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Supermolecular Ladder Chiral Double Helical Polymer by Helix-sense-selective Polymerization Controlled by Achiral Values

Research Project

Project/Area Number 16350061
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

AOKI Toshiki  Niigata University, Institute of Science and Technology, Professor, 自然科学系, 教授 (80212372)

Co-Investigator(Kenkyū-buntansha) KANEKO Takashi  Niigata University, Institute of Science and Technology, Professor, 超域研究機構, 教授 (90272856)
寺口 昌宏  新潟大学, 自然科学系, 講師 (30334650)
金 善永  新潟大学, 超域研究機構, 特別研究員
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥14,200,000 (Direct Cost: ¥14,200,000)
Fiscal Year 2006: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2005: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2004: ¥7,800,000 (Direct Cost: ¥7,800,000)
KeywordsHelix-sense-selective Polymerization / Supermolecule / Ladder Polymer / Chiral polymer / Double Helical Polymer / Control of Polymerization / Asymmetric Recognition
Research Abstract

The investigators of this research project found an induced chirality in the main chain when a phenylacetylene having a bulky chiral substituent was polymerized. We thought this chiral structure did not contain asymmetric centers and was caused only by one-handed helical conformation. However, this chiral polymer contained two kinds of chiral structures and therefore the recognition ability and the precise structure of the chiral main chain itself could not be confirmed.
To clarify it we realized synthesis of a chiral helical polyphenylacetylene which does not have any other chiral moieties by helix-sense-selective polymerization of an achiral monomer with a chiral catalytic system. In addition, we found the helix sense can be controlled by changing not only chiral amounts but also achiral amounts. And the chiral main-chain of the resulting polymer was found to be maintained by intramolecular hydrogen bonds, i.e., this polymer has a supermolecular ladder chiral double helical polymer structure. Therefore this main chain chirality disappeared when a polar solvent was added.
In this study, we studied further the following points on the new synthetic method and the new polymer obtained by the method.
(1) Generalization of the helix-sense-selective polymerization
(2) Discussion of the mechanism of the helix-sense-selective polymerization
(3) Development of new functions of the supermolecular ladder chiral double helical polymer
(4) Discussion of the molecular structure of the supermolecular ladder chiral double helical polymer

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (23 results)

All 2007 2006 2005 2004

All Journal Article (22 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Enantioselective Permeability through Membranes from a Poly(substituted phenylacetylene) Having a Chiral Helical Backbone and Achiral Bidentate Ligands as Pendant Groups2007

    • Author(s)
      Shingo Hadano
    • Journal Title

      Chem.Lett. 36(2)

      Pages: 220-221

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective Permeability through Membranes from a Poly(substituted phenylacetylene) Having a Chiral Helical Backbone and Achiral Bidentate Ligands as Pendant Groups2007

    • Author(s)
      Shingo Hadano
    • Journal Title

      Chem.Lett. 36 (2)

      Pages: 220-221

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective Permeability through Membranes from a Poly (substituted phenylacetylene) Having a Chiral Helical Backbone and Achiral Bidentate Ligands as Pendant Groups2007

    • Author(s)
      Shingo Hadano
    • Journal Title

      Chem. Lett 36(2)

      Pages: 220-221

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis of functional π-conjugated polymers from aromatic acetylenes2006

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polymer 47(14)

      Pages: 4867-4892

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Synthesis of functional n-conjugated polymers from aromatic acetylenes2006

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polymer 47(14)

      Pages: 4867-4892

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of poly (phenylacetylene)-based polydendrons consisting of a phenyleneethynylene repeating unit, and oxygen/nitrogen permeation behavior of their membranes2006

    • Author(s)
      Takashi Kaneko
    • Journal Title

      J. Membr. Sci., 278(1-2)

      Pages: 365-372

    • Related Report
      2006 Annual Research Report
  • [Journal Article] New Macromolecular Architectures for Permselective Membranes2005

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polym. J. 37(10)

      Pages: 717-735

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Assignment of Helical Sense for Poly (phenylacetylene) Bearing Achiral Galvinoxyl Chromophore Synthesized by Helix-Sense-Selective Polymerization2005

