Preparation and Characterization of Novel Modified-Electrodes with Metal Complexes as a Binder

以金属配合物为粘合剂的新型修饰电极的制备及表征

• 批准号: 14592001
• 负责人: NAKAMURA Nobuhumi
• 金额: $ 2.37万
• 依托单位: Tokyo University Agriculture And Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14592001/
• 关键词: Modified electrode; Ruthenium complex; Self-assembly; Electrochemistry; Electron transfer reaction; Mediator; Quinone; Cytochrome P450; 電極表面

Variable organic and inorganic compounds have been used to modify electrode surfaces in order to create novel functionalized electrodes. In this study, Ru complexes containing 1,10-phenanthroline-5,6-dione (dpq) were synthesized and used as electrode modifiers. Spectroscopic and electrochemical properties of the complexes were examined. And then, Ru complexes containing (dpq) were assembled on a gold electrode.The cyclic voltammogram of the Ru complex, which was assembled on a 4-pds modified gold electrode by using ligand substitution, shows two quasi-reversible redox-couples that are assigned to the quinone/semiquinone couple (E_<1,1/2>=80 mV vs. Ag ; ΔE_1=85mV) and the Ru^<II>/Ru^<III> couple (E_<2,1/2=863 mV vs. Ag ; ΔE=2=70 mV).No redox peaks were observed when using a gold electrode, which was prepared by refluxing a bare gold electrode under the same conditions. The surface coverage, calculated by integration of the charge under the voltammetric wave, was found to be 2.1×10^<-10>mol cm^<-1>. It is reasonable to conclude that close packing of the Ru complex moieties is achieved for monolayer. When a ligand which is a bipyridine privative containing a thiolate group was used, the Ru complex monolayer could be also formed. Since the cathodic peak density was found to increase linearly with the scan rate in both cases, it was conformed that the Ru complexes were adsorbed on the gold electrode.On the other hand, to prepare the stable enzyme for immobilization on the electrode, cytochrome P450 from thermoacidophilic crenarchaeon, Sulfolobus tokodaii strain 7,(P450st) has been expressed in E.coli and purified at high homogeneity. P45Ost was crystallized and the structure was determined at a 3.0Å resolution. Direct electrochemistry of P45Ost in a didodecyldimethylammonium bromide film on a plastic formed carbon electrode has also been demonstrated. A quasi-reversible redox response has been observed even at elevated temperatures of up to 80℃

可变的有机和无机化合物已被用于修饰电极表面，以创建新的功能化电极。本研究合成了含1，10-菲咯啉-5，6-二酮（dpq）的钌配合物，并将其用作电极修饰剂。研究了配合物的光谱和电化学性质。用配体取代法在4-pds修饰的金电极上组装了含（dpq）的钌配合物，其循环伏安曲线显示出两个准可逆的氧化还原电对，分别为醌/半醌电对（E1，1/2&gt;=80 mV vs. Ag ; Δ E1 = 85 mV）和Ru^<II>/Ru^<III>电对（E &lt;2，1/2=863 mV vs. Ag ; ΔE=2=70 mV）.在相同条件下，以裸金电极为基底制备的金电极没有氧化还原峰.通过伏安波下的电荷积分计算的表面覆盖度为2.1×10^<-10>mol cm^<-1>。可以合理地得出结论，对于单层，钌配合物部分实现了紧密堆积。当配体为含巯基的联吡啶配体时，也可以形成钌配合物单分子膜。另一方面，为了制备稳定的固定化酶，将嗜热嗜酸泉古菌Sulfolobus tokodaii strain 7（P450 st）的细胞色素P450在大肠杆菌中进行了表达和纯化。P45 Ost结晶，并在3.0 nm分辨率下确定结构。P45 Ost在塑料成型碳电极上的双十二烷基二甲基溴化铵膜中的直接电化学也已被证明。即使在高达80℃的高温下也观察到准可逆的氧化还原反应

项目成果

Y.Oku: "Structure and direct electrochemistry of cytochrome P450 from the thermoacidophilic crenarchaeon, Sulfolobus tokodaii strain 7"J.Inorg.Biochem. (In Press).

Y.Oku：“来自嗜热嗜酸细胞的细胞色素 P450 的结构和直接电化学，Sulfolobus tokodaii 菌株 7”J.Inorg.Biochem。

K.Niki: "Coupling to Lysine-13 Promotes Electron Tunneling through Carboxylate-Terminated Alkanethiol Self-Assembled Monolayers to Cytochrome c"J.Phys.Chem.B. 107. 9947-9949 (2003)

K.Niki：“与赖氨酸 13 的偶联促进通过羧酸盐封端的烷硫醇自组装单层到细胞色素 c 的电子隧道”J.Phys.Chem.B。

K.Niki, W.R.Hardy, M.G.Hill, H.Li, J.R.Sprinkle, E.Margoliash, K.Fujita, R.Tanimura, N.Nakamura, H.Ohno, J.H.Richards, H.B.Gray: "Coupling to Lysine-13 Promotes Electron Tunneling through Carboxylate-Terminated Alkanethiol Self-Assembled Monolayers to Cyt

K.Niki、W.R.Hardy、M.G.Hill、H.Li、J.R.Sprinkle、E.Margoliash、K.Fujita、R.Tanimura、N.Nakamura、H.Ohno、J.H.Richards、H.B.Gray：“与赖氨酸 13 的偶联促进

Y.Oku: "Structure and Direct Electrochemistry of Cytochrome P450 from the Thermoacidophilic crenarchaeon, Sulfolobus tokodaii Strain 7"J.Inorg.Biochem.. (in press).

Y.Oku：“来自嗜热嗜酸细胞的细胞色素 P450 的结构和直接电化学，Sulfolobus tokodaii Strain 7”J.Inorg.Biochem..（正在出版）。

Y.Oku, A.Ohtaki, S.Kamitori, N.Nakamura, M.Yohda, H.Ohno, Y.Kawarabayasi: "Structure and Direct Electrochemistry of Cytochrome P450 from the Thermoacidophilic Crenarchaeon, Sulfolobus tokodaii Strain 7"J. Inorg. Biochem.. (in press). (2004)

Y.Oku、A.Ohtaki、S.Kamitori、N.Nakamura、M.Yohda、H.Ohno、Y.Kawarabayasi：“来自嗜热嗜酸 Crenarchaeon、Sulfolobus tokodaii 菌株 7 的细胞色素 P450 的结构和直接电化学”J。