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特異な高次構造を持つ超分子ポリマーの設計と創製

Research Project

Project/Area Number 17J02520
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Nanostructural chemistry
Research InstitutionChiba University

Principal Investigator

新津 敬介  千葉大学, 融合理工学府, 特別研究員(DC1)

Project Period (FY) 2017-04-26 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2019: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2018: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2017: ¥1,000,000 (Direct Cost: ¥1,000,000)
Keywords超分子ポリマー / 超分子重合 / 分子認識 / 水素結合 / 環構造 / らせん構造 / 螺旋構造 / π共役 / 自己集合 / 超分子集合体 / 相補的水素結合 / ナフタレン
Outline of Annual Research Achievements

本研究は”特異な高次構造を持つ超分子ポリマーの設計と創製”を基盤とし、革新的な新現象の開拓を目的としている。本研究のモノマーの基本骨格は、芳香族部位に水素結合部位と長鎖アルキル鎖を導入した分子である。これまでに、コア部位にナフタレンを導入した脂溶性ナフタレンモノマーが環状超分子ポリマーを形成することが明らかとなっていた。昨年度は、芳香族部位に光応答性分子やナフタレンからπ共役系をより拡張した分子の超分子ポリマーの構造および特性を精査した。また、2種類の分子を混合したときの超分子重合過程についても調査してきた。
本年度は、長鎖アルキル鎖とπ共役系の結合部位に注目した。この結合部位へ電子求引性部位を導入し、これまでの超分子ポリマーと比較して、その影響を調査した。芳香族部位がアゾベンゼンの分子は、電子求引性基を導入することで、ランダムコイル状超分子ポリマーを形成し、熱をかけることでらせん状結晶へ相転移した。また、芳香族部位がナフタレンの場合はファイバー状超分子ポリマーを与えた。さらに、時間経過とともに分子間相互作用部位が組み替わり、これによって熱力学的に安定な結晶へ構造転移することが明らかとなった。これらの結果から、電子求引性基を導入した分子は、速度論的に超分子ポリマーを形成し、最終的に熱力学的に安定な結晶構造を形成することが明らかになった。
単一分子の調査で、電子求引性基を導入により芳香族部位が電子不足状態になっていたため、電子求引性基の有無での分子認識が起きることを期待した。そこで、電子求引性基の有無が異なる上記の2種類のナフタレン分子を混合した。すると、速度論的にアモルファス構造を形成し、時間経過とともに静電相互作用で単一分子では観察されないらせん状超分子ポリマーを形成した。さらに、このらせん構造は熱によってある温度で素早く崩壊することが明らかとなった。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Report

(3 results)
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • Research Products

    (26 results)

All 2020 2019 2018 2017 Other

All Int'l Joint Research (5 results) Journal Article (10 results) (of which Int'l Joint Research: 7 results,  Peer Reviewed: 10 results,  Open Access: 3 results) Presentation (8 results) (of which Int'l Joint Research: 5 results) Book (1 results) Remarks (2 results)

  • [Int'l Joint Research] キール大学(英国)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] ドイツ連邦材料試験所(ドイツ)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] フランス国立科学研究センター(フランス)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] キール大学(英国)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] サクレー研究所(フランス)

    • Related Report
      2017 Annual Research Report
  • [Journal Article] Effect of Solvent on the Thermodynamic Stability of Toroidal Supramolecular Polymers2020

    • Author(s)
      Aratsu Keisuke、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Yagai Shiki
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 2 Pages: 178-181

    • DOI

      10.1246/cl.190789

    • NAID

      130007795160

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen bond-directed supramolecular polymorphism leading to soft and hard molecular ordering2020

    • Author(s)
      Aizawa Takumi、Aratsu Keisuke、Datta Sougata、Mashimo Takaki、Seki Tomohiro、Kajitani Takashi、Silly Fabien、Yagai Shiki
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 31 Pages: 4280-4283

    • DOI

      10.1039/d0cc01636e

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Supramolecular copolymerization driven by integrative self-sorting of hydrogen-bonded rosettes2020

    • Author(s)
      Aratsu Keisuke、Takeya Rika、Pauw Brian R.、Hollamby Martin J.、Kitamoto Yuichi、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Yagai Shiki
    • Journal Title

      Nature Communications

      Volume: 11 Issue: 1 Pages: 1623-1623

    • DOI

      10.1038/s41467-020-15422-6

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Self‐Sorting of Rosette‐Forming Naphthalene Barbiturates into Distinct Toroidal Assemblies2019

    • Author(s)
      Aratsu Keisuke、Yagai Shiki
    • Journal Title

      ChemPlusChem

      Volume: 84 Issue: 6 Pages: 619-622

    • DOI

      10.1002/cplu.201900044

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Topological Impact on the Kinetic Stability of Supramolecular Polymers2019