    • Author(s)
      Takashi Kaneko
    • Journal Title

      Macromolecules 38(23)

      Pages: 9420-9426

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Chiral Helical Poly (hydroxyl-containing phenylacetylene) Membranes by In-situ Depinanylsilylation and Their Enantioselective Permeabilities2005

    • Author(s)
      Masahiro Teraguchi
    • Journal Title

      Macromolecules 38(15)

      Pages: 6367-6373

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] 主鎖のらせんのみに起因する不斉を持つポリフェニルアセチレンの合成2005

    • Author(s)
      青木俊樹
    • Journal Title

      高分子加工 54(12)

      Pages: 542-550

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Helix-Sense-Selective Polymerization of a Phenylacetylene Bearing an Achiral and Bulky Galvinoxyl Moiety2005

    • Author(s)
      Yasuhiro Umeda
    • Journal Title

      Chem.Lett. 34(6)

      Pages: 854-855

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] 主鎖のらせんのみに起因する不斉を持つポリフェニルアセチレンの合成-アキラルフェニルアセチレンのらせん選択重合とキラル置換ポリフェニルアセチレンの脱置換基-2005

    • Author(s)
      青木俊樹
    • Journal Title

      高分子加工 54(12)

      Pages: 542-550

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Helix-Sense-Selective Polymerization of a Phenylacetylene Bearing an Achiral and Bulky Galvinoxyl Moiety2005

    • Author(s)
      Yasuhiro Umeda
    • Journal Title

      Chem.Lett. 34 (6)

      Pages: 854-855

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Assignment of Helical Sense for Poly(phenylacetylene) Bearing Achiral Galvinoxyl Chromophore Synthesized by Helix-Sense-Selective Polymerization2005

    • Author(s)
      Takashi Kaneko
    • Journal Title

      Macromolecules 38(23)

      Pages: 9420-9426

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] New Macromolecular Architectures for Permselective Membranes-Gas Permselective Membranes from Dendrimers and Enantioselectively Permeable Membranes from One-handed Helical Polymers-2005

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polym.J. 37(10)

      Pages: 717-735

    • NAID

      130004769255

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] New Macromolecular Architecture for Permselective Membranes2005

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polym.J. 37(10)

      Pages: 717-735

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Synthesis of Chiral Helical Poly{p-(oligopinanylsiloxanyl)-phenylacetylene}s and Enantioselective Permeability of Their Membranes2004

    • Author(s)
      Toshiki Aoki
    • Journal Title

      J. Polym. Sci., Part A : Polym. Chem., 42

      Pages: 4502-4517

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Role of chiral amines in helix-sense-selective polymerization of a phenylacetylene using chiral amines as cocatalysts2004

    • Author(s)
      Takashi Sato
    • Journal Title

      Polymer 45(24)

      Pages: 8109-8114

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] アキラルフェニルアセチレンのらせん選択重合2004

    • Author(s)
      青木俊樹
    • Journal Title

      高分子 53(12)

      Pages: 946-946

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Chiral Helical Poly{p-(oligopinanylsiloxany1)- phenylacetylene}s and Enantioselective Permeability of Their Membranes2004

    • Author(s)
      Toshiki Aoki
    • Journal Title

      Polym.Sci., Part A : Polym.Chem. 42

      Pages: 4502-4517

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The role of chiral amines in helix-sense-selective polymerization of a phenylacetylene using chiral amines as cocatalysts2004

    • Author(s)
      Takashi Sato
    • Journal Title

      Polymer 45(24)

      Pages: 8109-8114

    • Related Report
      2004 Annual Research Report
  • [Journal Article] アキラルフェニルアセチレンのらせん選択重合-主鎖のらせんのみに起因する不斉を持つ高分子の合成-2004

    • Author(s)
      青木俊樹
    • Journal Title

      高分子 53(12)

      Pages: 946-946

    • Related Report
      2004 Annual Research Report
  • [Patent(Industrial Property Rights)] 光学分割法2007

    • Inventor(s)
      青木俊樹
    • Industrial Property Rights Holder
      新潟大学
    • Industrial Property Number
      2007-121411
    • Filing Date
      2007-05-02
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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