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In-Situ Measurements and Molecular Orientation by External Reflection Spectrometry of Liquid-Liquid Interfacial Adsorbates of Porphyrins.

Research Project

Project/Area Number 13650865
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 工業分析化学
Research InstitutionAkita University

Principal Investigator

MORIYA Yoshio  Akita University, Faculty of Engineering and Resourse Science, Research Assistant, 工学資源学部, 助手 (30241673)

Co-Investigator(Kenkyū-buntansha) OGAWA Nobuaki  Akita University, Faculty of Engineering and Resourse Science, Professor, 工学資源学部, 教授 (80169193)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 2002: ¥500,000 (Direct Cost: ¥500,000)
Keywordsliquid-liquid interface / protonated porphyrins / interfacial adsorbate / external reflection / partial internal reflection / molecular orientation / interface selection rule / aggregate / 吸着状態 / 界面配向 / p-偏光スペクトル / 界面濃度 / 部分反射 / J-会合体
Research Abstract

The authors investigated the interfacial adsorption states of lipophilic-porphyrins (H_2P) in a protonated form (H_4PX_2) at the inert organic solvent/aqueous inorganic acid (HX) solution interface by development of in situ measurement devices for partial reflection spectrometry, including external reflection (ER) and partial internal reflection (PIR).
1.Stoichiometric analysis of protonated tetraphenylporphyrin in an aggregate (H_4PX_2)_<n,i> was accomplished using a simple device comprising a liquid cell and prisms. (1)In the toluene-4 M H_2SO_4 system, ER spectrometry was effective to distinguish interfacial adsorbates from lipophilic solute in the organic phase (H_2P)_o. (2)In the dodecane-4 M H_2SO_4 system, all (H_2P)_o was protonated to yield (H_4PX_2)_<n,i> and aqueous species, H_4P^<2+>_<aq>. The relationship of reflection absorbance at each of bands for interfacial molecular density [H_4PX_2]_i suggested that the interfacial adsorption state changed from a monolayer form to a … More multilayer one with a different reflection coefficient. (3)The saturated interfacial molecular density in the dodecane-4 M H_2SO_4 system was estimated to be 1.20×10^<-10> mol cm^<-2> ; it yields a tilt angle 47°of pyrrole ring plane against the interface normal.
2.No aggregation was found in the lipophilic tetraphenylporphyrin derivatives with substituent at ortho-position in meso-phenyl group. Whereas, protonated tetra-p-torylporphyrin could associate to form some aggregate. These suggest the molecular association is depend on the rotation nature of phenyl-group to yield a planar-type molecular structure.
3.The incident angle dependence of reflection spectra was studied using a home-made variable-angle device. Positive and negative bands have been observed in the p-polarized PIR spectra, whose band location correspond to those in p-polarized ER spectra. Nevertheless, the bands in the p-PIR exhibited reversed sign to those of p-ER spectra. These suggest that the interface selection rule of the p-PIR spectrometry has a reversal rule of p-ER, and PIR can also be used for the analysis of molecular orientation. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] Yoshio Moriya: "Interfacial Adsorption of Diprotonated Tetraphenylporphyrin and Demrtalation of Some Metalloporphyrins in the Dodecane-Aqueous Sulfuric Acid System"Analytical Sciences. 17(supplement). i1253-i1256 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya: "Simple Devices Comprised of an Optical Cell and Prisms for Direct Spectrophotometric Measurement of Liquid-Liquid Interfacial Adsorbate"International Journal of the Society of Materials Engineering for Resources. 10(No.2). 147-152 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya: "Analysis by Partial Reflection Spectrometry of Protonated Tetraphenylporphyrin Adsorbed at a Liquid-Liquid Interface"Analytical and Bioanalytical Chemistry. 376. 374-378 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya: "Utilization of Partial Reflection Spectrometry for the Analysis of a Liquid-Liquid Interfacial Adsorbate"Scientific and Technical Reports of Faculty of Engineering and Resource Science, Akita University. Annual report No.24. 11-18 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Nobuaki Ogawa: "Interfacial Orientation of Porphyrin at the Liquid-Liquid Interface Using UV-vis External Reflection Spectroscopy"Proceedings of International Solvent Extraction Conference, ISEC2002 (Cape Tawn). 58-63 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya, et al.: "Interfacial Adsorption of Diprotonated Tetraphenylporphyrin and Demetalation of Some Metalloporphyrins in the Dodecane-Aqueous Sulfuric Acid System"Analytical Sciences. 17(Supplement). i1253-i1256 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya, et al.: "Simple Devices Comprised of an Optical Cell and Prisms for Direct Spectrophotometric Measurement of Liquid-Liquid Interfacial Adsorbate"International Journal of the Society of Materials Engineering for Resources. 10(No.2). 147-152 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya, et al.: "Analysis by Partial Reflection Spectrometry of Protonated Tetraphenylporphyrin Adsorbed at a Liquid-Liquid Interface"Analtycal and Bioanalytical Chemistry. 376. 374-378 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya, et al.: "Utilization of Partial Reflection Spectrometry for the Analysis of a Liquid-Liquid Interfacial Adsorbate"Scientific and Technical Reports of Faculty of Engineering and Resource Science, Akita University, Annual reports. No.24. 11-18 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Nobuaki Ogawa, et al.: "Interfacial Orientation of Porphyrin at the Liquid-Liquid Interface Using UV-vis External Reflection Spectroscopy"Proceedings of International Solvent Extraction Conference, ISEC2002(Cape Tawn). 58-63 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yoshio Moriya, et al.: "Analysis by partial reflection spectrometry of protonated tetraphenyl-porphyrin adsorbed at a liquid-liquid interface"Analytical and Bioanalytical Cnemistry. 376. 374-378 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshio Moriya, et al.: "Interfacial adsorption of diprotonated tetraphenylporphyrin and demetalation of some metalloporphyrins in the dodecane-aqueous sulfuric acid system"Analytical Sciences. 17Supplement. i1253-i1256 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] Nobuaki Ogawa, et al.: "Interfacial orientation of porphyrin at the liquid-liquid interface using UV-vis external reflection spectroscopy"Proceedings of the International Solvent Extraction Conference. ISEC2002. 58-63 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshio Moriya, et al.: "Simple devices comprised of an optical cell and prisms for direct spectrophotometric measurement of liquid-liquid interfacial adsorbate"International Journal of Materials Engineering for Resources. 10・2. 147-152 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshio Moriya, et al.: "Analysis of protonated tetraphenylporphyrin adsorbed at a liquid-liquid interface by partial reflection spectrometry"Analytical and Bioanalytical Chemistry. (in press). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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