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Synthesis of topological helical polymers by precise polymerization and their characterization

Research Project

Project/Area Number 21K04685
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 26040:Structural materials and functional materials-related
Research InstitutionKanazawa University

Principal Investigator

Nishimura Tatsuya  金沢大学, 物質化学系, 准教授 (00436528)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2023: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2022: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2021: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsリビング重合 / らせん高分子 / ポリフェニルアセチレン / 特殊構造高分子 / ボトルブラシポリマー / スターポリマー
Outline of Research at the Start

特殊構造をもつ高分子の合成は、重合反応の簡便かつ精密な制御が必須である。これまではリビングラジカル重合が主に用いられていたため、らせん高分子による特殊構造高分子の報告例はかなり限られている。我々が開発したポリアセチレン類のリビング重合は簡便かつ安定な原料を混ぜるだけで重合し、ほぼすべての官能基を両末端に導入する事ができる。本研究は、この新しいリビング重合方法を駆使してらせん高分子からなる特殊構造高分子の合成と、それを用いる不斉触媒および光学分割カラムの固定相などのキラルマテリアルの開発を行う。具体的には、スターポリマーとボトルブラシポリマーの合成を行い、キラルマテリアルへの応用を検討する。

Outline of Final Research Achievements

Living polymerisation of helical polymers was used to synthesise polymeric materials with distinctive structures, such as cyclic, brush and Janus polymers. The resulting brush polymers and bottle brush polymers were useful as chiral materials such as optical resolution materials. Furthermore, star polymers consisting of three poly(phenylacetylene) chains with precisely controlled chain lengths were synthesised through living polymerisation of phenylacetylene derivatives using a Rh-based multi-component catalyst system. The structure-function relationship of these star polymers was also explored. The resulting star polymers were thoroughly characterised using various spectroscopic techniques and their star-shaped structures were clearly visualised using atomic force microscopy (AFM).

Academic Significance and Societal Importance of the Research Achievements

本研究は最近我々が開発した新規重合触媒システムを駆使し、環状・表面ブラシ・ボトルブラシ・ヤヌス高分子を合成した。本研究成果の学術的意義は、材料科学およびナノテクノロジーに応用できる動的なヘリカル高分子からなるトポロジー的にユニークなスターポリマーの開発に貢献した。特にこの研究で新しく合成可能となるスターポリマーは機能材料の設計および合成に役立ち、社会に有用な特殊な潤滑剤やキラルマテリアルの応用に貢献すると期待される。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • Research Products

    (21 results)

All 2024 2023 2022 2021 Other

All Int'l Joint Research (1 results) Journal Article (19 results) (of which Int'l Joint Research: 7 results,  Peer Reviewed: 19 results,  Open Access: 12 results) Presentation (1 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results)

  • [Int'l Joint Research] ワイズマン研究所(イスラエル)

    • Related Report
      2021 Research-status Report
  • [Journal Article] Recovery of rhodium from glacial acetic acid manufacturing effluent using cellulose-based sorbent2024

    • Author(s)
      Biswas Foni B.、Endo Masaru、Rahman Shafiqur、Rahman Ismail M.M.、Nakakubo Keisuke、Mashio Asami S.、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro、Hasegawa Hiroshi
    • Journal Title

      Separation and Purification Technology

      Volume: 328 Pages: 124995-124995

    • DOI

      10.1016/j.seppur.2023.124995

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Development of Methods for Controlled Polymerization of Monosubstituted Acetylenes Enabling Versatile Design of Polymer End Structures2023

    • Author(s)
      Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 81 Issue: 6 Pages: 594-606

    • DOI

      10.5059/yukigoseikyokaishi.81.594

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2023-06-01
    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of optically active star polymers consisting of helical poly(phenylacetylene) chains by the living polymerization of phenylacetylenes and their chiroptical properties2023

    • Author(s)
      Inaba Ayato、Nishimura Tatsuya、Yamamoto Masato、Das Sandip、Yurtsever Ayhan、Miyata Kazuki、Fukuma Takeshi、Kawaguchi Seigo、Kikuchi Moriya、Taniguchi Tsuyoshi、Maeda Katsuhiro
    • Journal Title

      RSC Advances

      Volume: 13 Issue: 44 Pages: 30978-30984

    • DOI

      10.1039/d3ra05971e

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Revisiting the Synthesis of Cellulose Acrylate and Its Modification via Michael Addition Reactions2023

    • Author(s)
      Okamoto Hiroya、Taniguchi Tsuyoshi、Takekuma Motohiro、Mashio Asami S.、Wong Kuo H.、Hasegawa Hiroshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Biomacromolecules

      Volume: 24 Issue: 8 Pages: 3767-3774

    • DOI

      10.1021/acs.biomac.3c00436

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Low-Valent Niobium Catalysis for the Polymerization of Electron-Rich Diphenylacetylenes2023

    • Author(s)
      Nakaguchi Daisuke、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Macromolecules

      Volume: 56 Issue: 15 Pages: 5873-5880

    • DOI

      10.1021/acs.macromol.3c00740

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis2023

    • Author(s)
      Miyairi Mami、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 37 Pages: 2331-2344

    • DOI

      10.1002/anie.202302332

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of an Immobilized Three-state Switchable Chiral Stationary Phase for HPLC Using a Metal Cation-responsive Optically Active Poly(phenylacetylene) Derivative and Its Chiral Recognition Ability2023

    • Author(s)
      Fukuda Mayu、Nishimura Tatsuya、Hirose Daisuke、Maeda Katsuhiro
    • Journal Title

      Chemistry Letters

      Volume: 52 Issue: 3 Pages: 136-139

    • DOI

      10.1246/cl.220518

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s2022

    • Author(s)
      Echizen Kensuke、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 26 Pages: 2676-2686

