myoglobin molecules. (2) Computer calculation of the structure of ferredoxin showed that the modification of Ser-46 to Gly-46 introduced rather large distortion of the iron sulfur cluster, causing a large positive shift in redox potential. Less

在本研究中，对金属蛋白在功能电极上的电子转移反应进行了检查，以了解金属蛋白的生物功能并开发各种生物电化学反应。1．金属蛋白的界面电子转移反应及其生物电化学应用：(1)开发了用于金属蛋白快速电子转移的功能电极。 (2)在高亲水性氧化铟电极上，研究了一些人工修饰的肌红蛋白分子。 (3)对于细胞色素c，观察到吸附在金单晶表面的修饰剂的结构对电化学响应的明显影响。 (4)铁氧还蛋白的氨基酸残基已清楚地显示出其独特的生物学功能，例如控制氧化还原电位和与酶形成复合物。2．金属蛋白结构变化的动力学：（1）停流圆二色性（CD）光谱电化学技术已得到发展。 (2)细胞色素c和铁氧还蛋白在电子转移过程中逐步改变其结构，(3)获得了一些结构变化的动力学数据。 (4) 铁氧化还原蛋白随着温度的变化而发生精细的结构变化。3。铁氧还蛋白电化学在开发人工光合反应中的应用：(1)电化学还原的铁氧还蛋白可作为电子转移介体来开发新的生物电催化反应。例如，在铁氧还蛋白-NADP + -还原酶和苹果酸酶存在下通过二氧化碳固定获得L-苹果酸。还以酮戊二酸为原料，通过引入氨制备了L-谷氨酸，并通过数字模拟技术分析了它们的反应。 4．半人工设计的金属蛋白：(1)利用半人工重建的肌红蛋白分子发现了新的生物学功能。 (2)铁氧还蛋白结构的计算机计算表明，Ser-46向Gly-46的修饰引起了铁硫簇较大的畸变，导致氧化还原电位发生较大的正移。较少的

项目成果

NISHIYAMA,Katsuhiko: "Kinetics of Confromational Change in Cyanomyoglobin Following Electron Trasfer Monitored by Magnetically Induced Circular Dichroism Spectroscopy" Biochem.Biophys.Res.Commun.205. 1724-1728 (1994)

NISHIYAMA，Katsuhiko：“磁诱导圆二色性光谱监测电子转移后蓝肌红蛋白构象变化的动力学”Biochem.Biophys.Res.Commun.205。

HAWKRIDGE,Fred M.: "The Direct Electron Transfer Reactions of Cytochrome c at Electrode Surfaces" Comments on Inorg.Chem.17. 163-187 (1994)

HAWKRIDGE, Fred M.：“细胞色素 c 在电极表面的直接电子转移反应”对 Inorg.Chem.17 的评论。

TANIGUCHI,Isao: "Electrochemistry of Chlorella Ferredoxin at Modified Indium Oxide Electrodes and Its Application of Bioelectrocatalytic Reactions" Proc.2nd Japan-Korea Seminar on Electrochemistry. 11-12 (1996)

TANIGUCHI,Isao：“修饰氧化铟电极上小球藻铁氧还蛋白的电化学及其在生物电催化反应中的应用”Proc.第二届日韩电化学研讨会。

谷口,功: "二酸化炭素-化学、生化学、環境-(現代化学 増刊25)" 東京化学同人, 70-78(192) (1994)

谷口功：“二氧化碳-化学、生物化学、环境-（现代化学特刊25）”东京化学同人，70-78（192）（1994）

YAO,Qing: "Direct electron tansfer of hemoglobin adsorbed on the hydrophilic surface of an indium oxide electrode" J.Electroanal.Chem.(to be published).

姚庆：“氧化铟电极亲水表面吸附血红蛋白的直接电子转移”，J.Electroanal.Chem.（待出版）。