    • Author(s)
      Suzuki Atsuhito、Aratsu Keisuke、Datta Sougata、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Hollamby Martin、Silly Fabien、Yagai Shiki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 33 Pages: 13196-13202

    • DOI

      10.1021/jacs.9b06029

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Photoresponsive Circular Supramolecular Polymers: A Topological Trap and Photoinduced Ring-Opening Elongation2019

    • Author(s)
      Bimalendu Adhikari、Keisuke Aratsu、Joyal Davis、Shiki Yagai
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 12 Pages: 3764-3768

    • DOI

      10.1002/anie.201811237

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Self-folding of supramolecular polymers into bioinspired topology2018

    • Author(s)
      Prabhu Deepak D.、Aratsu Keisuke、Kitamoto Yuichi、Ouchi Hayato、Ohba Tomonori、Hollamby Martin J.、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Yagai Shiki
    • Journal Title

      Science Advances

      Volume: 4 Issue: 9 Pages: 8466-8466

    • DOI

      10.1126/sciadv.aat8466

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Two-Dimensional Chiral Self-Assembly of Barbituric Acid-Functionalized Naphthelene Derivatives2018

    • Author(s)
      Fabien Silly, Keisuke Aratsu, Shiki Yagai
    • Journal Title

      Journal of Physical Chemistry C

      Volume: 122 Issue: 11 Pages: 6412-6416

    • DOI

      10.1021/acs.jpcc.7b12460

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Light-induced unfolding and refolding of supramolecular polymer nanofibers2017

    • Author(s)
      Bimalendu Adhikari, Yuki Yamada, Mitsuaki Yamauchi, Kengo Wakita, Xu Lin, Keisuke Aratsu, Tomonori Ohba, Takashi Karatsu, Martin Hollamby, Nobutaka Shimizu, Hideaki Takagi, Rie Haruki, Shin-ichi Adachi, Shiki Yagai
    • Journal Title

      Nature Communications

      Volume: 8 Issue: 1 Pages: 15254-15254

    • DOI

      10.1038/ncomms15254

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Hydrogen-bonded rosettes comprising π-conjugated systems as building blocks for functional one-dimensional assemblies2017

    • Author(s)
      Bimalendu Adhikari, Xu Lin, Mitsuaki Yamauchi, Hayato Ouchi, Keisuke Aratsu, Shiki Yagai
    • Journal Title

      Chemical Communications

      Volume: 53 Issue: 70 Pages: 9663-9683

    • DOI

      10.1039/c7cc04172a

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] Induction of Chirality in Helical Supramolecular Copolymers2018

    • Author(s)
      新津 敬介、竹谷 梨佳 、矢貝 史樹
    • Organizer
      Molecular Chirality 2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 分子認識による高次螺旋超分子コポリマーの創製2018

    • Author(s)
      新津 敬介、竹谷 梨佳 、矢貝 史樹
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] Realization of Helically Folded Supramolecular Copolymer through Molecular Recognition2018

    • Author(s)
      Keisuke Aratsu 、Rika Takeya 、Shiki Yagai
    • Organizer
      10th Singapore International Chemistry Conference
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Transformation from Amorphous into Helical Supramolecular Coaggregates through Molecular Recognition2018

    • Author(s)
      Keisuke Aratsu, Shiki Yagai
    • Organizer
      CEMSuptra 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Transformation of amorphous into helical supramolecular co-aggregates through molecular recognition2018

    • Author(s)
      Keisuke Aratsu, Shiki Yagai
    • Organizer
      The Second Symposium of Chiral Molecular Science and Technology
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Emergence of Helical Supramolecular Copolymers through Molecular Recognition2018

    • Author(s)
      新津敬介、矢貝史樹
    • Organizer
      日本化学会第98春季年会2018
    • Related Report
      2017 Annual Research Report
  • [Presentation] Thermodynamically Stable Helical Supramolecular Copolymers2017

    • Author(s)
      Keisuke Aratsu, Shiki Yagai
    • Organizer
      IUMRS-ICAM2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Transformation from amorphous to helical supramolecular Co-aggregates through molecular recognition2017

    • Author(s)
      Keisuke Aratsu, Shiki Yagai
    • Organizer
      ICON2-2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Book] Photoactive Functional Soft Materials: Preparation, Properties, and Applications2019

    • Author(s)
      Yuichi Kitamoto 、Keisuke Aratsu、Shiki Yagai
    • Total Pages
      40
    • Publisher
      Wiley
    • ISBN
      9783527344826
    • Related Report
      2018 Annual Research Report
  • [Remarks] 分子集合体化学研究室

    • URL

      http://chem.tf.chiba-u.jp/yagai/publications.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 分子集合体化学研究室

    • URL

      http://chem.tf.chiba-u.jp/yagai/index.html

    • Related Report
      2017 Annual Research Report

URL: 

Published: 2017-05-25   Modified: 2024-03-26  

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