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2011 Fiscal Year Annual Research Report

異方性ハイブリッドゲル薄膜を有機相とする高次機能化HPLC分離剤の開拓

Research Project

Project/Area Number 23245018
Research Category

Grant-in-Aid for Scientific Research (A)

Research InstitutionKumamoto University

Principal Investigator

伊原 博隆  熊本大学, 自然科学研究科, 教授 (10151648)

Co-Investigator(Kenkyū-buntansha) 高藤 誠  熊本大学, 自然科学研究科, 准教授 (50332086)
澤田 剛  熊本大学, 自然科学研究科, 准教授 (90240902)
冨永 昌人  熊本大学, 自然科学研究科, 准教授 (70264207)
ガナパシー ヒュラシー  熊本大学, 大学院・先導機構, 特任助教 (90551276)
Keywords自己組織化 / 分子認識 / 超薄膜 / 界面・界面物性 / 液体クロマトグラフィ
Research Abstract

本研究は、微細構造が物理的細孔および化学吸着相によって精密に制御された微粒子剤を構築することによって、高い選択性を示すHPLC用分離剤の開発を目指している。これらの目標・目的を達成するために、(1)球状微粒子の物理界面機能の増幅や変換を通じた機能創出と、(2)ポリマー主鎖上に一次元的に官能基を集積する有機相の開発の2つのアプローチを設計し、研究を進めている。(1)については、申請者らがすでに確立しているSelf-assembing重合法を改良して、ナノサイズのコロイダルシリカをコア細孔内に封入した複合粒子の作製に着手し、初期目標を達成した。一方(2)については、ゲスト分子との相互作用の起点となる官能基を集積し、多重相互作用によって選択性を高める手法を採用した。具体的には、カルボニル基やその他の極性基を弱い相互作用点として選定し、これらを交互共重合あるいはイオン液体性のモノマーによる重合によってポリマー鎖上に集積する手法を試みた。これらのポリマーをグラフト化した微粒子剤をカラムに充填し、選択性について評価したところ、交互共重合成分に、申請者らが独自に開発したグルタミド系分子ゲル素子を導入したものは、芳香族性分子に対して著しく高い分子形状識別能を示した。この特性を利用して分離が難しいとされるビタミンE類の選択分離を試みたところ、β体とγ体の分離係数は(ベースライン分離が可能な)世界最高値に達した。また、イオン液体性のモノマーからなる重合物の場合は、グラフト化後に対アニオンをπ共役系有機素子に変換することが可能であり、これによって選択性の向上がみられるだけでなく、対アニオンの化学構造を選択することによってHPLCにおける選択性が制御できることを確認した。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

本研究は、物理細孔と化学吸着相の2つの視点から微細構造を制御し、高選択的なHPLC用分離剤を開発することを目標としている。当初の予定通り、前者においては、コロイダルシリカを粒子コア内に導入することに成功しており、後者においては、交互共重法あるいはイオン液体様のポリマー鎖を適用することにより、きわめて高い選択性が達成されている。なお、関連する発表論文数については、当初目標を大きく上回る7報に至っている。

Strategy for Future Research Activity

とくに研究計画の大きな見直しはないが、細孔内におけるコロイダルシリカ粒子の充填密度の制御、ならびに化学吸着サイトとなるポリマー鎖の充填密度の向上を目標の一つに置きながら、引き続き微粒子剤の微細構造の制御ならびに高選択的なHPLC分離剤の開発を目指す。

  • Research Products

    (30 results)

All 2012 2011 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results) Presentation (17 results) Book (4 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Molecular-shape selective HPLC : Stabilization effect of polymer main chain by alternating copolymerization2012

    • Author(s)
      A.K.Mallik,H.Qiu, T.Sawada, M.Takafuji, H.Ihara
    • Journal Title

      Journal of Chromatography A

      Volume: 1232 Pages: 183-189

    • DOI

      10.1016/j.chroma.2011.11.061

    • Peer Reviewed
  • [Journal Article] Enhancement of molecular shape-selectivity by in-tube anion-exchange in poly (octadecylimidazolium) silica column for reversed-phase chromatography2012

    • Author(s)
      H.Qiu, A.K.Mallik, M.Takafuji, X.Liu, S.Jiang, H.Ihara
    • Journal Title

      Journal of Chromatography A

      Volume: 1232 Pages: 116-122

    • DOI

      10.1016/j.chroma.2011.10.065

    • Peer Reviewed
  • [Journal Article] High molecular-shape selectivity by molecular gel-forming compounds : Bioactive and shape-constrained isomers through the integration and orientation of weak interaction sites2011

    • Author(s)
      A.K.Mallik, H.Qiu, M.Takafuji, H.Ihara
    • Journal Title

      Chemical Communication

      Volume: 47 Pages: 10341-10343

    • DOI

      10.1039/C1CC13397G

    • Peer Reviewed
  • [Journal Article] A facile and specific approach to new liquid chromatography adsorbents obtained by ionic self-assembly2011

