Study on Atomically Ordered Surfaces of Functional Electrodes for Electron Transfer Reactions of Metalloproteins

金属蛋白电子转移反应的功能电极原子有序表面研究

• 批准号: 08455399
• 负责人: TANIGUCHI Isao
• 金额: $ 4.86万
• 依托单位: Kumamoto 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 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455399/
• 关键词: Single crystal electrode; Monolayer; Thiol; Vacuum evaporation; STM; AFM; Electron transfer; Cytochrome c; Reconstructed myoglobin

In the present study, surface functions of modified electrodes for electron transfer reactions of metalloproteins have been examined by using gold single crystal electrode surfaces.1. Preparation and characterization of single crystal electrode surfaces :Gold single cryatal surfaces were prepared by both vacuum evaporation and flame-annealing-quenching methods, and their surfaces were characterized by STM/AFM and electrochemical measurements as a function of preparation conditions.2. Functional electrode surfaces for electron transfer reactions of metalloproteins :(1) Surface structures of modified Au single crystal electrodes for cytochrome c electrochemistry were studied by STM, surface-enhanced IR absorption spectroscopy (SEIRAS) and the electrochemical reductive desorption technique. On the Au(1 11) surface, for example, adsorbed 4-pyridinethiol (4-PySH) showed the rectangular unit cell of p(5*<square root>3R-3Oﾟ) structure with an interaction of two neighboring 4-PySH, while the 2 … More -PySH modified electrode showed a p(4*<square root>7R-4O.9ﾟ) structure with no dimer formation, suggesting that 2-PySH adsorbs at both thiolate S and pyridine N atoms.(2) Using highly hydrophilic sin-face of In203 electrodes, biological functions and electron transfer kinetics of native and reconstituted myoglobins were found to be related very much to the heme structure, such as the porphyrin backbone of the heme, type of metal ion of the redox center, coordination structure etc.3. Modification with thiols on single crystal gold electrode surfaces :A very small amount (ca. 1%) of sulfide impurity in a thiol modifier solution was found to make the modified surface structure complicated in some cases. However, the structure of modified surface was very much controlled by thermodynamic and kinetic aspects of the modification processes. The reductive desorption peak potentials of thiols adsorbed on the electrode surfaces were found to be used as an excellent measure for predicting the structures of the modified surfaces. Electrochemical fabrication for the thiol modified surface has also developed. Less

在介绍研究中，通过使用金单晶电极表面研究了金属蛋白电子转移反应的改性电极的表面功能。1。单晶电极表面的制备和表征：通过真空蒸发和防火式淬火方法制备金单晶表面，其表面的特征是通过STM/AFM和电化学测量结果作为制备条件的函数。2。金属蛋白的电子传递反应的功能电极表面：（1）通过STM进行了改性的AU单晶电极的表面结构，用于细胞色素C电化学，表面增强IR抽象光谱光谱（SEIRAS）和电化学减少的解答技术。 On the Au(1 11) surface, for example, adsorbed 4-pyridinethiol (4-PySH) showed the rectangular unit cell of p(5*<square root>3R-3Oﾟ) structure with an interaction of two neighboring 4-PySH, while the 2 … More -PySH modified electrode showed a p(4*<square root>7R-4O.9ﾟ) structure with no dimer formation, suggesting that 2-PySH （2）使用高度亲水性的In203电极，生物学功能和本机和重构肌球蛋白的电子传递动力学，发现与血红素结构非常相关，例如金属型金属的卟啉蛋白backentect，icsex Centorcorcorcorcorcorcorcorcorcorcorcorcorcordecordecor，redox中心是孢子骨的结构非常相关。用硫醇金电极表面进行修饰：发现在硫醇修饰剂溶液中硫化物杂质的少量（大约1％）的溶液中，发现在某些情况下，修饰的表面结构变得复杂。然而，修饰表面的结构受到修饰过程的热力学和动力学方面的很大控制。发现吸附在电极表面上的硫醇的脱附峰值的降低被用作预测改良表面结构的极好度量。硫醇改性表面的电化学制造也已经发展。较少的

项目成果

I.Taniguchi,: "Functional Electrodes for Probing Metalloproteins and Bioelectrochemical Systems," Interface,. 6,. 34-37 (1997)

I.Taniguchi，：“用于探测金属蛋白和生物电化学系统的功能电极”，Interface，。

I.Taniguchi, S.Yoshimoto, M.Yoshida, S.Kobayashi, T.Miyawaki, Y.Aono, Y.Sunatsuki, H.Taira: "Simple methods for preparation of a well-defined 4-pyridinethiol modified surface on Au (111) electrodes for cytochrome c electrochemistry" Electrochim.Acta. (in

I.Taniguchi、S.Yoshimoto、M.Yoshida、S.Kobayashi、T.Miyawaki、Y.Aono、Y.Sunatsuki、H.Taira：“在 Au 上制备明确的 4-吡啶硫醇修饰表面的简单方法（

TANIGUCHI,Isao: "Atomically-defined Surfaces and Artificially-designed Molecules for New Protein Electrochemistry" Proc. The 3rd Korea-Japan Joint Seminar on Electrochemistry.127-132 (1997)

TANIGUCHI,Isao：“用于新蛋白质电化学的原子定义的表面和人工设计的分子”Proc。

MIE,Yasuhiro: " Electrochemisty of myoglobins reconstituted with azahemes and mesohemes" Bioelectrochem.Bioenerg.,. 42(2). 175-184 (1998)

MIE，Yasuhiro：“用 azahemes 和 mesohemes 重建肌红蛋白的电化学”Bioelectricchem.Bioenerg.，。

I.Taniguchi,: "Preparation of Semi-Artificial Myoglobins and Their Electrochemical Reactions" Proc.7th Int.Symp.on Electrochemistry,. 36-37 (1996)

I.Taniguchi，：“半人工肌红蛋白的制备及其电化学反应”Proc.7th Int.Symp.on Electrochemistry，。