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Kinetic and structural study of interfacial reaction in analytical separation system

Research Project

Project/Area Number 07404042
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 分離・精製・検出法
Research InstitutionOsaka 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)
KeywordsHigh-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.

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

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

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Watarai: "Interfacial mechanism in the extraction kinetics of Ni(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and molecular dynamics simulation of interfacial reactivity of the ligand" Bull.Chem.Soc.Jpn.70. 957-964 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Hinoue: "Complex formation betweem water-soluble porphyrin and cationic surfactant under the critical micelle concentration" Chem.Lett.763-764 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Watarai: "Microemulsions in separation sciences" J.Chromatography A. 780. 93-102 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Onoe: "Evaluation of the interfacial adsorptivity of 2-hydroxy-5-nonylbenzophenone oxime by a molecular dynamics simulation" Anal.Sci.14. 237-239 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Nagatani: "Formation and interfacial adsorption of the μ-oxo dimer of (5,10,15,20-tetraphenylporphyrinato) iron (III) in dodecane/aqueous acid system" J.Chem.Soc.,Faraday Trans.94. 247-252 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Nagatani and H.Watarai: "Specific adsorption of metal complexes of tetraphenylporphyrin at dodecane-water interface" Chem.Lett.167-168 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Watarai, M.Gotoh and N.Gotoh: "Interfacial mechanism in the extraction kinetics of Ni(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and molecular dynamics simulation of interfacial reactivity of the ligand" Bull.Chem.Soc.Jpn.70. 957-964 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Hinoue, J.Kobayashi, T.Ozeki and H.Watarai: "Complex formation between water-soluble porphyrin and cationic surfactant under the critical micelle concentration" Chem.Lett.763-765 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Watarai: "Microemulsions in separation sciences" J.Chromatography A. 780. 93-102 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Nagatani and H.Watarai: "Formation and interfacial adsorption of the mu-oxo dimer of (5,10,15,20-tetraphenylporphyrinato) iron(III) in dodecane/aqueous acid system" J.Chem.Soc., Faraday Trans.94. 247-252 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Nagatani: "Specific adsorption of metal complexes of tetraphenylporphyrin at dodecane-water interface" Chem.Lett.167-168 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Watarai: "Interfacial mechanism in the extraction kinetics of Ni (II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and molecular dynamics simulation of interfacial reactivity of the ligand" Bull.Chem.Soc.Jpn.70. 957-964 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Hinoue: "Complex formation between water-soluble porphyrin and cationic surfactant under the critical micelle concentration" Chem.Lett.763-764 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Watarai: "Microemulsions in separation sciences" J.Chromatography A. 780. 93-102 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Onoe: "Evaluation of the interfacial adsorptivity of 2-hydroxy-5-nonylbenzophenone oxime by a molecular dynamics simulation" Anal.Sci.14. 237-239 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Nagatani: "Formation and interfacial adsorption of the μ-oxo dimer of (5,10,15,20-tetraphenylporphyrinato) iron (III) in dodecane/aqueous acid system" J.Chem.Soc.Faraday Trans.94. 247-252 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Saitoh: "Total internal reflection flurometric study of the ion-association adsorption of ionic derivatives of porphyrin at liquid-liquid interface" Bull.Chem.Soc.Jpn.70. 351-358 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Watarai: "Total internal reflection fluorescence measurements of protonation equilibria of Rhodamine B and cctadecylrhodamine B at a toluene/water Interface" Langmuir. 12. 6717-6720 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Nagatani: "Two-phase stopped flow measurement of the protonation of tetraphenylporphyrin at the liquid-liquid interface" Anal.Chem.68. 1250-1253 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] R.Okumura: "Ion-association adsorption of water-soluble porphyrin at a liquid-liquid interface and an external electric field effect on the adsorption" Anal.Sci.12. 393-397 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 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)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Chida: "Interfacial adsorption and ion-association extraction of protonated tetraphenylporphyrin and octaethylporphrin" Bull.Chem.Soc.Jpn.69. 341-347 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Chida: "Interfacial adsorption and ion-association extraction of protonated tetraphenylporphyrin and octaethylporphyrin" Bull. Chem. Soc. Jpn.69. 341-347 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Watarai: "Interfacial reaction in the synergistic extraction rate of Ni(II)with dithizone and 1,10-phenanthroline" Talanta. 42. 1691-1700 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Watarai: "Total internal reflection fluorescence measurements of ion-association adsorption of water-soluble porphyrins" Chem. Lett.1995. 283-284 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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