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Mechanisms of Noncatalytic Organic Chemical Reactions in Super- and Subcritical Water

Research Project

Project/Area Number 13640509
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

MATUBAYASI Nobuyuki  Institute for Chemical Research, Instructor, 化学研究所, 助手 (20281107)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2002: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
Keywordsenergy representation / distribution function / chemical potential / solvation free energy / solute-solvent interaction / computer simulation / hydrophobicity / supercritical fluid / 水溶液
Research Abstract

The energy representation of the molecular configuration in a dilute solution is introduced to express the solvent distribution around the solute over a one-dimensional coordinate specifying the solute-solvent interaction energy. In this representation, the correspondence is shown to be one-to-one between the set of solute-solvent interaction potentials and the set of distribution functions On the basis of the one-to-one correspondence, an approximate functional for the chemical potential of a solute in solution is constructed by adopting the Percus-Yevick-like approximation in the repulsive region of the solute-solvent interaction and the hypernetted-chain-like approximation in the attractive region. The chemical potential is then given exactly to second order with respect to the solvent density and to the solute-solvent interaction. It is demonstrated that the chemical potentials of nonpolar, polar, and ionic solutes in water are evaluated accurately and efficiently from the single functional over a wide range of thermodynamic conditions. Furthermore, the conformation of a nanoscale molecule such as protein varies strongly in response to solute-solvent interactions. An approach to the solvation free energy of a solute molecule with conformational flexibility thus needs to be established toward treating a solution system of functional importance. The method of energy representaion is extended to treat the solvation free energy of a flexible solute molecule, In this work, we examined solute systems in water with stretching and/or torsioal degrees of freedom for intramolecular motion, and demonstrated the performance of the method over a wide range of thermodynamic conditions including both ambient and supercritical. The aggregation behaviors of hydrophobic and hydrophilic solutes in water are also treated within the same framework.

Report

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

    (29 results)

All Other

All Publications (29 results)

