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Studies on the Cooperativie Transformation of Hydrogen-Bonds During the Intramolecular First-Order Transitions of Polypeptides-An Application of ^2H NMR Analysis in the Liquid Crystalline State

Research Project

Project/Area Number 15550111
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionTokyo Polytechnic University

Principal Investigator

ABE Akihiro  Tokyo Polytechnic University, Nano-Science Research Center, Professor, 工学研究科, 教授 (50114848)

Co-Investigator(Kenkyū-buntansha) HIEJIMA Toshihiro  Tokyo Polytechnic University, Department of Nano-Chemistry, Associate Professor, 工学部, 助教授 (30288112)
Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2004: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2003: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsPoly(aspartate)s / Intramolecular hydrogen-bond / Helix-coil transition / Normal transition / Helix-helix transition / _χ1 conformer / Mainchain liquid crystal / Dipole moment / ポリL-アスパルテート / 共重合構造 / 分子内転移の相図 / 長い側鎖 / van der Waals解析 / ポリ(α-アミノ酸エステル) / ヘリックスらせんの反転 / 3成分系相図 / リオトロピック液晶 / ^2H-^1H交換反応速度 / ^2HNMR解析
Research Abstract

1.Screw-sense inversion behaviors (left- to right-handed or vice versa) of α-helical polyaspartates differ substantially depending on the chemical structure (X) of the ester group at the side-chain terminals. The cause of such phenomenological differences among polymers (X=benzyl, chlorobenzyl, and phenethyl) have been investigated by constructing the phase diagram as a function of solvent composition (TCE/TFA) and temperature.
2.The helix-coil transition of polyaspartates (X=benzyl and X=phenethyl) in m-cresol at elevated temperature (a normal-type transition) has been studied by NMR methods. The observed ^1H-^1H vicinal coupling constant around the _χ1 bond rotation suggests that the g^- conformation decreases from 〜50% to 〜30% with increasing temperature in the transition region from the left-handed to random-coil state.
3.The nematic conformation of main-chain liquid crystals has been studied to examine the possible incorporation of the intramolecular hydrogen-bond. The spectroscopic as well as thermodynamic (PVT) analyses led to a conclusion that a group of partially oriented conformation persists over the entire range of the nematic state. This is an encouraging evidence for the molecular design of a new class of chemical structures.

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (21 results)

All 2005 2004 2003 Other

All Journal Article (15 results) Publications (6 results)

  • [Journal Article] Screw-Sense Inversion Characteristic of α-Helical Poly(β-p-chlorobenzyl L-aspartate) and Comparison with Other Related Polyaspartates2005

    • Author(s)
      A.Abe, K.Hiraga, Y.Imada, T.Hiejima, H.Furuya
    • Journal Title

      Biopolymers (Peptide Science) In press

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] On the Applicability of the van der Waals Potential E=-η/V^m to Chain Molecule Liquids2005

    • Author(s)
      A.Abe, Z.Zhou, H.Furuya
    • Journal Title

      Polymer In press

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stepwise Phase Transition of Chain Molecules : Crystallization/ Melting via a Nermatic LC Phase2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci. In press

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Screw-Sense Inversion Characteristic of α-Helical Poly(β-p-chlorobenzyl L-aspartate) and Comparison with Other Related Polyaspartates2005

    • Author(s)
      A.Abe, K.Hiraga, Y.Imada, T.Hiejima, H.Furuya
    • Journal Title

      Biopolymers (Peptide Science) (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] On the Applicability of the van der Waals Potential E=^-η/V^m to Chain Molecule Liquids2005

    • Author(s)
      A.Abe, Z.Zhou, H.Furuya
    • Journal Title

      Polymer (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stepwise Phase Transition of Chain Molecules : Crystallization/Melting via a Nermatic LC Phase2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] On the Applicability of the van der Waals Potential E=-η/V^m to Chain Molecule Liquids2005

    • Author(s)
      A.Abe, Z.Zhou, H.Furuya
    • Journal Title

      Polymer (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Stepwise Phase Transition of Chain Molecules : Crystallization/ Melting via a Nermatic LC Phase2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci. (accepted)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A RIS Treatment of the Mean-Square Dipole Moment of PMMA Chains in Consideration of the Pendant Ester Group Orientations2004

    • Author(s)
      Z.Zhou, A.Abe
    • Journal Title

      Polymer 45

      Pages: 1313-1320

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Nematic Conformation of Oxyethylene Spacers Involved in Main-Chain Liquid Crystals2003

    • Author(s)
      H.Furuya, H.Iwanaga, T.Nakajima, A.Abe
    • Journal Title

      Macromol.Symp. 192

      Pages: 239-250

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Orientational and Conformational Characteristics of Oxyethylene-type Spacers Involved in Dimer Liquid Crystals2003

    • Author(s)
      T.Hiejima, K.Seki, Y.Kobayashi, A.Abe
    • Journal Title

      J.Macromol.Sci., Part B.Phys. B42

      Pages: 431-439

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Orientational Order and Thermodynamic Properties of Mainchain Trimer Liquid Crystals : a Combined Use of ^2HNMR, PVT and High-pressure DTA2003

    • Author(s)
      A.Abe, T.Hiejima, T.Takeda, C.Nakafuku
    • Journal Title

      Polymer 44

      Pages: 3117-3123

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Effect of the Pendant Ester Group Orientationon the Dipole Moment of Poly(alkyl acrylate)s2003

    • Author(s)
      Z.Zhou, A.Abe
    • Journal Title

      Macromolecules 36

      Pages: 7366-7371

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Phase Behavior of Ternary Systems Involving a Conformationally Variable Chain and a Randomly Coiled Polymer2003

    • Author(s)
      J.Lin, S.lin, P.Liu, T.Hiejima, H.Furuya, A.Abe
    • Journal Title

      Macromolecules 36

      Pages: 6267-6272

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Effect of the Pendant Ester Group Orientations on the Dipole Moment of Poly(alkyl acrylate)s2003

    • Author(s)
      Z.Zhou, A.Abe
    • Journal Title

      Macromolecules 36

      Pages: 7366-7371

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] H.Furuya, H.Iwanaga, T.Nakajima, A.Abe: "Nematic Confirmation of Oxyethylene Spacers Involved in Main-Chain Liquid Crystals"Macromol.Symp.. 192. 239-250 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Hiejima, K.Seki, Y.Kobayashi, A.Abe: "Orientational and Conformational Characteristics of Oxyethylene-type Spacers Involved in Dimer Liquid Crystals"J.Macromol.SCi., Part B.Phys.. B42. 431-439 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Abe, T.Hiejima, T.Takeda, C.Nakafuku: "Orientational Order and Thermodynamic Properties of Mainchain Trimer Liquid Crystals : a Combined Use of ^2HNMR, PVT and High-pressure DTA"Polymer. 44. 3117-3123 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Z.Zhou, A.Abe: "Effect of the Pendant Easter Group Orientations on the Dipole Moment of Poly(alkyl acrylate)s"Macromolecules. 36. 7366-7371 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] J.Lin, S.Lin, P.Liu, T.Hiejima, H.Furuya, A.Abe: "Phase Behavior of Ternary systems Involving a Conformationally Variable Chain and a Randomly Coiled Polymer"Macromolecules. 36. 6267-6272 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Z.Zhou, A.Abe: "A RIS Treatment of the Mean-Square Dipole Moment of PMMA Chains in Consideration of the Pendant Group Orientations"Polymer. 45. 1313-1320 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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