Dioxygen Activation on Transition Metal Centers Tuned by Mimicking Non-heme Iron Active Sites

2012 Fiscal Year Final Research Report

• Project/Area Number: 22550060
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka University (2012); Nagoya Institute of Technology (2010-2011)
• Principal Investigator: FUNAHASHI Yasuhiro 大阪大学, 理学研究科, 教授 (00321604)
• Project Period (FY): 2010 – 2012
• Keywords: 酸素活性化 / 二核銅錯体モデル / チロシナーゼ / 反応機構解析 / 非ヘム鉄型モデル / 非ヘム鉄型オキシゲナーゼ / 高原子価マンガン錯体

Research Abstract

We succeeded in synthesizing a substrate-binding dicopper μ-η^2:η^2-peroxo complex and characterizing it spectroscopically. We also found that substrate binding to the copper center could accelerate formation of the active dioxygen intermediate species. In the manganese and iron complex systems, we obtained several findings involving the corresponding high-covalent metal oxo species.

Research Products

• [Journal Article] Highly Selective Binding of Nitric Oxide by Co^III and Fe^III Complexes (2013)
  • Author(s): Z. Zhang, T. Suwabe, M. Ishikawa, Y. Funahashi, T. Inomata, T. Ozawa, H. Masuda
  • Journal Title: Dalton Trans Volume: 42 Pages: 4470
• [Journal Article] Creation of a Binuclear Purple Copper Site within a de Novo Coiled-Coil Protein (2012)
  • Author(s): D. Shiga, Y. Funahashi, H. Masuda, A. Kikuchi,M. Noda, S. Uchiyama, K. Fukui, K. Kanaori, K. Tajima, Y. Takano, H. Nakamura, M. Kamei, T. Tanaka
  • Journal Title: Biochemistry Volume: 51 Pages: 7901
• [Journal Article] Tuning the Geometries of a De Novo Blue Copper Protein by Axial Interactions (2012)
  • Author(s): D. Shiga, Y. Hamano, M. Kamei, Y. Funahashi, H. Masuda, M. Sakaguchi, T. Ogura, T. Tanaka
  • Journal Title: T. J. Biol. Inorg. Chem Volume: 17 Pages: 1025
• [Journal Article] Adsorption Behavior of Microbes on a QCM Chip Modified with an Artificial Siderophore-Fe^3+Complex (2012)
  • Author(s): T. Inomata, H. Eguchi, Y. Funahashi, T. Ozawa, H. Masuda
  • Journal Title: Langmuir Volume: 28 Pages: 1611
• [Journal Article] Magnetostructural Property of a Twisted Bis(μ-hydroxo) Dicopper(II) core and Its Relevance to Formation of an Active Dioxygen Intermediate (2011)
  • Author(s): Y. Funahashi, T. Toyama, K. Yoshii, T. Nishikawa, M. Kishida, Y. Kajita, T. Inomata, T. Ozawa, Y. Wasada-Tsutsui, H. Masuda
  • Journal Title: Japanese Journal of Applied Physics Volume: 50 Pages: 01AJ07/1
• [Journal Article] Nitrile Hydration by Co(III) Complex with Oxygenated S Atoms Inserted into Mesoporous Silica (2011)
  • Author(s): T. Ozawa, T. Shibayama, T. Yano, Y.Funahashi, H. Masuda
  • Journal Title: Japanese Journal of Applied Physics Volume: 50 Pages: 01AJ04
• [Journal Article] Visible Light-induced Catalytic Oxidation Using Zeolite Encapsulating Two Distinct Metal Complexes (2011)
  • Author(s): T. Inomata, Y. Nagai, N. Ohata, Y. Funahashi,T. Ozawa, H. Masuda
  • Journal Title: Japanese Journal of Applied Physics Volume: 50 Pages: 01AJ03
• [Journal Article] Synthesis and Crystal Structures of Iron(II) Dichloride Complexes with α-Isosparteine, β-Isosparteine and 2-Methylsparteine (2010)
  • Author(s): B. Jasiewicz, T. Inazumi, Y. Inagaki, Y. Wasada-Tsutsui, Y. Funahashi, H. Masuda
  • Journal Title: Journal of Molecular Structure Volume: 984 Pages: 176
• [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: StructuralConversion Driven by Addition of a Strong Donor Ligand in the High Oxidation State (2010)
  • Author(s): D. Nakane, Y. Funahashi, T. Ozawa, H. Masuda
  • Journal Title: Chem. Lett Volume: 39 Pages: 344
• [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 Superoxide (2010)
  • Author(s): D. Nakane, Y. Funahashi, T. Ozawa, H. Masuda
  • Journal Title: Chem. Commun Volume: 46 Pages: 2142
• [Presentation] 金属酵素モデルの最前線と展望 (2013)
  • Author(s): 舩橋 靖博
  • Organizer: 分子研研究会「生体配位化学の最前線と展望」
  • Place of Presentation: 分子科学研究所
  • Year and Date: 2013-02-05
• [Presentation] TypeIII 銅型の二核銅-酸素中間体種の Entatic state モデル (2013)
  • Author(s): 舩橋 靖博
  • Organizer: 東北大学卓越大学院研究会「金属錯体の固体物性最前線;金属錯体と固体物性物理と生物物性の連携新領域を目指してー」
  • Place of Presentation: 東北大学
  • Year and Date: 2013-02-04
• [Presentation] 歪んだ配位構造を持つ二核銅酸素錯体によるチロシナーゼ活性中間体 (2012)
  • Author(s): 城田 剛志、外山 智章、小澤 智宏、猪股 智彦、舩橋 靖博、増田 秀樹
  • Organizer: 第45回酸化反応討論会
  • