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: 23105537
• 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): 2011-04-01 – 2013-03-31
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2012: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 金属酵素 / バイオインスパイアード / ビタミンB12 / 酸化チタン / 光増感剤 / ラジカル反応 / 可視光応答型 / 触媒反応 / 超求核性 / ルテニウム錯体 / ローズベンガル / ポリマー

Outline of Annual Research Achievements

金属酵素は環境適合型触媒系の１つである。本研究ではラジカル酵素であるビタミンB12の機能に着目し、新しい分子活性化法の開拓とラジカル型直截的物質変換反応を行った。　酸化チタン(TiO2)の可視光応答化の手法としてTiO2表面にカテコールを修飾する手法が報告されている。本研究では、カテコール基をビタミンB12誘導体に導入し、TiO2表面に修飾することにより界面錯体形成を利用した可視光応答型B12-TiO2複合触媒の作製および触媒能の評価を行った。可視光応答型B12-TiO2ハイブリッド触媒を創製し、メタノール中でトリエタノールアミンを犠牲還元剤として反応を行った。トリクロロメチルベンゼンを基質として用い、420nm以上の可視光を照射するとスチルベンが主生成物として生成した。通常の酸化チタンをもつB12-TiO2ハイブリッド触媒を用いた場合には反応は全く進行せず、界面錯体形成が可視光活性化に極めて有効であることが明らかになった。　これまでルテニウム錯体を可視光応答型光増感剤として用いた触媒系を報告してきた。そこで希少金属を用いない光増感系として、有機光増感剤とビタミンB12誘導体の組み合わせで反応が効率良く進行する系を検討した。昨年度は有機増感剤としてローズベンガルを用いたラジカル型有機合成反応に成功したが、反応が完結するとローズベンガルの自己還元反応が起こり、光増感剤が失活するという欠点があった。今年度は有機増感剤としてローダミンBを用いることで、耐久性の高い可視光駆動型触媒反応系の開発に成功した。 この反応系は、ラジカル生成剤であるスズ化合物の代替としての利用が期待できる。

