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分子インプリント法によるレドックス活性高分子ゲルの合成と分子認識への応用

Research Project

Project/Area Number 13128203
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionYamagata University (2003)
Nagoya University (2001-2002)

Principal Investigator

幅上 茂樹  山形大学, 工学部, 助教授 (30252266)

Co-Investigator(Kenkyū-buntansha) 波多野 豊平  山形大学, 工学部, 助手 (20333990)
中野 環  奈良先端科学技術大学, 大学院・物質創成科学研究科, 助教授 (40227856)
覚知 豊次  北海道大学, 大学院・工学研究科, 教授 (80113538)
山本 智代  名古屋大学, 大学院・工学研究科, 助手 (80314045)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥33,000,000 (Direct Cost: ¥33,000,000)
Fiscal Year 2003: ¥10,800,000 (Direct Cost: ¥10,800,000)
Fiscal Year 2002: ¥10,800,000 (Direct Cost: ¥10,800,000)
Fiscal Year 2001: ¥11,400,000 (Direct Cost: ¥11,400,000)
Keywords分子インプリント / らせん高分子 / α-(置換)アクリル酸 / 高分子ゲル / 不斉分子認識能 / 光学活性高分子 / ラジカル重合 / らせん状空孔 / 分子インプリント法 / 光学活性ポリマー / α-(アルコキシメチル)アクリル酸 / 不斉識別能 / らせん / ポリメタクリル酸エステル / 不斉アニオン重合
Research Abstract

一方向巻きのらせん構造を有するポリ(メタクリル酸エステル)誘導体をテンプレートとして用い,分子インプリント法を応用することにより,キラルならせん状空孔の形成,さらには,多様なキラル分子に対する不斉認識能を有する新規高分子ゲルの構築について検討した.これまでの研究より,共重合モノマーとしてα-(ベンジルオキシメチル)アクリル酸誘導体を用いることにより,通常分子インプリント法で用いられるメタクリル酸などに比べ,.より効果的にキラルゲルを構築できることを明らかにしている.これはテンプレートと2点で相互作用することが可能なこの2官能性モノマーの特徴的な構造に基づくものであると考えられる.そこで,実用性の観点から,市販の種々の2官能性モノマーを共重合モノマーとして用いた新規キラルゲル構築法について検討した.2官能性モノマーとしてマレイン酸誘導体などを用い,これまでに確立した方法を応用し,キラルゲルの構築を行った.その結果,いずれの場合にもほぼ定量的にゲルを合成することができた.得られたゲルの不斉認識能をtrans-スチルベンオキシド,トレガー塩基などのラセミ体を用いて不斉吸着実験による評価を行った.その結果,いずれのゲルも不斉識別能を示した.たとえばマレイン酸から得られたゲルは,特にtrans-スチルベンオキシドに対して高い不斉識別能を示し,市販の2官能性モノマーを用いた本手法が,有効であることが示された.しかし,α-(ベンジルオキシメチル)アクリル酸誘導体を用いて合成したゲルの性能には及ばず,モノマー設計がキラルらせん状空孔のより精密な構築を行う上で,非常に重要であると言える.

Report

(3 results)
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (35 results)

All Other

All Publications (35 results)

