| Project/Area Number |
04403011
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
分析・地球化学
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| Research Institution | Nagoya University |
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Principal Investigator |
FUNAHASHI Shigenobu Nagoya Univ., Faculty of Science, Professor, 理学部, 教授 (30022700)
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| Co-Investigator(Kenkyū-buntansha) |
INADA Yasuhiro Nagoya Univ., Faculty of Science, Research Associate, 理学部, 助手 (60242814)
AIZAWA Sen-ishi Nagoya Univ., Faculty of Science, Research Associate, 理学部, 助手 (60231099)
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| Project Period (FY) |
1992 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥40,500,000 (Direct Cost: ¥40,500,000)
Fiscal Year 1994: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1993: ¥9,400,000 (Direct Cost: ¥9,400,000)
Fiscal Year 1992: ¥30,000,000 (Direct Cost: ¥30,000,000)
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| Keywords | Kinetic analysis / Reaction intermediate / Solvation structure / EXAFS method / Stopped-flow method / Porphyrin / Organotin (IV) / 動態分析 / 溶媒交換反応 / 錯形成反応 / エチレンジアミン / 金属イオンの溶媒和構造 / テトラメチル尿素 / ポルフィリン錯体 |
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| Research Abstract |
Our purpose is to develop ﾞdynamic analytical chemistryﾞespecially on the basis of dynamic processes of metal complex formation. We proposed the kinetic analyzes on the basis of clarified mechanisms of complexation reactions in aqueous and non-aqueous solutions.The structural analysis of short-lived reaction intermediates was pursued by newly developed techniques. The following research results were obtained.
(1) Techniques to follow the dynamic processes were newly developed such as rapid-injection and high-pressure stopped-flow NMR methods and time-resolved stopped-flow EXAFS methods.
(2) Solvation structures of metal (II,III) ions in solutions were determined by the EXAFS method and the reactivities of the metal ions were clarified on the basis of the pressure effect in terms of bulkiness and chelate effects of solvent molecules.
(3) Deformation effect of the porphine ring on metalloporphyrin formation rate was demonstrated and the reactivity and selectivity of porphyrins for metal ions in kinetic analysis were clarified.
(4) Ternary metal complexes involving oxoacids were investigated in terms of structural aspects and selectivity for analysis.
(5) Structures and reactivities of unstable and short-lived reaction intermediates were successfully determined such as Hg (II) /Cu (II) heterodinuclear porphyrin intermediate, peroxochromium (VI) intermediate, radical intermediate of ascorbic acid, and 5-coordinate chromium (III) porphyrin intermediate.
In conclusion, we presented the trend of dynamic analyzes.
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