| Project/Area Number |
10640487
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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 |
Physical chemistry
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| Research Institution | Shinshu University |
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Principal Investigator |
KOJIMA Masanobu Shinshu University, Fac. Agriculture, Professor, 農学部, 助教授 (20153538)
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| Co-Investigator(Kenkyū-buntansha) |
TAKEYA Haruhiko COSMO Research Institute, Reseacher, 研究員
KURIYAMA Yasunao Kitasato Univ., Fac. Science, Lecturer, 理学部, 講師 (50225273)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1999: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1998: ¥1,700,000 (Direct Cost: ¥1,700,000)
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| Keywords | Zeolite Nanocavities / Adsorption / Aromatic Alkenes / Azobenzene / Cis-Trans Photoisomerization / Photooxygenation / Electrostatic Interaction / Effects of Metal Cations / ゼオライト / シスートランス光異性化 / スチルベン / 濃度効果 / 自由体積 / 金属イオン / 超分子 / 4-メトキシスチレン / 吸着水の効果 / 金属イオンの効果 / シス_トランス異性化 / シス-トランス異性化 / 光誘起電子移動反応 / 電荷移動吸収スピクトル / 二量化反応 / イオンラジカル |
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| Research Abstract |
In order to elucidate the spectroscopic and photochemical behavior of guest molecules included in zeolite nanocavities, we (1) took the spectroscopic measurements of the BrΦnsted and Lewis acidities in the cavities, and studied (2) the dark reaction of aromatic alkenes caused by the BrΦnsted and Lewis acid sites, (3) the effects of alkali-metal cations in the cavities on the cis-trans photoisomerization of stilbene and azobenzene, and (4) the effects of alkali-metal cations in the cavities on the photooxygenation of aromatic alkenes. From these investigations, we obtained the following significant information about the cavities:
1. Using 2-quinolone as a probe, the BrФnsted and Lewis acidities in the cavities were determined more precisely than by previous procedures such as the Hammett method.
2. When electron-rich aromatic alkenes were adsorbed in proton-exchanged zeolites, their dark reaction proceeded readily due to the BrΦnsted and Lewis acid sites in the cavities. Therefore, it seems likely that alkali-metal cation exchanged zeolites are suitable photochemical reaction vessels for the alkenes.
3. It was found that the co-adsorbed water in the cavities accelerated the above dark reactions.
4. Due to the electrostatic interaction between guest molecules and metal cations in the cavities, the photodimerization of styrenes and the intramolecular cycloaddition of stilbenes were suppressed. As a result, the photooxygenation of the alkenes occurred more efficiently in the cavities than in solutions.
5. It was found that the photochemical behavior of guest molecules adsorbed in the cavities depends on the site in which the molecules electrostatically interact with the metal cations.
These results clearly indicate that the characteristics of zeolite cavities can be explained to regulate the photochemical behavior of guest molecules.
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