金属酵素に学びそれを凌駕する分子活性化の新手法開拓

• Project Area: Molecule Activation Directed toward Straightforward Synthesis
• Project/Area Number: 25105744
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyushu University
• Principal Investigator: 久枝 良雄 九州大学, 工学(系)研究科(研究院), 教授 (70150498)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: ビタミンB12 / 光増感剤 / イオン液体 / 人工酵素 / 多孔性錯体フレームワーク / 環境汚染物質の分解 / 官能基1,2-転位反応 / 触媒反応 / 酸化チタン / 界面錯体 / 脱ハロゲン化反応 / 官能基転位反応 / 可視光 / 超求核性 / コバルト錯体

Outline of Annual Research Achievements

生体関連金属錯体であるビタミンB12とRu光増感剤を組み合わせた光駆動型の新しいビタミンB12人工酵素システムの開発を行った。以前に高分子の側鎖に両錯体を導入したハイブリッドポリマーを合成し、ポリマー内での高効率な光誘起電子移動反応が進行することを見出した。またイオン液体を反応溶媒とすると、ビタミンB12錯体の反応性が向上し、ビタミンB12錯体のリサイクル化が容易であることを報告した。そこで、本研究ではこれらの結果を踏まえ、イオン液体構造を高分子に導入し、さらに側鎖にビタミンB12誘導体とRu光増感剤を導入したハイブリッド型高分子化イオン液体を創製した。高分子化イオン液体はイオン伝導材料やCO2吸着材料として魅力的であるが、触媒としての応用例は少ない。本研究では、高分子化イオン液体を光駆動型ビタミンB12人工酵素に応用することに成功した。
また、多孔性錯体フレームワークに新たに光増感機能を付与した錯体フレームワークを創製し、可視光を駆動力とした固体触媒の開発を行った。光増感剤としてはルテニウム錯体を用い、触媒分子としてはビタミンB12モデル錯体を用いた。多孔性錯体フレームワークを構成できる金属イオンとして亜鉛(II)イオンを採用し、補助配位子、光増感能をもつルテニウム錯体の組み合わせにより、大きな空孔を有する多孔性錯体フレームワークを構築した。多孔性錯体フレームワークに導入した光増感剤は可視光により励起され、ビタミンB12モデル錯体を還元して活性なCo(I)種を生成した。本固体触媒を用いた可視光照射による有機ハロゲン化物（環境汚染物質）の分解反応および官能基の1,2-転位反応に成功した。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Development of Metal-Organic Framework (MOF)-B12 system as new bio-inspired heterogeneous catalyst (2015)
  • Author(s): Xu, J.; Shimakoshi, H.; Hisaeda, Y.
  • Journal Title: J. Organometal. Chem. Volume: 782 Pages: 89-95
  • DOI: 10.1016/j.jorganchem.2014.11.015
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Molecular structures, redox properties, and photosubstitution of ruthenium(II) carbonyl complexes of porphycene (2015)
  • Author(s): Okawara, T.; Abe, M.; Ashigara, S.; Hisaeda, Y.
  • Journal Title: J. Porphyrins Phthalocyanines Volume: 未定 Issue: 01-03 Pages: 233-241
  • DOI: 10.1142/s1088424614501120
  • Peer Reviewed
• [Journal Article] Synthesis and X-ray crystallography of bipyrroles: impacts of a Co-π interaction on their structure (2015)
  • Author(s): Toru Okawara, Akane Doi, Toshikazu Ono, Masaaki Abe, Kenji Takehara, Yoshio Hisaeda
  • Journal Title: Tetrahedron Letters Volume: 11 Issue: 11 Pages: 1407-1410
  • DOI: 10.1016/j.tetlet.2015.01.159
  • Peer Reviewed / Open Access
• [Journal Article] Crystal Structure Dependence for Reactivities of B12-TiO2 Hybrid Catalysts with Anatase and Rutile Forms (2015)
  • Author(s): Shiamkoshi, H.; Nagami, Y.; Hisaeda, Y.
  • Journal Title: Rapid Communication in Photoscience Volume: 未定 Issue: 1 Pages: 9-11
  • DOI: 10.5857/rcp.2015.4.1.9
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Characterizations, and Intramolecular Quenching Behavior of an Axially-Linked Trinuclear Molecular Wire Containing Ruthenium(II) Porphycenes (2015)
  • Author(s): Abe, M.; Ashigara, S.; Okawara, T.; Hisaeda, Y.
  • Journal Title: Rapid Communication in Photoscience Volume: 未定 Issue: 1 Pages: 22-24
  • DOI: 10.5857/rcp.2015.4.1.22
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] B12-TiO2 Hybrid Catalyst for Light-Driven Hydrogen Production and Hydrogenation of C-C Multiple Bonds (2014)
  • Author(s): Shimakoshi, H.; Hisaeda,Y.
