Synthesis of topological helical polymers by precise polymerization and their characterization

• Project/Area Number: 21K04685
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 26040:Structural materials and functional materials-related
• Research Institution: Kanazawa University
• Principal Investigator: 西村 達也 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: ¥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 / 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 / らせん高分子

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 Annual Research Achievements

特殊構造をもつ高分子は、物性や集合構造に特徴があるため、次世代の材料として注目を集めている。本研究では、これまでに報告例のほとんど無かったポリフェニルアセチレン類の重合の精密制御を行ない、特殊構造高分子の合成を目指している。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ため、上記の特殊構造をもつ材料の合成に非常に有利である。
最終年度に実施した研究は、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ポリマーブラシ基板の合成と、それを用いる不斉認識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った。具体的には、左巻きらせんポリマーブラシ基板の合成を行った。シリコン基板に開始剤としてフェニルボロン酸誘導体を反応させ、そこから均一な重合を行い、最大800nmの厚みのポリマーブラシ基板を合成した。また、このらせん高分子が溶媒や温度変化によって、側鎖間の水素結合をオンオフをくり返し、まるでバネが伸び縮みするような変化を示す事を見出した。興味深い事に、らせんの巻き方向によりキラルなカルボン酸と相互作用させた際に、エナンチオマーの違いを認識することも見出した。この主鎖の伸び縮みを利用した厚みの変化、および光学活性体の認識を利用した色変化について、詳細に検討した。これらの材料を用いて、新しいキラルマテリアルの開発が加速すると期待される。

Research Products

• [Int'l Joint Research] ワイズマン研究所(イスラエル)
• [Journal Article] Recovery of rhodium from glacial acetic acid manufacturing effluent using cellulose-based sorbent (2024)
  • 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
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Development of Methods for Controlled Polymerization of Monosubstituted Acetylenes Enabling Versatile Design of Polymer End Structures (2023)
  • 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
  • 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 properties (2023)
  • 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
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Revisiting the Synthesis of Cellulose Acrylate and Its Modification via Michael Addition Reactions (2023)
  • 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
  • Peer Reviewed
• [Journal Article] Low-Valent Niobium Catalysis for the Polymerization of Electron-Rich Diphenylacetylenes (2023)
  • 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
  • Peer Reviewed
• [Journal Article] Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis (2023)
  • 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
  • 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 Ability (2023)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s (2022)
  • 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
  • Peer Reviewed
• [Journal Article] Well‐Controlled Living Polymerization of N‐Propargylamides and Their Derivatives by Rhodium Catalysis (2022)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of Pentaarylcyclobutenylrhodium(I) Complexes and Their Reactivity and Initiation Mechanism in Polymerization of Monosubstituted Acetylenes (2022)
  • 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
  • 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
  • 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 microscopy (2021)
  • 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
  • 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 matrices (2021)
  • 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
  • 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 Situ (2021)
  • 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
  • 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‐Hexatrienes (2021)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Helical springs as a color indicator for determining chirality and enantiomeric excess (2021)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Highly selective and straightforward recovery of gold and platinum from acidic waste effluents using cellulose-based bio-adsorbent (2021)
  • 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
  • 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 Phenylacetylenes (2021)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Selective recovery of silver and palladium from acidic waste solutions using dithiocarbamate-functionalized cellulose (2021)
  • 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
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Development of Organic Spintronics Devices Using Precise Synthesis of Helical Poly(phenylacetylene)s (2023)
  • Author(s): Tatsuya Nishimura
  • Organizer: International Seminar “Frontiers in Chemistry-2023"
  • Int'l Joint Research / Invited