  • [Publications] S.Habaue, T.Seko, Y.Okamoto: "Copper(I)-Catalyzed Asymmetric Oxidative Coupling Polymerization of 2,3-Dihydroxynaphthalene Using Bisoxazoline Ligands"Macromolecules. 36(8). 2604-2608 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Habaue, M.Asai, M.Morita, Y.Okamoto, H.Uyama, S.Kobayashi: "Chemospecific Ring-Opening Polymerization of α-Methylenemacrolides"Polymer. 44(18). 5195-5200 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Habaue, T.Seko, M.Isonaga, H.Ajiro, Y.Okamoto: "Stereoselective Synthesis of (R,R)-, (S,S)-, and (R,S)-Poly(2,3-dihydroxy-1,4-naphthylene) Derivatives by Asymmetric Oxidative Coupling Polymerization"Polym.J.. 35(7). 592-597 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Habaue, T.Seko, Y.Okamoto: "Synthesis of Poly(1,4-naphthylene) Bearing Crown Ether Side Chain by Asymmetric Oxidative Coupling Polymerization"Polymer. 44(25). 7377-7381 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Habaue: "Catalytic Stereocontol during Radical of Acrylic Monomers"Kobunshi Ronbunshu (Special Issue). 60(8). 319-399 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Ajiro, S.Habaue, Y.Okamoto: "Anionic Polymerization of Novel Styrene Derivatives Bearing Various Amino Groups at ortho-Position"Polym.J.. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nakano, T.Yade, Y.Okamoto: "Revised Interpretation for N-Cyclohexylmalemide Polymerization in the Presence of an Optically Active Cobalt(II) Complex 1: Polymerization Mediated by Anionic Species Formed through Monomer-Co(II) Complex-O_2 Interaction"Macromolecules. 36(10). 3498-3504 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nakano, T.Yade: "Synthesis, Structure, and Photophysical and Electrochemical Properties of a-Stacked Polymer"J.Am.Chem.Soc.. 125(50). 15474-15484 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nakano, O.Nakagawa, M.Tsuji, M.Tanikawa, T.Yade, Y.Okamoto: "Poly(2,7-di-n-pentyldibenzofulvene) showing chiroptical properties in the solid state based purely on a chiral conformation"Chem.Commun.. (1). 144-145 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nakano, T.Yade, M.Yokoyama, N.Nagayama: "Charge Transport in a pi-Stacked Poly(dibenzofulvene) Film"Chem.Lett.. 33(3). 296-297 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Habaue, T.Seko, Y.Okamoto: "Asymmetric Oxidative Coupling Polymerization of Optically Active Tetrahydroxybinaphthalene Derivative"Macromolecules. 35(7). 2437-2439 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Habaue, M.Morita, Y.Okamoto: "Anionic Polymerization of Macrocyclic a-(Alkoxymethyl)acrylates Leading to Novel Vinyl Polymers with Crown Ether-type Side Chains"Macromolecules. 35(7). 2432-2434 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Habaue, M.Morita, Y.Okamoto: "Stereospecific Anionic Polymerization of a-(Alkoxymethyl)acrylate Derivatives Affording Novel Vinyl Polymers with Macrocyclic Side Chains"Polymer. 43(12). 3469-3474 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 幅上茂樹, 森田昌武, 岡本佳男: "新規ポリ(クラウンエーテル)の合成と機能"高分子論文集. 59(12). 717-724 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Habaue, T.Seko, Y.Okamoto: "Copper(I)-Catalyzed Asymmetric Oxidative Coupling Polymerization of 2,3-Dihydroxynaphthalene Using Bisoxazoline Ligands"Macromolecules. (in press).

