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配位環境の協奏的制御によるアルカン・アルケンの水酸化反応

Research Project

Project/Area Number 20037029
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionNagoya Institute of Technology

Principal Investigator

増田 秀樹  Nagoya Institute of Technology, 工学研究科, 教授 (50209441)

Project Period (FY) 2008 – 2009
Project Status Completed (Fiscal Year 2009)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2009: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2008: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords協奏機能 / 酸化反応 / エポキシ化 / ペルオキソ / シリカ多孔体 / ベンゼンの水酸化 / 銅錯体 / ルテニウム錯体
Research Abstract

生体系に存在する金属含有酸化酵素は、酸素種を活性化し、基質を部位特異的に酸化している。この時、発現される酵素の基質特異性は、高選択性、高機能であり、いわゆる基質反応場と金属イオンの活性化である。本研究では、酸素を活性化する金属イオンの活性化と、基質特異的な反応場を合わせ持つ触媒の構築を目指した。特に、歪みを導入した銅錯体を開発し、ベンゼンをフェノールへ一段階で水酸化する錯体の合成に成功し、現在常温常圧下でTON200回程度を示した。この錯体の反応系へ水を添加すると、触媒としての効率が上昇した。これはベンゼンとフェノールが水の添加により溶解度の差が表れ、収率が上昇したものと思われる。また、フタロシアニン内包ゼライトについて酸化反応を行ったところ、触媒的酸化反応を示すことが分かったが、これに光応答性ルテニウムトリスビピリジンを挿入したところ、光照射下で酸化反応を遂行したところ、触媒効率が上昇した。これは、明らかに光照射により電子移動あるいはエネルギー移動が起こり、反応効率を上昇させたものと思われる。これらの研究は未来の物質・エネルギーの変換触媒として期待され、低環境負荷で持続可能な社会への貢献が待たれる。

Report

(2 results)
  • 2009 Annual Research Report
  • 2008 Annual Research Report
  • Research Products

    (12 results)

All 2010 2009 2008 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (2 results) Book (1 results) Remarks (1 results)

  • [Journal Article] A Square-planar Ni(II) Complex with an N2S2 Donor Set Similar to the Active Centre of Nickel-containing Superoxide Dismutase and Its Reaction with Superoxide2009

    • Author(s)
      D.Nakane, S.Kuwasako, M.Tsuge, M.Kubo, Y.Funahashi, T.Ozawa, T.Ogura, H.Masuda
    • Journal Title

      Chem.Commun. 46

      Pages: 2142-2144

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Square-planar Ni(II) Complex with an Asymmetric N2S2 Donor Set as a Model for the Active Site of Nickel-containing SOD : Structural Conversion Driven by Addition of a Strong Donor Ligand in the High Oxidation State2009

    • Author(s)
      D.Nakane, Y.Funahashi, T.Ozawa, H.Masuda
    • Journal Title

      Chem.Lett. 39

      Pages: 344-346

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of a Benzene-Dimolybdenum Complex with a New Bridging Mode.2009

    • Author(s)
      Y.Kajita, T.Ogawa, J.Matsumoto, H.Masuda
    • Journal Title

      Inorganic Chemistry 130

      Pages: 762-765

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nano-film structures constructed by self-assembly of Co (II) biuretato complexes and long alkylimidazolium cations2009

    • Author(s)
      K. Yamada, Y. Okazaki, T. Inomata, K. Kuroiwa, N. Kimizuka, T. Ozawa, Y. Funahashi, and H. Masuda
    • Journal Title

      J. Nanosci. & Nanotech. 9

      Pages: 307-312

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Self-assembled Mononuclear Electrode of a Diiron Complex with a Phenoxo-based Dinuclear Ligand : Observation of Molecular Oxygen Adsorption/Desorption in Aqueous Media2008

    • Author(s)
      T. Inomata, K. Shiozaki, Y. Hayashi, H. Arii, Y. Finahashi, T. Ozawa, and H. Masuda
    • Journal Title

      Chem. Commun. 2008

      Pages: 392-394

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] H-atom Abstraction Reaction for Organic Substrates via Mononuclear Copper (II)-superoxo Species as a Model for DβM and PHM2008

    • Author(s)
      T. Fujii, ; S. Yamaguchi, S. Hirota, and H. Masuda
    • Journal Title

      Dalton Trans 2008

      Pages: 164-170

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Characterization, and Reactivities of (m-h 2 : h 2-Disulfido) dicopper (II) Complexes with N-Alkylated cis, cis-1, 3, 5-Triaminocyclohexane Derivatives2008

    • Author(s)
      Y. Kajita, J. Matsumoto, I. Takahashi, S. Hirota, Y. Funahashi, T. Ozawa, and H. Masuda
    • Journal Title

      Eur. J. Inorg. Chem. 2008

      Pages: 3977-3986

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formation of a Bridged Butterfly-Type μ-η^2 : η^2-Peroxo Dicopper Core Structure with a Carboxylate Group2008

    • Author(s)
      Y. Funanasm, T. Nisasrnicawa, Y. Wasada-Tsutsui, Y. Kajita, S. Yamaguchi, H. Arii, T. Ozawa, K. Jitsukawa, T. Tosha, S. Hirota, T. Kitagawa. and H.Masuda
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 16444-16445

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Presentation] Binding and Activation of Oxygen Species by Bio-inspired Cu(II) Complexes2010

    • Author(s)
      H.Masuda
    • Organizer
      Tenth International Symposium on Biomimetic Materials Processing (BMMP-10)
    • Place of Presentation
      Nagoya (Japan)
    • Related Report
      2009 Annual Research Report
  • [Presentation] Synthesis, Characterization and Reactivity of μ-1,2-Peroxodiiron(III) Complexes as a Structural/Functional Model for sMMO's Active Center2009

    • Author(s)
      H.Masuda
    • Organizer
      International Conference on Biological Inorganic Chemistry (ICBIC14)
    • Place of Presentation
      Nagoya (Japan)
    • Related Report
      2009 Annual Research Report
  • [Book] 生体機能を模倣した金属錯体の修飾による機能性電極の構築2008

    • Author(s)
      猪股智彦、高橋勇雄、舩橋靖博、増田秀樹
    • Publisher
      触媒学会
    • Related Report
      2008 Annual Research Report
  • [Remarks]

    • URL

      http://www.ach.nitech.ac.jp/~inorg/masuda/Japanese/

    • Related Report
      2009 Annual Research Report

URL: 

Published: 2008-04-01   Modified: 2018-03-28  

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