    • Author(s)
      H.Qiu, A.K.Mallik, M.Takafuji, H.Ihara
    • Journal Title

      Chemistry : A European Journal

      Volume: 17 Pages: 7288-7297

    • DOI

      10.1002/chem.201100137

    • Peer Reviewed
  • [Journal Article] Preparation of multilayered organic-inorganic hybrid core-shell particles by stepwise surface formation2011

    • Author(s)
      T.Wakiya T.Morisaki, N.Ishibashi, S.Nishimura, M.Takafuji, S.Nagaoka, Y.Yamada, S.Nozato, H.Ihara
    • Journal Title

      Materials Letters

      Volume: 65 Pages: 1407-1409

    • DOI

      10.1016/j.matlet.2011.02.015

    • Peer Reviewed
  • [Journal Article] Facile and versatile method for preparing core-shell microspheres with controlled surface structures based on silica particles-monolayer2011

    • Author(s)
      A.Uchimura, S.Kubota, S.Yamada, T.Wakiya, M.Takafuji, T.Shirosaki, S.Nagaoka, H.Ihara
    • Journal Title

      Materials Chemistry and Physics

      Volume: 129 Pages: 871-880

    • DOI

      10.1016/j.matchemphys.2011.05.029

    • Peer Reviewed
  • [Journal Article] Strategic achievement for the baseline separation of tocopherol isomers by integration of weak interaction sites on alternating copolymer2011

    • Author(s)
      A.K.Mallik, H.Qiu, M.Takafuji, H.Ihara
    • Journal Title

      Analytical Methods

      Volume: 3 Pages: 1277-1279

    • DOI

      10.1039/clay05198a

    • Peer Reviewed
  • [Presentation] Poly(octadecylimidazolium)-Silica Hybrid Materials for HPLC2011

    • Author(s)
      Hongdeng Qiu, Abul K.Mallik, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      Pusan-Gyeognam/Kyushu-Seibu Joint Symposium On High Polymaers (15th) and Fibers (13th)
    • Place of Presentation
      Pusan, Korea
    • Year and Date
      20111027-20111029
  • [Presentation] Alternating Copolymer-Grafted Silica : A High-Selective Liquid Chromatographic Stationary Phase for the Separation of Shape-Constrained Isomers2011

    • Author(s)
      Abul K.Mallik, Tsuyoshi Sawada, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      Pusan-Gyeognam/Kyushu-Seibu Joint Symposium On High Polymaers (15th) and Fibers (13th)
    • Place of Presentation
      Pusan, Korea
    • Year and Date
      20111027-20111029
  • [Presentation] Development of Silica-Confined Ionic Liquid Stationary Phases for High-Performance Liquid Chromatography2011

    • Author(s)
      Hongdeng Qiu, Abul K.Mallik, Makoto Takafuji, Shengxiang Jiang, Hirotaka Ihara
    • Organizer
      37th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Dalian, China
    • Year and Date
      20111008-20111011
  • [Presentation] Separation of Bioactive- and Shape-Constrained Isomers by Molecular Gel Forming Compounds-Grafted Silica in RP-HPLC2011

    • Author(s)
      Abul K.Mallik, Hongdeng Qiu, Tsuyoshi Sawada, Makoto Takafuj, Hirotaka Ihara
    • Organizer
      37th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Dalian, China
    • Year and Date
      20111008-20111011
  • [Presentation] マルチレイヤー構造をもつコアシェル粒子の作製2011

    • Author(s)
      森崎剛史、脇屋武司、高藤誠、伊原博隆
    • Organizer
      第60回高分子討論会
    • Place of Presentation
      名古屋工業大学、岡山
    • Year and Date
      20110928-20110930
  • [Presentation] 界面自己組織化ナノ粒子をシェルとするコア・シェルハイブリッド微粒子の作製2011

    • Author(s)
      伊原博隆、高藤誠
    • Organizer
      第60回高分子討論会
    • Place of Presentation
      名古屋工業大学、岡山
    • Year and Date
      20110928-20110930
  • [Presentation] Polymeric Ionic Liquid-immobilized Silica for High Molecular Shape-Selective HPLC2011

    • Author(s)
      Kaori Shingo, Hongdeng Qiu, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      3rd Asian Symposium on Advanced Materials
    • Place of Presentation
      Kyushu University Fukuoka, Japan
    • Year and Date
      20110919-20110922
  • [Presentation] Core-Shell Hybrid Particles with Controlled Shell Thicknessby Using Nanoparticle Adsorption2011

    • Author(s)
      Tsuyoshi Morisaki, Takeshi Wakiya, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      3rd Asian Symposium on Advanced Materials
    • Place of Presentation
      Kyushu University Fukuoka, Japan
    • Year and Date
      20110919-20110922
  • [Presentation] Ultra-High-Selective HPLC Packing Materials from Ionic Self-Assembly of Azobenzene Dye with Poly(Ionic Liquid)-Modified Silica2011