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Satoh, H.Imai, N.Sugie, R.Nonokawa, K.Yokota, T.Kakuchi: "Bulk cyclopolymerization of 1,2:5,6-diepithio-3,4-di-O-methyl-1,2:5,6-tetradeoxy-D-mannitol with quaternary ammonium salts leading to gel-free thiosugar polymer"J.Polym.Sci., Part A : Polym.Chem.. 40(8). 965-970 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Kakuchi, M.Obata: "Synthesis and mechanism of a main-chain chiral polymer based on asymmetric cyclopolymerization"Macromol.Rapid Commun.. 23(7). 395-406 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Narumi, T.Matsuda, H.Kaga, T.Satoh, T.Kakuchi: "Synthesis of amphiphilic triblock copolymer of polystyrene and poly(4-vinylbenzyl glucoside) via TEMPO-mediated living radical polymerization"Polymer. 43(17). 3835-3840 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Kusuno, M.Mori, T.Satoh, M.Miura, H.Kaga, T.Kakuchi: "Enantioseparation property of (1→6)-α-D-glucopyranan and (1→6)-α-D-mannopyranan tris(phenylcarbamate)s as chiral stationary phases in HPLC"Chirality. 14(6). 498-502 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Imai, K.Hayakawa, T.Satoh, H.Kaga, T.Kakuchi: "Enantiomer-selective polymerization of (RS)-(phenoxymethyl)thiirane with diethylzinc/L-amino acid"J.Polym.Sci., Part A : Polym.Chem.. 40(20). 3443-3448 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tsuji, R.Sakai, T.Satoh, H.Kaga, T.Kakuchi: "Enantiomer-selective radical cyclopolymerization of rac-2,4-pentanediyl dimethacrylate using ATRP initiating system with chiral amine ligand"Macromolecules. 35(22). 8255-8257 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tsuji, R.Sakai, T.Satoh, H.Kaga, T.Kakuchi: "Enantiomer-selective radical cyclopolymerization of rac-2,4-pentanediyl dimethacrylate using by 2,2'-azobisisobutyronitrile/copper(II) trifluoromethanesulfonare/chiral diamine as asymmetric reverse atom transfer radical polymerization initiating system"Polym.J.. 35(1). 84-87 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Sugimoto, A.Narumi, T.Satoh, H.Kaga, T.Kakuchi: "A convenient synthesis of functionalized alkoxyamines as initiators for living free radical polymerization"Polym.Bull.. 49(5). 337-340 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Nakano, O.Nakagawa, T.Yade, Y.Okamoto: "Solid-State Polymerization of Dibenzofulvene Leading to a Copolymer with Oxygen"Macromolecules. (in press).

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Kubota, C.Yamamoto, Y.Okamoto: "Preparation of Chiral Stationary Phase for HPLC Based on Immobilization of Cellulose 3,5-Dimethyilphenylcarbamate Derivatives on Silica Gel"Chirality. 15(1). 77-82 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Habaue, O.Ikeshima, H.Ajiro, Y.Okamoto: "Surface Structure Control of Macroporous Silica Gel by Atom Transfer Radical Polymerization"Polym.J.. 33・11. 902-905 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Habaue, M.Morita, Y.Okamoto: "Anionic Polymerization of Macrocyclic α-(Alkoxymethyl)acrylates Leading to Novel Vinyl Polymers with Crown Ether-type Side Chains"Macromolecules. 35(in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Habaue, T.Seko, Y.Okamoto: "Asymmetric Oxidative Coupling Polymerization of Optically Active Tetrahydroxybinaphthalene Derivative"Macromolecules. 35(in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Habaue, M.Morita, Y.Okamoto: "Stereospecific Anionic Polymerization of α-(Alkoxymethyl)acrylate Derivatives Affording Novel Vinyl Polymers with Macrocyclic Side Chains"Polymer. 43(in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Nakano: "Optically Active Synthetic Polymers as Chiral Stationary Phases in HPLC"J.Chromatogr.A. 906. 205-225 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Nakano, Y.Okamoto: "Helical Polymers : Synthesis, Conformation, and Function"Chem.Rev.. 101. 4013-4038 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 中野 環: "不斉ラジカル重合(Asymmetric Radical Polymerization)"高分子論文集. 58・8. 411-426 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Nakano, K.Tsunematsu, Y.Okamoto: "Synthesis of Single-Handed Helical Poly(1-dibenzosuberyl methacrylate) via Radical Polymerization in the Presence of an Optically Active Cobalt(II) Complex"Chem.Lett.. 42-43 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Kubota, T.Kusano, C.Yamamoto, E.Yashima, Y.Okamoto: "Cellulose 3,5-Dimethylphenylcarbamate Immobilized onto Silica Gel via Copolymerization with a Vinyl Monomer and Its Chiral Recognition Ability as a Chiral Stationary Phase for HPLC"Chem. Lett.. 724-725 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Wakita, B.Chankvetadze, C.Yamamoto, Y.Okamoto: "Chromatographic Enantioseparation on a Wall-coated Open Tubular Capillary Column Containing Covalently Bound Cellulose (3,5-Dichlorophenylcarbamate) as Chiral Selector"J.Sep.Sci.. 25. 167-169 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2018-03-28  

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