2003 Fiscal Year Final Research Report Summary
Preparation and Characterization of Novel Modified-Electrodes with Metal Complexes as a Binder
| Project/Area Number |
14592001
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
機能物質化学
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| Research Institution | Tokyo University Agriculture And Technology |
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Principal Investigator |
NAKAMURA Nobuhumi Tokyo University Agriculture And Technology, Faculty of Technology, Associate Professor, 工学部, 助教授 (60313293)
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| Project Period (FY) |
2002 – 2003
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| Keywords | Modified electrode / Ruthenium complex / Self-assembly / Electrochemistry / Electron transfer reaction / Mediator / Quinone / Cytochrome P450 |
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| Research Abstract |
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℃
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Research Products
(4 results)
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[Publications] 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 Cytochiome c"J. Phys. Chem. B.. 107. 9947-9949 (2003)
Description
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