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Synthesis of chiral helical polymers by highly selective photocyclic aromatization(SCAT) using light as asymmetric source, and asymmetric amplification

Research Project

Project/Area Number 16K05790
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Polymer chemistry
Research InstitutionNiigata University

Principal Investigator

TERAGUCHI Masahiro  新潟大学, 自然科学系, 助教 (30334650)

Co-Investigator(Kenkyū-buntansha) 青木 俊樹  新潟大学, 自然科学系, 教授 (80212372)
金子 隆司  新潟大学, 自然科学系, 教授 (90272856)
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2016: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Keywords光学活性高分子 / らせん高分子 / らせん巻き方向選択的分解反応 / らせん選択重合 / 円偏光 / 光環化芳香族化反応 / 片巻きらせん高分子 / 環化芳香族化分解 / らせん巻方向選択的分解 / 速度論的光学分割 / 絶対不斉合成 / キラル増幅 / キラル転写 / キラル / 光環化反応 / 不斉増幅
Outline of Final Research Achievements

In this project, at first synthesis of an optically active one-handed helical polymer from a racemic helical polymer using only circularly polarized light(CPL) as an asymmetric source without using an optically active chemical substance was achieved, and then by using the obtained a one-handed helical polymer as chiral cocatalyst which was generated by CPL as an asymmetric source , we achieved helix-sense-selective polymerization(HSSP) of achiral phenylacetylene derivatives. It has been revealed that a racemic helical polymer obtained from a phenylacetylene monomer having a planar substituent such as a diphenylazomethine group is efficiently decomposed in helix-sense-selective manner by CPL irradiation to give a chiral one-handed helical polymer. In addition, using a one-handed helical polymer obtained by HSSP as a chiral cocatalyst (asymmetric source), a new one-handed helical polymer was successfully obtained by HSSP (chiral transfer).

Academic Significance and Societal Importance of the Research Achievements

人工的にキラル分子を合成する際には、キラルの源となるものがなければ、右手、左手に相当する両方のエナンチオマー(鏡像異性体)が生成する。一方、自然界に存在するアミノ酸や糖などの生体分子は一方のエナンチオマーのみからなるホモキラリティーな状態にあるが、どのようにしてホモキラリティーが生まれたかやキラルの源は何であったかについては謎であり、生命誕生の起因と並んで非常に興味がもたれている。本研究は自然界のホモキラリティーの起源やホモキラリティーに至る過程のモデルとして学術的意義があるだけでなく、光不斉反応による光学活性高分子の入手法を新たに提供でき、さらに光学分割膜といった実用への利用も容易である。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (35 results)

All 2018 2017 2016

All Journal Article (17 results) (of which Int'l Joint Research: 17 results,  Peer Reviewed: 17 results,  Open Access: 17 results) Presentation (18 results)

  • [Journal Article] Synthesis and Ultrahigh Oxygen Permeability of Silicon-containing <i>cis</i>-<i>cisoidal</i> Poly(substituted phenylacetylene)s2018

    • Author(s)
      Chenxi Xu, Toshiki Aoki, Liqun Ma, Hongge Jia, Massahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 10 Pages: 1314-1317

    • DOI

      10.1246/cl.180641

    • NAID

      130007496064

    • ISSN
      0366-7022, 1348-0715
    • Year and Date
      2018-10-05
    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] [Rh(L-alanine)(1,5-Cyclooctadiene)] Catalyzed Helix-Sense-SelectivePolymerizations of Achiral Phenylacetylenes2018

    • Author(s)
      Qingyu Wang, Hongge Jia, Yongqiang Shi, Liqun Ma, Guoxing Yang, Yazhen Wang, Shuangping Xu, Jianjun Wang, Yu Zang, Toshiki Aoki,
    • Journal Title

      Polymers

      Volume: 10(11) Issue: 11 Pages: 1223-1223

    • DOI

      10.3390/polym10111223

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis and oxygen permeability of novel graft copolymers consisting of a polyphenylacetylene backbone and long oligosiloxane grafts from phenylacetylene-type macromonomers2018