Research Progress Status

24年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

24年度が最終年度であるため、記入しない。

Research Products

• [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] Aquabis(1,1,1,5,5,5-hexafluoro- acetylacetonato)[4'-(4-pyridyl)-2,2':6',2"-terpyridine]ytterbium(III) chloride methanol monosolvate monohydrate (2012)
  • Author(s): Toru Okawara, Jiang Feng, Masaaki Abe, Yoshio Hisaeda
  • Journal Title: Acta Crystallographica Secion E Structure Report Online Volume: 68 Issue: 1 Pages: 29-30
  • DOI: 10.1107/s1600536811052378
  • Peer Reviewed
• [Journal Article] Synthesis and photosensitizing properties of porphycene with imidazolium tag (2012)
  • Author(s): Hisashi Shimakoshi, Kenichi Sasaki, Yusuke Iseki, Yoshio Hisaeda
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 16 Issue: 05n06 Pages: 530-536
  • DOI: 10.1142/s1088424612500551
  • Peer Reviewed
• [Journal Article] Hydrogenation effects in metalloporphycenes : synthesis and redox behavior of Ni(II)-tetra(n-propyl)-dihydroporphycene (2012)
  • Author(s): Toru Okawara, Koichi Hashimoto, Masaaki Abe, Hisashi Shimakoshi, Yoshio Hisaeda
  • Journal Title: Chemical Communications Volume: 48 Issue: 44 Pages: 5413-5415
  • DOI: 10.1039/c2cc30991b
  • Peer Reviewed
• [Journal Article] Oxo-centered Trimetallic Clusters Supported by Electron-withdrawing Carboxylates: Highly Inert Character in Ligand Exchange Kinetics of Dichloroacetate-bridged Complex [Ru3(μ3-O)(μ-CHCl2COO)6(pyridine)3] (2012)
  • Author(s): A. Inatomi
  • Journal Title: Aust. J. Chem. Volume: - Issue: 12 Pages: 1599-1607
  • DOI: 10.1071/ch12378
  • Peer Reviewed
• [Journal Article] Vitamin B12 derivatives as activators of soluble guanylyl cyclase (2012)
  • Author(s): Keith #243; Proinsias
  • Journal Title: J. Med. Chem. Volume: 55 Issue: 20 Pages: 8943-8947
  • DOI: 10.1021/jm3006959
  • Peer Reviewed
• [Journal Article] A Pd(II)-hydroxyporphycene : synthesis, characterization, and photoinduced proton-coupled electron transfer (2012)
  • Author(s): T.Okawara, et al
  • Journal Title: Res.Chem.Int. Volume: (In press)
  • Peer Reviewed
• [Journal Article] Synthesis and photosensitizing properties of porphycene with imidazolium tag (2012)
  • Author(s): H.Shimakoshi, et al
  • Journal Title: J.Porphyrins Phthalocyanines Volume: (In press)
  • Peer Reviewed
• [Journal Article] Electrochemical Catalytic Carbon-skeleton Rearrangement Mediated by Imine/Oxime-type B12 Model Complex (2011)
  • Author(s): K.Tahara, et al
  • Journal Title: Chemistry Letters Volume: 40 Issue: 2 Pages: 177-179
  • DOI: 10.1246/cl.2011.177
  • NAID: 10027814839
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Methyl-transfer Reaction to Alkylthiol Catalyzed by a Simple Vitamin B_<12> Model Complex Using Zinc Powder (2011)
  • Author(s): L.Pan, et al
  • Journal Title: Inorg.Chim.Acta Volume: 368 Issue: 1 Pages: 194-199
  • DOI: 10.1016/j.ica.2011.01.004
  • Peer Reviewed
• [Journal Article] Supramolecular Assemblies of Crown-substituted Dinickel and Dicobalt Complexes with Guest Cation Binding (2011)
  • Author(s): H.Shimakoshi, et al
  • Journal Title: Supramol.Chem. Volume: 23 Issue: 1-2 Pages: 131-139
  • DOI: 10.1080/10610278.2010.514910
  • Peer Reviewed
• [Journal Article] Eco-friendly Molecular Transformations Catalyzed by Vitamin B_<12> Derivative with Visible-Light-Driven System (2011)
  • Author(s): K.Tahara, et al
  • Journal Title: Green Chem Volume: 13 Issue: 3 Pages: 558-561
  • DOI: 10.1039/c0gc00478b
  • Peer Reviewed
• [Journal Article] Photocatalytic function of polymer-supported B_<12> complex with ruthenium trisbipyridine photosensitizer (2011)
  • Author(s): H.Shimakoshi, et al
  • Journal Title: Chem.Commun. Volume: 47 Issue: 23 Pages: 6548-6550
  • DOI: 10.1039/c1cc11970b
  • Peer Reviewed
• [Journal Article] Hydroxy-functionalized porphycenes : structure, spectroscopy, and electrochemistry (2011)
  • Author(s): Toru Okawara, Masaaki Abe, Hisashi Shimakoshi, Yoshio Hisaeda
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 84 Issue: 7 Pages: 718-728
  • DOI: 10.1246/bcsj.20110072
  • NAID: 130004152936
  • Peer Reviewed
• [Journal Article] Photosensitizing catalysis of B_<12> complex without additional photosensitizer (2011)
  • Author(s): H.Shimakoshi, et al
  • Journal Title: Chem.Commun. Volume: 47 Issue: 39 Pages: 10921-10923
  • DOI: 10.1039/c1cc12482j
  • Peer Reviewed
• [Presentation] Bioinspired Catalysts with Vitamin B12 Function (2012)
  • Author(s): Yoshio Hisaeda
  • Organizer: 第12回国際有機化学京都会議（IKCOC-12）
  • Place of Presentation: 京都
  • Year and Date: 2012-11-12
• [Presentation] Bioinspired Catalysts with Photosensitizers (2012)
