Project/Area Number |
07404042
|
Research Category |
Grant-in-Aid for Scientific Research (A)
|
Allocation Type | Single-year Grants |
Section | 一般 |
Research Field |
分離・精製・検出法
|
Research Institution | Osaka University |
Principal Investigator |
WATARAI Hitoshi Graduate School of Science, Osaka University, Professor, 大学院・理学研究科, 教授 (30091771)
|
Co-Investigator(Kenkyū-buntansha) |
TSUKAHARA Satoshi Graduate School of Science, Osaka University, Research Associate, 大学院・理学研究科, 助手 (50207338)
FUKIMOTO Takao Graduate School of Science, Osaka University, Research Associate, 大学院・理学研究科, 助手 (10199268)
HINOUE Teruo Graduate School of Science, Osaka University, Research Associate, 大学院・理学研究科, 助手 (50143821)
WATANABE Iwao Graduate School of Science, Osaka University, Assistant Prof., 大学院・理学研究科, 助教授 (50028239)
文珠四郎 秀昭 大阪大学, 理学部, 助手 (80191071)
|
Project Period (FY) |
1995 – 1997
|
Project Status |
Completed (Fiscal Year 1997)
|
Budget Amount *help |
¥39,300,000 (Direct Cost: ¥39,300,000)
Fiscal Year 1997: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1996: ¥8,200,000 (Direct Cost: ¥8,200,000)
Fiscal Year 1995: ¥27,800,000 (Direct Cost: ¥27,800,000)
|
Keywords | High-speed stirring method / Interfacial adsorption / Liquid-liquid interface / Interfacial complexation / Interfacial ligand-exchange / Pyridylazo compounds / Porphyrin / Molecular dynamics / 高速撹拌法 / 界面緩和法 / 界面錯生成反応 / 界面プロトン付加反応 |
Research Abstract |
(1) Interfacial adsorptivity of metal(II,III) -porphyrins was determined by means of high-speed stirring method. The results showed that Zn(II) complex was most adsorbable at the interface among neutral complexes and that metal(III) complexes were generally adsorbable because of their positive charges. Iron(III) complex inverted to mu -oxo complex at the interface. (2) The rate-controlling step of the extraction of Ni(II) with a hydrophobic pyridylazo ligand was the formation of 1 : 1 complex at the interface. The magnitude of the interfacial rate constant was larger in heptane/water than that in toluene/water. This solvent effect was explained from the difference in the location of the adsorbed ligand which was depicted by MD simulation ; the location of the ligand at the heptane.water interface is closer to the aqueous phase than that in toluene/water interface and is more favorable to react with metal ions in aqueous phase. (3) It was found that an anionic porphyrin and a cationic surfactant formed a 1 : 4 complex in aqueous solution. (4) New approach to predict an interfacial adsorptivity by MD simulation was developed and applied for the explanation of the adsorptivity of hydrophobic hydroxyoximes. Thus, in this year, the interfacial reaction was examined not only by experimental approach but also by computational simulation.
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