    • Author(s)
      Yu Zang, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi, Liqun Ma, Hongge Jia, Fengjuan Miao,
    • Journal Title

      Polymer

      Volume: 156 Pages: 66-70

    • DOI

      10.1016/j.polymer.2018.09.048

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Chiral Teletransmission in the Cis-cisoidal Sequence of Copoly(substituted acetylene)s by Multiple Stage Solvent Exchange of the Copolymer Solution through a Membrane2018

    • Author(s)
      Lijia Liu, Yuanyuan Gu, Yudan Wang, Toshiki Aoki*, Guan Wang, Takashi Kaneko, Masahiro Teraguchi
    • Journal Title

      Polymer

      Volume: 154 Pages: 253-257

    • DOI

      10.1016/j.polymer.2018.09.023

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Enhanced performances of enantioselective permeation through one-handed helical polymer membranes by enantioselective imine exchange reaction with permeants and by partially decomposed reaction of the membrane2018

    • Author(s)
      Yanqing Qu, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Polymer

      Volume: 156 Pages: 39-43

    • DOI

      10.1016/j.polymer.2018.09.009

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Solvent-tuned dual emission of a helical poly[3,5-bis(hydroxymethyl)phenylacetylene] connected with a π-conjugated chromophore2018

    • Author(s)
      Shi Zhichun、Kwak Giseop、Jin Young-Jae、Teraguchi Masahiro、Aoki Toshiki、Kaneko Takashi
    • Journal Title

      Polymer Journal

      Volume: 50 Issue: 7 Pages: 533-537

    • DOI

      10.1038/s41428-018-0045-7

    • NAID

      40021575871

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Ultrahigh oxygen permeability of chemically-modified membranes of novel (co)polyacetylenes having a photodegradative backbone and crosslinkable side chains2018

    • Author(s)
      Mingyu Zhang, Toshiki Aoki*, Lijia Liub, Jianjun Wang, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Polymer

      Volume: 149 Pages: 117-123

    • DOI

      10.1016/j.polymer.2018.06.075

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis of soluble oligsiloxane-end-capped hyperbranched polyazomethine and their application to CO2/N2 separation membranes2018

    • Author(s)
      Liang Xu, Tianyang Lei, Boyu Jing, Yu Zang*, Fengjuan Miao, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Des. Monomers Polym.

      Volume: 21(1) Issue: 1 Pages: 99-104

    • DOI

      10.1080/15685551.2018.1472720

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis and oxygen permeation of novel well-defined homopoly(phenylacetylene)s with different sizes and shapes of oligosiloxanyl side groups2018

    • Author(s)
      Yu Zang, Toshiki Aoki, Kazuki Shoji, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia, Fengjuan Miao
    • Journal Title

      J. Membrane. Sci.

      Volume: 561 Pages: 26-38

    • DOI

      10.1016/j.memsci.2018.04.031

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis of two well-defined quadruple-stranded copolymers having two kinds of backbones by post polymerization of a helical template polymer2017

    • Author(s)
      Yu Zang*, Toshiki Aoki*, Hiroyoki Tanagi, Kana Matsui, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia, Ken-ichi Shinohara
    • Journal Title

      Macromol. Rapid Commun.

      Volume: 39(4) Issue: 4 Pages: 1700556-1700560

    • DOI

      10.1002/marc.201700556

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Transformer of Achiral Amounts to Chirality: Double Reversal of Enantioselectivity Using a Single Cocatalyst in Asymmetric Polymerization2017

    • Author(s)
      Guanwu Yin, Geng Zhang, Toshiki Aoki,* Masahiro Teraguchi, Takashi Kaneko, Jesus Rodriguez Castanon, Masashi Shiotsuki, Fumio Sanda
    • Journal Title

      Macromolecules

      Volume: 50(19) Issue: 19 Pages: 7468-7474

    • DOI

      10.1021/acs.macromol.7b01671

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Oxygen permselectivities through supramolecular polymer membranes prepared by highly selective photocyclic aromatization of poly(substituted acetylene)2017

    • Author(s)
      Guanwu Yin, Eri Ohtaka, Toshiki Aoki, Jianjun Wang, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Polymer

