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POLYPEPTIDE STRUCTURE AND DYNAMICS CONTROLLED BY PHOT0-ISOMERIZATION

Research Project

Project/Area Number 10650875
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 InstitutionHOKKAIDO UNIVERSITY

Principal Investigator

HIRAOKI Toshifumi  Hokkaido Univ., Grad. School of Eng., Ass. Pro., 大学院・工学研究科, 助教授 (10125346)

Co-Investigator(Kenkyū-buntansha) TSUTSUMI Akihiro  Hokkaido Univ., Grad. School of Eng., Pro., 大学院・工学研究科, 教授 (80000884)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1999: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1998: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordshelix-sense inversion / poly (β-n-propy L-aspartate) / right-handed α-hellx / p-phenylazobenzene / the side-chain conformation / photo-isomerization / ヘリックスセンス
Research Abstract

In order to clarify the mechanism of the helix-sense inversion of poly(β-n-propyl L-aspartate)(PnPLA), the conformational transition of PnPLA and its derivative with azobenzene group were investigated by means of NMR.
1) The right-handed α-helix (αィイD2RィエD2)of PnPLA can change thermoreversibly to the left-handed (αィイD2LィエD2) with increasing temperature from 30 to 70℃ in CDClィイD23ィエD2. The midpoint is 50℃, the transition free energy is 110 kJ/mol, and the exchange rate between both conformations is 5 /s at about 50℃. All the ィイD113ィエD1C signals of PnPLA can separate completely between the right- and left-helices, although only the NH and βィイD2sィエD2 proton resonances show the conformational dependence. These results indicate that the side-chain conformation of αィイD2RィエD2-helical PnPLA is different from that of αィイD2LィエD2-helix, as well as the main chain conformation. The αィイD2RィエD2-helix conformation of PnPLA changes to the left-handed, and subsequently to the random-coil with increasing the trifluoroacetic acid concentration. The coil conformation of PnPLA can change to the αィイD2LィエD2-helix with increasing the temperature, and the αィイD2RィエD2-helix is not detected in the high temperatures.
2) PnPLA containing 30% p-phenylazobenzene group in the side chain do not show the helix-sense inversion with the photo-isomerization of azobenzene group. The PnPLA containing more than 50% p-phenylazobenzene group is preparing for further experiments.
3) The internal rotational angle from the spin-spin coupling constant ィイD13ィエD1Jαβ is necessary to determine the side chain conformation. The monomer of L-asp-βィイD2RィエD2-d was successfully synthesized from the fumaric acid in DィイD22ィエD2O/NDィイD24ィエD2OD with the enzyme of L-aspartase to remove the contribution of the residual geminal ィイD12ィエD1Jββ in the signal of βィイD2sィエD2 proton. PnPLA-βィイD2RィエD2-d is preparing for further experiments.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (25 results)

All Other

All Publications (25 results)