    • Author(s)
      Hongdeng Qiu, Abul K.Mallik, Makoto Takafuji, Shengxiang Jiang, Hirotaka Ihara
    • Organizer
      36th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Budapest, Hungary
    • Year and Date
      20110619-20110623
  • [Presentation] New approach for high integration of weak interaction sites for selectivity enhancement in HPLC : Synthesis of new monomers and their alternating copolymerization on silica2011

    • Author(s)
      Abul K.Mallik, Hondeng Qiu, Tsuyoshi Sawada, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      36th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Budapest, Hungary
    • Year and Date
      20110619-20110623
  • [Presentation] New proposal of hydrophilic but nonionic polymer phase for high-selective normal phase liquid chromatography2011

    • Author(s)
      Abul K.Mallik, Kaori Shingo, Aika Ezaki, Tsuyoshi Sawada, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      36th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Budapest, Hungary
    • Year and Date
      20110619-20110623
  • [Presentation] High-Density Grafting of Polymer Brushes on Silica Particles under Supercritical CO2 and their Application in RP-HPLC2011

    • Author(s)
      H.S.Ganapathy, M.Doi, M.Takafuji, H.Ihara
    • Organizer
      36th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Budapest, Hungary
    • Year and Date
      20110619-20110623
  • [Presentation] Amplification of molecular shape selectivity with self-assembled molecular gel-immobilized silica in reversed-phase HPLC2011

    • Author(s)
      Makoto Takafuji, Thiraporn Charoenraks, Jin Izumi, Hirotaka Ihara
    • Organizer
      36th International Symposium on High-Performance Liquid Phase Separations and Related Techniques
    • Place of Presentation
      Budapest, Hungary
    • Year and Date
      20110619-20110623
  • [Presentation] Poly(ionic liquid)-grafted silica stationary phases for high-performance liquid chromatography2011

    • Author(s)
      Hongdeng Qiu, Makoto Takafuji, Xia Liu, Shengxiang Jiang, Hirotaka Ihara
    • Organizer
      IUPAC International Congress on Analytical Sciences 2011
    • Place of Presentation
      Kyoto International Conference Center Kyoto, Japan
    • Year and Date
      20110522-20110526
  • [Presentation] Separation of shape-constrained isomers by newly developed organic phase in RP-HPLC2011

    • Author(s)
      Abul K.Mallik, Hongdeng Qiu, Makoto Takafuji, Hirotaka Ihara
    • Organizer
      IUPAC International Congress on Analytical Sciences 2011
    • Place of Presentation
      Kyoto International Conference Center Kyoto, Japan
    • Year and Date
      20110522-20110526
  • [Presentation] 微粒子から美粒子まで2011

    • Author(s)
      伊原博隆
    • Organizer
      高分子学会九州支部特別講演会
    • Place of Presentation
      大分東洋ホテル、大分(招待講演)
    • Year and Date
      2011-12-09
  • [Presentation] Molecular organogel system for nano-fabrication2011

    • Author(s)
      H.Ihara
    • Organizer
      Engineering Workshop at Shangdong University
    • Place of Presentation
      Jinan, China(招待講演)
    • Year and Date
      2011-10-14
  • [Book] Handbook of Ionic Liquids 分筆(Ionic Liquids in Liquid Chromatography)2012

    • Author(s)
      H.Qiu, A.K.Mallik, M.Takafuji, S.Jiang, H.Ihara
    • Total Pages
      25
    • Publisher
      Nova Science Publishers, Inc.
  • [Book] Tocopherol : Sources, Uses and Health Benefits分筆(Chromatographic separation of tocopherol isomers.)2012

    • Author(s)
      K.Mallik, H.Qiu, T.Sawada, M.Takafuji, H.Ihara
    • Publisher
      Nova Science Publishers, Inc.(印刷中)
  • [Book] Metal, Ceramic and Polymeric Composites for Various Uses分筆(Noncrystalline L-phenylalanine-silica hybrid composite materials for high selective reversed phase liquid chromatography)2011

    • Author(s)
      M.M.Rahman, M.Takafuji, H.Ihara
    • Total Pages
      12
    • Publisher
      InTech
  • [Book] Polymer Initiators分筆(Surface-initiated ATRP as a versatile method to hybrid materials.)2011

    • Author(s)
      M.Czaun, A.K.Mallik, M.Takafuji, H.Ihara
    • Total Pages
      36
    • Publisher
      Nova Science Publishers, Inc.
  • [Remarks]

    • URL

      http://www.chem.kumamoto-u.ac.jp/~ihara/papers_select2011A.html

  • [Patent(Industrial Property Rights)] 複合材料及びその製造方法2011

    • Inventor(s)
      野里省二、中壽賀章、伊原博隆、マラテイ・ソバン・ガナパテイ、高藤誠
    • Industrial Property Rights Holder
      積水化学工業株式会社、国立大学法人熊本大学
    • Industrial Property Number
      特願2011-125471
    • Filing Date
      2011-06-03

URL: 

Published: 2013-06-26   Modified: 2014-06-02  

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