      Volume: 127 Pages: 232-235

    • DOI

      10.1016/j.polymer.2017.08.066

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Subnanoporous Highly Oxygen Permselective Membranes from Poly(conjugated hyperbranched macromonomer)s Synthesized by One-pot Simultaneous Two-mode Homopolymerization of 1,3-Bis(silyl)phenylacetylene Using a Single Rh Catalytic System : Control of their Structures and Permselectivities2017

    • Author(s)
      Jianjun Wang, Jun Li, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi, Zhichun Shi, Hongge Jia
    • Journal Title

      Macromolecules

      Volume: 50(18) Issue: 18 Pages: 7121-7136

    • DOI

      10.1021/acs.macromol.7b01458

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A New Analysis Method for Quantitative Determination of Triads of Copoly(Substituted Acetylene)s’ Backbones by Highly Selective Photocyclic Aromatization2017

    • Author(s)
      Guanwu Yin, Nennei Nagaoka, Lijia Liu, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Chem. Lett.

      Volume: 46(11) Issue: 11 Pages: 1608-1611

    • DOI

      10.1246/cl.170697

    • NAID

      130006837434

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Oxygen permselectivities of novel multi-bridged copolymers synthesized by imine metathesis between N-imines and C-imines in the pendant groups of two poly(substituted acetylene)s2017

    • Author(s)
      Yinghui Lun, Yu Zang, Toshiki Aoki*, Masahiro Teraguchi, Takashi Kaneko
    • Journal Title

      Chem Lett.

      Volume: 46 Issue: 3 Pages: 401-404

    • DOI

      10.1246/cl.161104

    • NAID

      130005436585

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Helix-sense-selective Polymerization of Achiral Phenylcetylenes and Unique Properties of the Resulting Cis-cisoidal Polymers2016

    • Author(s)
      Liu Lijia*, Yu Zang*, Hongge Jia, Toshiki Aoki*, Takashi Kaneko, Shingo Hadano, Masahiro Teraguchi, Mari Miyata, Geng Zhang, Takeshi Namikoshi
    • Journal Title

      Polym. Rev.

      Volume: 56 Issue: 1 Pages: 89-118

    • DOI

      10.1080/15583724.2016.1160930

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Highly Emissive, Optically active Poly(diphenylacetylene) Having Bulky Chiral Side Group2016

    • Author(s)
      Hyojin Kim, Kyo-Un Seo, Young-Jae Jin, Chang-Lyoul Lee, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki*, Giseop Kwak*
    • Journal Title

      ACS Macro Letters

      Volume: 5 Issue: 5 Pages: 622-625

    • DOI

      10.1021/acsmacrolett.6b00184

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] タイトならせん置換ポリフェニルアセチレンよりのスターマルチストランドコポリマーの合成と酸素選択透過性2018

    • Author(s)
      大野貴也、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第67回高分子学会北陸支部研究発表会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Enantioselective permeation through one?handed helical polymer membranes improved by enantioselective imine exchange reaction with permeants and by partially decomposed reaction of the membrane2018

    • Author(s)
      Qu Yanqing、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      膜シンポジウム2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] Excellent oxygen permeability of novel silicon?containing cis?cisoidal poly (substituted phenylacetylene) membranes2018

    • Author(s)
      張明宇、徐晨曦、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      膜シンポジウム2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] ルースまたはタイトならせん置換ポリフェニルアセチレンのペンダント官能基の後重縮合によるスターマルチストランドコポリマーの合成と酸素透過性2018

    • Author(s)
      大野貴矢、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第67回高分子討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ジメシチルボリル基を側鎖に有するポリジフェニルアセチレンの合成と蛍光特性2018

    • Author(s)
      荒木大地、寺口昌宏、金子隆司、青木俊樹、ジン ヤンジェ、郭 起燮
    • Organizer
      第67回高分子討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 多分岐ポリフェニレンエチニレンとポリフェニルアセチレンとの複合膜の酸素選択透過性2018