  • [Publications] T.Hiraoki,A.Kogame,N.Nishi,A.Tsutsumi: "Deuterium NMR sstidoes on phenylring dynamics of Poly(L-phenylalanine)"J.Mol.Struc.. 441. 43-250 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Izumikawa,S.Kubata,T.Hiraoki,A.Tsutsumi: "^2H-NMR of α-helical poly(γ-benzyl L-[Nα-^2H_1]glutamate)in the solid state I.Molecular orientation in the film cast from chloroform solution"Rept.Prog.Polym.Phys.Jpn.. 41. 525-526 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Tani,T.Hiraoki,M.Takekawa,A.Tsutsumi: "Deuterium NMR studies of Benzyl Alcohol-d_5 in Poly(γ-benzyl L-glutamate)Gel"Rept.Prog.Polym.Phys.Jpn.. 41. 571-572 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Kawase,T.Hiraoki,A.Tsutsumi: "Dynamics of Polyglycine I by solid state ^2H-NMR.II"Rept.Prog.Polym.Phys.Jpn. 41. 573-574 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Takewaka,K.Sagawa,T.Hiraoki,H.J.Vogel,A.Tsutsumi: "Side Chain Dynamics on the surface of Bovine α-lactalbumin by solid state ^2H-NMR"Rept.Prog.Polym.Phys.Jpn. 41. 579-580 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Kameda,Y.Ohkawa,K.Yoshizawa,E.Nakano,T.Hiraoki,他: "Dynamics of the Tyrosine side chain in Bombyx mori and Samia cynthia ricini silk Fibroin studied by soild state ^2H NMR"Macromolecules. 32. 8491-8495 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A.Tsutsuni,T.Ozawa,M.Okada,T.Hiraoki,F.Ishii: "Electron spin resonance study on the sol-gel transition of gellan gum aqueous solution by the addition of paramagnetic metal-ions"Progr.Colloid Polym. Sci.. 114. 31-35 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Okada,T.Hiraoki,and A.Tsustumi: "Electron spin resonance of Hydrated Mn(II)in Gellan Gum aqueous solution"Rept.Prog.Polym.Phys.Jpn.. 42. 475-476 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Hiraoki, A. Kogame, N, Nishi, A. Tsutsumi: "Deuterium NMR sstidoes on phenylring dynamics of Poly (L-phenylalanine)."J. Mol. Struc.. 441. 43-250 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Izumikawa, S. Kubata, T. Hiraoki, A. Tsutsumi: "ィイD12ィエD1H-NMR of α-helical Poly(γ-benzyl L-[Nα-ィイD12ィエD1HィイD21ィエD2] glutamate) in the solid state I. Molecular orientation in the film cast from chloroform solution."Rept. Prog. Polym. Phys. Jpn.. 41. 525-526 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Tani, T. Hiraoki, M. Takekawa, A. Tsutsumi: "Deuterium NMR studies of Benzyl Alcohol-d5 in Poly (γ-benzyl L-glutamate) Gel."Rept. Prog. Polym. Phys. Jpn.. 41. 571-572 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kawase, T. Hiraoki, A. Tsutsumi: "Dynamics of Polyglycine I by solid state ィイD12ィエD1H-NMR. II"Rept. Prog. Polym. Phys. Jpn.. 41. 573-574 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Takewaka, K. Segawa, T. Hiraoki, H. J. Vogel, A. Tsutsumi: "Side Chain Dynamics on the surface of Bovine a-lactalbumin by solid state ィイD12ィエD1H-NMR."Rept. Prog. Polym. Phys. Jpn.. 41. 579-580 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Kameda, Y. Ohkawa, K. Yoshizawa, E. Nakano, T. Hiraoki, A. S. Ulrich, and T. Asakura: "Dynamics of the Tyrosine side chain in Bombyx mori and Samia cynthia ricini silk Fibroin studied by soild state ィイD12ィエD1H NMR."Macromolecules. 32. 8491-8495 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Tsutsumi, T. Ozawa, M. Okada, T. Hiraoki, F. Ishii: "Electron spin resonance study on the sol-gel transition of gellan gum aqueous solution by the addition of paramagnetic metal-ions."Progr. Colloid Polym. Sci.. 114. 31-35 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Okada, T. Hiraoki, and A. Tsutsumi: "Electron spin resonance of Hydrated Mn(II) in Gellan Gum aqueous solution."Rept. Prog. Polym. Phys. Jpn.. 42. 475-476 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Kameda, Y.Ohkawa, K.Yoshizawa, E.Nakano, T.Hiraoki,他: "Dynamics of the Tyrosine side chain in Bombyx mori and Samia cynthia ricini silk Fibroin studied by solid state ^2 HNMR"Macromolecules. 32. 8491-8495 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Tsutsumi, T.Ozawa, M.Okada, T.Hiraoki, F.Ishii: "Electron spin resonance study on the sol-gel transition of gellan gum aqueous solution by the addition of paramagnetic metal-ions"Rrogr. Colloid Polym. Sci.. 114. 31-35 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Okada, T.Hiraoki,and A.Tsutsumi: "Electron spin resonance of Hydrated Mn(II) in Gellan Gum aqueous solution"Rept. Prog. Polym. Phys. Jpn.. 42. 475-478 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Hiraoki: "Deuterium NMR sstidoes on phenylring dynamics of Poly (L-phenylalanine)" J.Mol.Struc.441. 243-250 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Izumikawa: "^2H-NMR of α-helical Poly (γ-benzyl L-[N_η-^2H_1]glutamate) in the solid state I. Molecular orientation in the film cast from chloroform solution" Rept.Prog.Polym.Phys.Jpn.41. 525-526 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Kubata: "^2H-NMR of α-helical Poly (γ-benzyl L-[N_η-^2H_1]glutamate) in the solid state II. Molecular orientation in the film cast from chloroform solution" Rept.Prog.Polym.Phys.Jpn.41. 527-528 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Tani: "Deuterium NMR studies of Benzyl Alcohol-d_5 in Poly (γ-benzyl L-glutamate) Gel" Rept.Prog.Polym.Phys.Jpn.41. 571-572 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Kawase: "Dynamics of Polyglycine I by solid state ^2H-NMR. II" Rept.Prog.Polym.Phys.Jpn.41. 573-574 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Takekawa: "Side Chain Dynamics on the surface of Bovine α-lactalbumin by solid state ^2H-NMR" Rept.Prog.Polym.Phys.Jpn.41. 579-580 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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