Kinetic and structural study of interfacial reaction in analytical separation system

分析分离系统中界面反应的动力学和结构研究

• 批准号: 07404042
• 负责人: WATARAI Hitoshi
• 金额: $ 25.15万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07404042/
• 关键词: 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

(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.

(1)用高速搅拌法测定了金属卟啉的界面吸附率。结果表明，Zn（Ⅱ）配合物在中性配合物界面上吸附最强，而金属（Ⅲ）配合物由于带正电荷，一般都能吸附。铁（III）络合物在界面处转化为μ-氧代络合物。(2)疏水吡啶偶氮配体萃取Ni（II）的速率控制步骤是在界面形成1：1的络合物。庚烷/水体系的界面速率常数大于甲苯/水体系。分子动力学模拟结果表明，配体在庚烷/水界面上的吸附位置比在甲苯/水界面上更靠近水相，更有利于与水相中的金属离子发生反应. (3)发现阴离子卟啉与阳离子表面活性剂在水溶液中形成1：4的络合物。(4)开发了通过分子动力学模拟预测界面吸附性的新方法，并将其应用于解释疏水性羟基肟的吸附性。因此，今年不仅通过实验方法，而且通过计算机模拟来研究界面反应。

项目成果

H.Watarai: "Synergistic extraction rate of Ni(II) with dithizone and 4,7-diphenyl-1,10-phenanthroline" Solv.Extr.Res.Devel.Jpn.3. 109-116 (1996)

H.Watarai：“Ni(II) 与双硫腙和 4,7-二苯基-1,10-菲咯啉的协同萃取率”Solv.Extr.Res.Devel.Jpn.3。

H.Watarai: "Interfacial reaction in the synergistic extraction rate of Ni(II)with dithizone and 1,10-phenanthroline" Talanta. 42. 1691-1700 (1995)

H.Watarai：“Ni(II) 与双硫腙和 1,10-菲咯啉的协同萃取率中的界面反应”Talanta。

H.Nagatani: "Specific adsorption of metal complexes of tetraphenylporphyrin at dodecane-water interface" Chem.Lett.167-168 (1997)

H.Nagatani：“四苯基卟啉金属配合物在十二烷-水界面的特异性吸附”Chem.Lett.167-168 (1997)

H.Watarai: "Microemulsions in separation sciences" J.Chromatography A. 780. 93-102 (1997)

H.Watarai：“分离科学中的微乳液”J.Chromatography A. 780. 93-102 (1997)

Y.Onoe and H.Watarai: "Evaluation of the interfacial adsorptivity of 2-hydroxy-5-nonylbenzophenone oxime by amolecular dynamics simulation" Anal.Sci.14. 237-239 (1998)

Y.Onoe 和 H.Watarai：“通过分子动力学模拟评估 2-羟基-5-壬基二苯甲酮肟的界面吸附性”Anal.Sci.14。