    • Author(s)
      宮沢菜美、王 建、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      日本膜学会第40年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 定量的光環化3量体生成物による置換アセチレン重合体の構造の定量分析 (1)GPCまたはNMRによる共重合体の三連子の決定2017

    • Author(s)
      長岡年寧、尹官武、金子隆司、寺口昌宏、青木俊樹
    • Organizer
      第66回高分子学会北陸支部研究発表会
    • Related Report
      2017 Research-status Report
  • [Presentation] ラセミc-t動的らせんと片巻きc-c静的らせんの連鎖よりなるポリフェニルアセチレンブロック共重合体の調製2017

    • Author(s)
      鈴木純平、尹官武、金子隆司、寺口昌宏、青木俊樹
    • Organizer
      第66回高分子学会北陸支部研究発表会
    • Related Report
      2017 Research-status Report
  • [Presentation] シリル基含有フェニルアセチレンのペンダント末端修飾による気体選択透過性の改良2017

    • Author(s)
      宮沢菜美、王建軍、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      膜シンポジウム2017
    • Related Report
      2017 Research-status Report
  • [Presentation] 二つのN-アルケニルアミド基を持つ片巻きらせん置換ポリアセチレンのポストADMET重縮合による二重らせんポリマーの合成2017

    • Author(s)
      大友 諒平、寺口 昌宏、金子 隆司、青木俊樹
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] タイトならせんポリフェニルアセチレン膜のペンダントビニルエーテル基の分子内カチオン重合および主鎖の高選択光環化芳香族化分解による気体透過性の最適化2017

    • Author(s)
      坂田俊、浪越 毅、寺口 昌宏、金子 隆司、青木 俊樹
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 規則性ポリ置換フェニルアセチレンのペンダントビニル基のADMET重縮合の前駆体ポリマー構造による分子内・分子間制御:マルチストランドコポリマーと含環コポリマーの合成と環構造の酸素選択透過性への効果2017

    • Author(s)
      園佳央理、武尾駿、森谷まどか、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第66回高分子学会年次大会
    • Related Report
      2017 Research-status Report
  • [Presentation] 6つの水酸基と3つのビニル基を有するC3対称ベンゼン誘導体を基本構造とする異なる経路で得られた種々のADMET重縮合体による酸素選択透過性の改良2017

    • Author(s)
      武尾駿、園佳央理、森谷まどか、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第66回高分子学会年次大会
    • Related Report
      2017 Research-status Report
  • [Presentation] ペンダントに種々の縮合性官能基を有する規則性ポリ置換フェニルアセチレンよりの種々の含環ポリマー膜の気体選択透過性2017

    • Author(s)
      森谷まどか、園佳央理、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      日本膜学会第39年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 6 つの水酸基を有するC3 対称ベンゼン誘導体よりの超分子ポリマー含有高分子膜の酸素選択透過能2017

    • Author(s)
      大高絵里、武尾 駿、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      日本膜学会第39年会
    • Related Report
      2017 Research-status Report
  • [Presentation] シスシソイダルラセミらせんポリフェニルアセチレンの円偏光を用いた高選択光環化芳香族化分解(SCAT):らせん巻き方向選択的SCATの選択性と反応速度の向上2016

    • Author(s)
      宮田真理、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第65回高分子学会年次大会
    • Place of Presentation
      神戸国際会議場・展示場(兵庫県神戸市)
    • Related Report
      2016 Research-status Report
  • [Presentation] 不斉源非共存下でのアキラルアセチレンのらせん選択重合2016

    • Author(s)
      尹官武、寺口昌宏、金子隆司、青木俊樹
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学横浜キャンパス(神奈川県横浜市)
    • Related Report
      2016 Research-status Report
  • [Presentation] 円偏光を用いたシス-シソイダルラセミらせんポリ置換アセチレンのらせん巻き方向選択的光環化芳香族化分解(SCAT): らせん巻き方向選択分解の機構と選択性の向上2016

    • Author(s)
      宮田真理、寺口昌宏、金子隆司、青木 俊樹
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学横浜キャンパス(神奈川県横浜市)
    • Related Report
      2016 Research-status Report

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Published: 2016-04-21   Modified: 2020-03-30  

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