| Project/Area Number |
16350042
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Analytical chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
OYAMA Munetaka Kyoto University, Graduate School of Engineering, Associate Professor (90221861)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,240,000 (Direct Cost: ¥15,700,000、Indirect Cost: ¥540,000)
Fiscal Year 2007: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2006: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2005: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2004: ¥10,700,000 (Direct Cost: ¥10,700,000)
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| Keywords | Stopped-flow method / Electron transfer reaction / cation radicals / Aromatic amines / Dimerization reaction / reaction mechanism / precursor effect / Electro-oxidation / ストップフロー法 |
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| Research Abstract |
In this project, as the advanced investigations of the electron-transfer stopped flow method, we analyzed the reactions of short lived aromatic cation radicals in acetonitrile. For the reactions of anisidine and N-methyl anisidine cation radicals, it was found that the reaction mechanism changed as well as the reactivity. In addition, the electron-transfer stopped-flow method was revealed the effects of the substituents on the meta-and ortho- positions in the reactions of aniline derivative cation radicals and the differences in the reactivity of the dimmer and trimer cation radicals of thiophene derivative. In relation with the former case, systematic investigations were performed for the meta- chloro-, methyl- and methoxy-substituted diphenylamine cation radicals in acetonitrile. As the result, it was clarified from the kinetic view point that there are the two types of the consecutive reactions, i.e., the cation radical-cation radical coupling reaction and to the cyclization reaction of single cation radical depending on the substituents.
Furthermore, the electron-transfer stopped flow method was applied to the measurement of the time-resolved visible absorption spectra of the cation radicals and dications of triarylamine derivative molecules, which should give information about the, reactivity and the stability depending on the substituents and molecular structures. Consequently, some bulky substituents were found to affect the reactivities of the di cations significantly. In addition, the electronic optical properties of the oxidized states of amine-based organic high-spin systems were investigated.
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