  • [Publications] M.Nakahara, N.Matubayasi, C.Wakai, Y.Tsujino: "Structure and dynamics of water : from ambient to supercritical"Journal of Molecular Liquids. 90. 75-83 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Matubayasi, N.Nakao, M.Nakahara: "Structural study of supercritical water. III. Rotational dynamics"Journal of Chemical Physics. 114. 4107-4115 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Yamaguchi, N.Matubayasi, M.Nakahara: "A mode-coupling approach to the attractive interaction effect on the solute diffusion in liquids"Journal of Chemical Physics. 115. 422-432 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Kubo, R.M.Levy, P.J.Rossky, N.Matubayasi, M.Nakahara: "Chloride Ion Hydration and Diffusion in Supercritical Water Using Polarizable Water Model"Journal of Physical Chemistry B. 106. 3979-3986 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Matubayasi, M.Nakahara: "Theory of solutions in the energy representation. II. Functional for the chemical potential"Journal of Chemical Physics. 117. 3605-3616 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Kimura, N.Matubayasi, H.Sato, F.Hirata, M.Nakahara: "Enthalpy and entropy decomposition of free-energy changes for side-chain conformations of aspartic acid and asparagine in acidic, neutral, and basic aqueous solutions"Journal of Physical Chemistry B. 106. 12336-12343 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Nagai, C.Wakai, N.Matubayasi, M.Nakahara: "Noncatalytic Cannizzaro-type Reaction of Acetaldehyde in Supercritical Water"Chemistry Letters. 2003. 310-311 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 松林 伸幸, 若井 千尋, 中原 勝: "2章 超臨界流体のミクロ物性、2節NMRによる超臨界流体の構造解析"超臨界流体のすべて(荒井 康彦監修)(テクノシステム). 23-26 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 若井 千尋, 松林 伸幸, 中原 勝: "4.2章 液体・溶液物性への応用"新しい高圧科学(毛利 信男)(講談社サイエンティフィク). 147-201 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 松林 伸幸: "化学便覧 基礎編"丸善(印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Nakahara, N. Matubayasi., C. Wakai, and Y. Tsujino: "Structure and dynamics of water from ambient to supercritical"J. Mol. Liq. 90. 75-83 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Yamagudhi, N. Matubayasi, and M. Nakahara: "A mode-coupling approach to the attractive interaction effect on the solute diffusion in liquids"J. Chem. Phys. 115. 422-432 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kubo, R. M. Levy, P. J. Rossky, N. Matubayasi, and M. Nakahara: "Chloride ion hydration and diffusion in supercritical water using a polarizable water model"J. Phys. Chem. B106. 3979-3986 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N. Matubayasi, and M. Nakahara: "Theory of solutions in the energy representation. II. Functional for the chemical potential"J. Chem. Phys. 117. 3605-3616 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Kimura, N. Matubayasi, H. Sato, F. Hirata, and M. Nakahara: "Enthalpy and entropy decomposition of free-energy changes for side-chain conformations of aspartic acid and asparagine in acidic, neutral, and basic aqueous solutions"J. Phys. Chem. B106. 12336-12343 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Nagai, C. Wakai, N. Matubayasi, and M. Nakahara: "Noncatalytic Cannizzaro-type Reaction of Acetaldehyde in Supercritical Water"Chem. Lett. 32. 310-311 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Kubo, R.M.Levy, P.J.Rossky, N.Matubayasi, M.Nakahara: "Chloride Ion Hydration and Diffusion in Supercritical Water Using Polarizable Water Model"Journal of Physical Chemistry B. 106. 3979-3986 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Matubayasi, M.Nakahara: "Theory of solutions in the energy representation. II. Functional for the chemical potential"Journal of Chemical Physics. 117. 3605-3616 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Kimura, N.Matubayasi, H.Sato, F.Hirata, M.Nakahara: "Enthalpy and entropy decomposition of free-energy changes for side-chain conformations of aspartic acid and asparagine in acidic., neutral, and basic aqueous solutions"Journal of Physical Chemistry B. 106. 12336-12343 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Nagai, C.Wakai, N.Matubayasi, M.Nakahara: "Noncatalytic Cannizzaro-type Reaction of Acetaldehyde in Supercritical Water"Chemistry Letters. 2003. 310-311 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 松林 伸幸, 若井 千尋, 中原 勝: "超臨界流体のすべて 2章 超臨界流体のミクロ物性、2節 NMRによる超臨界流体の構造解析"荒井 康彦監修、テクノシステム. 23-26 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 若井 千尋, 松林 伸幸, 中原 勝: "新しい高圧科学 4.2章 液体・溶液物性への応用"毛利 信男、講談社サイエンティフィク. 147-201 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 松林 伸幸: "化学便覧 基礎編"丸善(印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Nakahara, N.Matubayasi, C.Wakai, Y.Tsujino: "Structure and dynamics of water : from ambient to supercritical"Journal of Molecular Liquids. 90. 75-83 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] N.Matubayasi, N.Nakao, M.Nakahara: "Structural study of supercritical water. III. Rotational dynamics"Journal of Chemical Physics. 114. 4107-4115 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Yamaguchi, N.Matubayasi, M.Nakahara: "A mode-coupling approach to the attractive interaction effect on the solute diffusion in liquids"Journal of Chemical Physics. 115. 422-432 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Kubo, R.M.Levy, P.J.Rossky, N.Matubayasi, M.Nakahara: "Chloride Ion Hydration and Diffusion in Supercritical Water Using Polarizable Water Model"Journal of Physical Chemistry A. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 松林 伸幸, 若井 千尋, 中原 勝: "「超臨界流体のすべて」NMRによる超臨界流体の構造解析"テクノシステム(印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 若井 千尋, 松林 伸幸, 中原 勝: "「新しい高圧力の科学」液体・溶液物性研究への応用"講談社(印刷中). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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