  • Journal Title: ChemPlusChem Volume: 79 Pages: 1250-1253
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Polymerized Ionic Liquid-supported B12 Catalyst with a Ruthenium Trisbipyridine Photosensitizer for Photocatalytic Dechlorination in Ionic Liquids (2014)
  • Author(s): Zhang, W.; Shimakoshi, H.; Houfuku, N.; Song,X.; Hisaeda, Y.
  • Journal Title: Dalton Trans. Volume: 43 Issue: 37 Pages: 13972-13978
  • DOI: 10.1039/c4dt01360c
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Alkylcobyrinate from sucralose and mechanistic aspects of its Co-C bond cleavage (2014)
  • Author(s): H. V. Motwani, H. Shimakoshi, B. T. Golding, M. Tornqvist, Y. Hisaeda
  • Journal Title: Tetrahedron letters Volume: 未定 Issue: 16 Pages: 2667-2670
  • DOI: 10.1016/j.tetlet.2014.03.028
  • Peer Reviewed
• [Journal Article] Synthesis of a series of multiply meso-acetoxylated porphycenes (2014)
  • Author(s): Okawara, T.; Abe,M.; Hisaeda,Y.
  • Journal Title: Tetrahedron Lett. Volume: 55 Issue: 45 Pages: 6193-6197
  • DOI: 10.1016/j.tetlet.2014.09.057
  • Peer Reviewed
• [Journal Article] A Heterometallic Protocol for Turn-On Fluorescence. Synthesis, Structure, and Luminescence Behavior of Diruthenium(III)-Magnesium(II) Complex Decorated with Four Pyrenecarboxylates (2014)
  • Author(s): Atsushi Ikegami, Masaaki Abe, and Yoshio Hisaeda
  • Journal Title: Chem. Lett. Volume: 43 Issue: 4 Pages: 456-458
  • DOI: 10.1246/cl.131093
  • NAID: 130004868029
  • Peer Reviewed
• [Journal Article] Construction of Molecular Communication Interface Formed from Cerasome and Hydrophobic Vitamin B₁₂ on Glassy Carbon Electrode (2014)
  • Author(s): Qiao, Y.; Tahara, K.; Zhang, Q.; Song, X.-M.; Hisaeda, Y.; Kikuchi. J.
  • Journal Title: Chemistry Letters Volume: 43 Issue: 5 Pages: 684-686
  • DOI: 10.1246/cl.140025
  • NAID: 130004868138
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Co(II)/Co(I) Reduction-induced Axial Histidine-flipping in Myoglobin Reconstituted with a Cobalt Tetradehydrocorrin as a Methionine Synthase Model (2014)
  • Author(s): Takashi Hayashi, Yoshitsugu Morita, Eiichi Mizohata, Koji Oohora, Jun Ohbayashi, Tsuyoshi Inoue, and Yoshio Hisaeda
  • Journal Title: Chem. Commun. Volume: 50 Issue: 83 Pages: 12560-12563
  • DOI: 10.1039/c4cc05448b
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Proton-Coupled Electron Transfer of a Pd(II) Hydroxyporphycene Complex (2013)
  • Author(s): Toru Okawara, Masaaki Abe, Hisashi Shimakoshi, and Yoshio Hisaeda
  • Journal Title: Res. Chem. Intermed. Volume: 39 Issue: 1 Pages: 161-176
  • DOI: 10.1007/s11164-012-0640-8
  • Peer Reviewed
• [Journal Article] Dechlorination of DDT Catalyzed by Visible-Light-Driven System Composed of Vitamin B_<12> Derivative and Rhodamine B (2013)
  • Author(s): K. Tahara, K. Mikuriya, T. Masuko, J. Kikuchi, Y. Hisaeda
  • Journal Title: J. Porphyr. Phthalocya Volume: Vol.17, No.1-2 Issue: 01n02 Pages: 135-141
  • DOI: 10.1142/s1088424612501398
  • Peer Reviewed
• [Journal Article] Metallopolymer Films Exhibiting Three-color Electrochromism in the UV/Vis and Near-IR Region: Remarkable Utility of Trimetallic Clusters Bearing Thienyl Pendants and Their Mixed-valent Charge Transfer Transitions (2013)
  • Author(s): Rumiko Matsuse, Masaaki Abe, Yuki Tomiyasu, Atsushi Inatomi, Hiroaki Yonemura, Sunao Yamada, and Yoshio Hisaeda
  • Journal Title: J. Inorg. Organomet. Polym. Volume: 23 Issue: 1 Pages: 136-146
  • DOI: 10.1007/s10904-012-9758-9
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization, Co-S Bond of a Vitamin B12 Model Complex Having Pentafluorophenylthiolate as an Axial Ligand (2013)
  • Author(s): Tahara, K.; Matsuzaki, A.; Masuko, T.; Kikuchu, J.; Hisaeda, Y.