    • DOI

      10.1002/anie.202202676

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Well‐Controlled Living Polymerization of N‐Propargylamides and Their Derivatives by Rhodium Catalysis2022

    • Author(s)
      Ito Kosuke、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 17

    • DOI

      10.1002/anie.202117234

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of Pentaarylcyclobutenylrhodium(I) Complexes and Their Reactivity and Initiation Mechanism in Polymerization of Monosubstituted Acetylenes2022

    • Author(s)
      Sakamoto Shiori、Taniguchi Tsuyoshi、Sakata Yoko、Akine Shigehisa、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Organometallics

      Volume: 41 Issue: 4 Pages: 472-479

    • DOI

      10.1021/acs.organomet.1c00712

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Speciation analysis of inorganic selenium in wastewater using a highly selective cellulose-based adsorbent via liquid electrode plasma optical emission spectrometry,2022

    • Author(s)
      K.Nakakubo, T. Nishimura, F.B. Biswas, M. Endo, K. H. Wong, A. S. Mashio, T. Taniguchi, T. Nishimura, K. Maeda, H. Hasegawa
    • Journal Title

      J. Hazard. Mater.

      Volume: 424 Pages: 127250-127250

    • DOI

      10.1016/j.jhazmat.2021.127250

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Visualisation of helical structures of poly(diphenylacetylene)s bearing chiral amide pendants by atomic force microscopy2021

    • Author(s)
      A. Yurtsever, S. Das, T. Nishimura, R. Rodriguez, D. Hirose, K. Miyata, A. Sumino, T. Fukuma, K. Maeda
    • Journal Title

      Chemical Communications

      Volume: 57(92) Issue: 92 Pages: 12266-12269

    • DOI

      10.1039/d1cc05341h

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Comparative evaluation of dithiocarbamate-modified cellulose and commercial resins for the recovery of precious metals from aqueous matrices2021

    • Author(s)
      F.B. Biswas, I.M.M. Rahman, K.Nakakubo, K. Yunoshita, M. Endo, A. S. Mashio, T. Taniguchi, T. Nishimura, K. Maeda, H. Hasegawa
    • Journal Title

      J. Hazard. Mater.

      Volume: 418 Pages: 126308-126308

    • DOI

      10.1016/j.jhazmat.2021.126308

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Understanding the Polymerization of Diphenylacetylenes with Tantalum(V) Chloride and Cocatalysts: Production of Cyclic Poly(diphenylacetylene)s by Low-Valent Tantalum Species Generated in Situ2021

    • Author(s)
      Sueyoshi Shingyo、Taniguchi Tsuyoshi、Tanaka Saki、Asakawa Hitoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 39 Pages: 16136-16146

    • DOI

      10.1021/jacs.1c06811

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Rhodium(I) Complexes Bearing an Aryl‐Substituted 1,3,5‐Hexatriene Chain: Catalysts for Living Polymerization of Phenylacetylene and Potential Helical Chirality of 1,3,5‐Hexatrienes2021

    • Author(s)
      Sakamoto Shiori、Taniguchi Tsuyoshi、Sakata Yoko、Akine Shigehisa、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 41 Pages: 22201-22206

    • DOI

      10.1002/anie.202108032

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Helical springs as a color indicator for determining chirality and enantiomeric excess2021

    • Author(s)
      Maeda Katsuhiro、Hirose Daisuke、Nozaki Mai、Shimizu Yoichi、Mori Taro、Yamanaka Kentaro、Ogino Koji、Nishimura Tatsuya、Taniguchi Tsuyoshi、Moro Munetsugu、Yashima Eiji
    • Journal Title

      Science Advances

      Volume: 7 Issue: 27 Pages: 5381-5389

    • DOI

      10.1126/sciadv.abg5381

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Highly selective and straightforward recovery of gold and platinum from acidic waste effluents using cellulose-based bio-adsorbent2021

    • Author(s)
      F.B. Biswas, I.M.M. Rahman, K.Nakakubo, K. Yunoshita, M. Endo, K. Nagai, A. S. Mashio, T. Taniguchi, T. Nishimura, K. Maeda, H. Hasegawa
    • Journal Title

      J. Hazard. Mater.

      Volume: 410 Pages: 124569-124569

    • DOI

      10.1016/j.jhazmat.2020.124569

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis of Stereoregular Telechelic Poly(phenylacetylene)s: Facile Terminal Chain-End Functionalization of Poly(phenylacetylene)s by Terminative Coupling with Acrylates and Acrylamides in Rhodium-Catalyzed Living Polymerization of Phenylacetylenes2021

    • Author(s)
      Echizen Kensuke、Taniguchi Tsuyoshi、Nishimura Tatsuya、Maeda Katsuhiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 9 Pages: 3604-3612

    • DOI

      10.1021/jacs.1c00150

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Selective recovery of silver and palladium from acidic waste solutions using dithiocarbamate-functionalized cellulose2021

    • Author(s)
      F.B. Biswas, I.M.M. Rahman, K.Nakakubo, K. Yunoshita, M. Endo, K. Nagai, A. S. Mashio, T. Taniguchi, T. Nishimura, K. Maeda, H. Hasegawa
    • Journal Title

      Chem. Eng. J.

      Volume: 407 Pages: 127225-127225

    • DOI

      10.1016/j.cej.2020.127225

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Development of Organic Spintronics Devices Using Precise Synthesis of Helical Poly(phenylacetylene)s2023

    • Author(s)
      Tatsuya Nishimura
    • Organizer
      International Seminar “Frontiers in Chemistry-2023"
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited

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Published: 2021-04-28   Modified: 2025-01-30  

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