  • Author(s): Hisaeda, Y.
  • Organizer: The International Symposium on Preparative Chemistry of Advanced Materials-2012
  • Place of Presentation: Shenyang, China
  • Year and Date: 2012-09-14
  • Invited
• [Presentation] Bioinspired Catalysts with Vitamin B12 Derivative and Photosensitizer (2012)
  • Author(s): Yoshio Hisaeda
  • Organizer: 9th JCSMCC（第9回日中クラスター会議）
  • Place of Presentation: 福岡
  • Year and Date: 2012-08-14
• [Presentation] Bioinsspired Catalysts with Vitamin B12 Enzyme Functions (2012)
  • Author(s): Hisaeda, Y.
  • Organizer: XXIVth IUPAC Symposium on Photochemistry
  • Place of Presentation: Coimbra, Portugal
  • Year and Date: 2012-07-15
  • Invited
• [Presentation] Photochemical Oxygen Activation by Molybdenum Porphycene Complex (2012)
  • Author(s): Hisaeda, Y.
  • Organizer: 7th International Conference on Porphyrins and Phthalocyanines (ICPP-7)
  • Place of Presentation: Jeju, Korea
  • Year and Date: 2012-07-01
  • Invited
• [Presentation] 酵素に学ぶ触媒設計：バイオインスパイアード触媒―物質変換と環境浄化への挑戦― (2012)
  • Author(s): 久枝良雄
  • Organizer: 広島大学理学部 特別講演
  • Place of Presentation: 広島
  • Year and Date: 2012-06-19
  • Invited
• [Presentation] 光で動くバイオインスパイアード触媒--物質変換と環境浄化への挑戦-- (2012)
  • Author(s): 久枝良雄
  • Organizer: 熊本大学理学部 特別講演
  • Place of Presentation: 熊本
  • Year and Date: 2012-06-08
  • Invited
• [Presentation] バイオインスパイアード触媒の創製と環境浄化への応用 (2011)
  • Author(s): 久枝良雄
  • Organizer: Seminar on Green and Sustainable Chemistry in Tottori 2011
  • Place of Presentation: 鳥取大学共通教務棟A20大講義室(招待講演)
  • Year and Date: 2011-12-15
• [Presentation] Bioinspired Catalysts with Cyclic Tetrapyrrole Compounds (2011)
  • Author(s): Yoshio Hisaeda
  • Organizer: The 2011 Global COE International Symposium on Future Molecular Systems
  • Place of Presentation: 九州大学・稲盛ホール(招待講演)
  • Year and Date: 2011-11-25
• [Presentation] Bioinspired Catalysts with Vitamin B_<12> Function Using Visible Light (2011)
  • Author(s): Yoshio Hisaeda, et al
  • Organizer: 第10回有機反応に関する国際シンポジウム10th International Symposium on Organic Reactions (ISOR10)
  • Place of Presentation: 横浜市・慶應義塾大学(招待講演)
  • Year and Date: 2011-11-22
• [Presentation] Bioinsspired Catalysts with Vitamin B_<12> Enzyme Functions (2011)
  • Author(s): Yoshio Hisaeda
  • Organizer: The 3rd Dalton Transactions International Symposium
  • Place of Presentation: 九州大学・稲盛ホール(招待講演)
  • Year and Date: 2011-11-16
• [Presentation] ポルフィセン誘導体の光化学的挙動と酸化反応 (2011)
  • Author(s): 久枝良雄, et al
  • Organizer: 第44回酸化反応討論会
  • Place of Presentation: 大阪大学吹田キャンパス銀杏会館
  • Year and Date: 2011-11-04
• [Presentation] Bioinspired Catalysts Composed of Vitamin B_<12> Derivative and Photosensitizers (2011)
  • Author(s): Yoshio Hisaeda
  • Organizer: 第3回アジア錯体化学会議(3rd Asian Conference on Coordination Chemistry)
  • Place of Presentation: インド・ニューデリーIndia Habitat Center(招待講演)
  • Year and Date: 2011-10-19
• [Presentation] Redox Behavior and Electrochemical Catalytic Function of B_<12>-Hyperbranched Polymer (2011)
  • Author(s): Yoshio Hisaeda, et al
  • Organizer: 第62回国際電気化学会年次大会(ISE-2011)
  • Place of Presentation: 新潟・朱鷺メッセ
  • Year and Date: 2011-09-12
• [Presentation] Bioorganometallic Catalysts with Vitamin B_<12> Derivative and Photosensitizers (2011)
  • Author(s): Yoshio Hisaeda, et al
  • Organizer: 第15回生物無機化学国際会議(ICBIC-15)
  • Place of Presentation: カナダ・バンクーバー
  • Year and Date: 2011-08-10
• [Presentation] Photochemical property and oxygen activation of molybdenum porphycene complex (2011)
  • Author(s): Yoshio Hisaeda
  • Organizer: 2011年酸素の活性化および均一系酸化触媒反応に関する国際会議(ADHOC-2011)
  • Place of Presentation: 沖縄・万国津梁館(招待講演)
  • Year and Date: 2011-07-06
• [Presentation] Carbon-Skeleton Rearrangement Reaction Mediated Simple Vitamin B_<12> Model Complex with Electrochemical Duet Process (2011)
  • Author(s): Yoshio Hisaeda, et al
  • Organizer: 219th ECS Meeting
  • Place of Presentation: カナダ・モントリオール(招待講演)
  • Year and Date: 2011-05-01
• [Book] バイオインダストリー：ビタミンB12をモデルとしたバイオインスパイアード触媒の開発 (2013)
  • Author(s): 嶌越 恒
  • Total Pages: 8
  • Publisher: CMC出版
• [Book] 有機合成化学協会誌：環状および非環状シッフ塩基型化合物の合成と錯形成による超分子機能の創製 (2012)
  • Author(s): 嶌越 恒
  • Total Pages: 11
  • Publisher: 有機合成化学協会
• [Book] 化学と工業：バイオミメティックからバイオインスパイアード触媒へ (2012)
  • Author(s): 久枝良雄
  • Total Pages: 3
  • Publisher: 日本化学会
• [Remarks] 久枝研究室 HISAEDA's Laboratory
  • URL: http://www.chem.kyushu-u.ac.jp/~hisaeda/
• [Remarks]
  • URL: http://www.chem.kyushu-u.ac.jp/~hisaeda/
• [Patent(Industrial Property Rights)] 可視光応答型複合触媒 (2013)
  • Inventor(s): 嶌越恒、久枝良雄、米村俊佑
  • Industrial Property Rights Holder: 嶌越恒、久枝良雄、米村俊佑
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2013-045909
  • Filing Date: 2013-03-07