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Role of Hydrogen Bond in Polypeptides - ^2HNMR Studies in the Lyotropic Liquid Crystalline State

Research Project

Project/Area Number 13650959
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子構造・物性(含繊維)
Research InstitutionTOKYO INSTITUTE OF POLYTECHNICS

Principal Investigator

ABE Akihiro  TOKYO INSTITUTE OF POLYTECHNICS, 工学部, 教授 (50114848)

Co-Investigator(Kenkyū-buntansha) HIEJIMA Toshihiro  TOKYO INSTITUTE OF POLYTECHNICS, 工学部, 講師 (30288112)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsPoly(L-glutamate) / Poly(L-aspartate) / Helix-Coil Transition / Monodisperse PBLG / Re-entrant Isopropic Phase / Intramolecular Hydrogen Bond / Helix Sense Inversion / Chemical Modification of Side Chain Terminals / ペンタフルオロフェネチル基の導入 / らせんセンスの反転 / ヘリックス-コイル転移 / ^2H-^1H交換法 / p-クロロベンジル基の導入 / 蛍光顕微鏡法
Research Abstract

1. Monodisperse PBLG samples having DP of 25 〜 50 have been prepared by using a solid-state peptide synthesizer. The helix-coil transitions in a mixed solvent comprising CHCl_3 and DCA were followed by ^1H- and ^<13>C-NMR. These samples exhibited two separate chemical shifts over the entire biphasic region : one from the helical and the other from the coil part. These observations are in contraditoin to those previously reported by Nagayame et al.
2. The helix-sense inversion phenomena peculiar to poly(aspartic acid ester)s has been studies for systems such as poly (β-p-chlorobenzyl L-aspartate) and poly(β-pentafluorophenethyl L-aspartate). Chemical modifications at the sidechain terminal were found to cause appreciable changes in the solubility of polymers, and eventually the helix-helix transition temperatures were shifted. These results indicate that the stability of hydrogen bonds involved in the α-helix conformation sensitively alters with the sidechain structure as well as the character of the surrounding solvents. Further investigations are underway to elucidate these unique characteristics of the internal hydrogen-bonds.

Report

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

    (13 results)

All Other

All Publications (13 results)

  • [Publications] A.Abe: "Thermodynamics of Polymeric Fluids : Effect of Volume on the Configurational Entropy of Chain Molecules"Macromol. Symp.. 174. 383-391 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Abe: "The Order-Disorder of Polymeric Chains and Thermodynamic Significance"Rep. Prog. Polym. Phys. Jpn.. 43. 21-42 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Abe: "A Critical Study of the Entropy-Volume Relation of Chain Molecules in the Fluid State -Computer Simulation of n-Undecane and Comparison with Experimental PVT Data"Macromolecules. 34. 6450-6455 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ushiyama: "The Mechanism of the Helix-Sense Inversion of Polyaspartates as Revealed by the Study of Model Block Copolymers"Polym. J.. 34. 450-454 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Furuya: "Nematic Conformation of Oxyethylene Spacers Involved in Main-Chain Liquid Crystals"Macromol. Symp.. 192. 239-250 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Abe: "Orientational Order and Thermodynamic Properties of Mainchain Trimer Liquid Crystals : a Combined Use of ^2HNMR, PVT and High-pressure Differential Thermal Analysis"Polymer. 44. 3117-3123 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Abe, T. Takeda, T. Hiejima, H. Furuya: "Thermodynamics of Polymeric Fluids : Effect of Volume on the Configurational Entropy of Chain Molecules"Macromol. Symp.. Vol. 174. 383-391 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Abe: "The Order-Disorder of Polymeric Chains and Thermodynamic Significance"Rep. Prog, Polym. Phys. Jpn.. Vol.43. 21-42 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Abe, T. Takeda, T. Hiejima, H. Furuya: "A Critical Study of the Entropy-Volume Relation of Chain Molecules in the Fluid State - Computer Simulation of n-Undecane and Comparison with Experimental PVT Data"Macromolecules. Vol.34. 6450-6455 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ushiyama, H. Furuya, A. Abe, T. Yamazaki: "The Mechanism of the Helix-Sense Inversion of Polyaspartates as Revealed by the Study of Model Block Copolymers"Polym. J.. Vol. 34. 450-454 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Furuya, H. Iwanaga, T. Nakajima, A. Abe: "Nematic Conformation of Oxyethylene Spacers Involved in Main-Chain Liquid Crystals"Macromol. Symp.. Vol 192. 239-250 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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 Differential Thermal Analysis"Polymer. Vol. 44. 3117-3123 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Ushiyama, H.Furuya, A.Abe, T.Yamazaki: "The Mechanism of the Helix-Sense Inversion of Polyaspartates as Revealed by the Study of Model Block Copolymers"Polymer Journal. 34,(no.6). 450-454 (2002)

    • Related Report
      2002 Annual Research Report

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

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