  • Journal Title: Dalton Trans. Volume: 42 Issue: 18 Pages: 6410-6416
  • DOI: 10.1039/c3dt00042g
  • Peer Reviewed
• [Journal Article] Photoinduced Electron Transfer in Supramolecular Donor-Acceptor dyad of Zn Corrphycene (2013)
  • Author(s): M. Fujitsuka, Y. Hisaeda, T. Majima
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 15 Issue: 15 Pages: 5677-5683
  • DOI: 10.1039/c3cp43795g
  • Peer Reviewed
• [Journal Article] Bioinspired catalytic reactions with vitamin B12 derivative and photosensitizers (2013)
  • Author(s): Y. Hisaeda, K. Tahara, H. Shimakoshi, T. Masuko
  • Journal Title: Pure and Applied Chemistry Volume: 85 Issue: 7 Pages: 1415-1426
  • DOI: 10.1351/pac-con-12-10-05
  • Peer Reviewed
• [Journal Article] Synthesis and Characterizations of meso-Disubstituted Asymmetric Porphycenes (2013)
  • Author(s): Masatsugu Taneda, Akihiro Tanaka, Hisashi Shimakoshi, Atsushi Ikegami, Koichi Hashimoto, Masaaki Abe, and Yoshio Hisaeda
  • Journal Title: Tetrahedron Lett. Volume: 54 Issue: 42 Pages: 5727-5729
  • DOI: 10.1016/j.tetlet.2013.08.026
  • Peer Reviewed
• [Presentation] バイオインスパイアード錯体化学＜ピロール系金属錯体の化学＞ (2014)
  • Author(s): 久枝 良雄
  • Organizer: 第3回錯体化学若手の会 九州・沖縄支部勉強会
  • Place of Presentation: 九州大学理学研究院、福岡
  • Year and Date: 2014-11-29
  • Invited
• [Presentation] Electrochemical Bioinspired Catalytic Reactions Mediated by Hydrophobic Vitamin B12 (2014)
  • Author(s): Hisaeda, Y.
  • Organizer: Electrochemistry 2014
  • Place of Presentation: Mainz, Germany
  • Year and Date: 2014-09-22 – 2014-09-24
  • Invited
• [Presentation] Bioinspired Catalytic Reactions:Lessons from Vitamin B12 Enzymes (2014)
  • Author(s): Hisaeda, Y.
  • Organizer: XXVI Internatioal Conference on Organometallic Chemistry (ICOMC 2014)
  • Place of Presentation: Sapporo, Japan
  • Year and Date: 2014-07-13 – 2014-07-18
  • Invited
• [Presentation] Redox Behavior and Reaction of Cobalt Porphycene Derivative (2014)
  • Author(s): Hisaeda, Y.
  • Organizer: The 225th ECS Meeting
  • Place of Presentation: Orlando, USA
  • Year and Date: 2014-05-11 – 2014-05-16
  • Invited
• [Presentation] Bioinspired Catalysts with Cobalt Complexes and Photosensitizers:Lessons from Vitamin B12-dependent Enzymes (2013)
  • Author(s): Hisaeda, Y.
  • Organizer: 6th International Conference on Green & Sustainable Chemistry (GSC-6)
  • Place of Presentation: Nottingham, UK
  • Invited
• [Presentation] Bioinspired Catalysts with Vitamin B12 Derivative and Photoseneitizers (2013)
  • Author(s): Hisaeda, Y.
  • Organizer: 20th International SPACC Symposium
  • Place of Presentation: Changchun, China
  • Invited
• [Presentation] Preparation and Reactions of Porphycenes and Cobalt Prophycene (2013)
  • Author(s): Hisaeda, Y.
  • Organizer: The 11th International Symposium on Organic Reactions (ISOR-11)
  • Place of Presentation: Taipei, Taiwan
  • Invited
• [Presentation] Photochemical and Electrochemical Reactions of Porphycenes and Cobalt Porphycene (2013)
  • Author(s): Hisaeda, Y.
  • Organizer: Korea-Japan Symposium on Frontier Photoscience (KJFP-2013)
  • Place of Presentation: Seoul, Korea
  • Invited
• [Presentation] Bioinspired Matrials: Lessons from Metalloenzymes with Tetrapyrrole Compounds
  • Author(s): Hisaeda, Y.
  • Organizer: Special Lecture on Lucite International UK Ltd.
  • Place of Presentation: Lucite International UK Ltd., Darlington, UK
  • Invited
• [Book] 環境問題解決のための先進的技法 (2015)
  • Author(s): 嶌越恒, 久枝良雄
  • Total Pages: 13
  • Publisher: 花書院
• [Book] ゾル-ゲル法の最新応用と展望 (2014)
  • Author(s): 嶌越恒, 久枝良雄
  • Total Pages: 6
  • Publisher: シーエムシー出版
• [Book] 光化学の辞典 (2014)
  • Author(s): 久枝良雄
  • Total Pages: 2
  • Publisher: 朝倉書店
• [Book] Encyclopedia of Applied Electrochemistry, 1st Edition (2014)
  • Author(s): Shimakoshi, H.; Hisaeda, Y.
  • Total Pages: 8
  • Publisher: Springer
• [Book] バイオインダストリー (2013)
  • Author(s): 嶌越 恒, 久枝良雄
  • Total Pages: 8
  • Publisher: シーエムシー出版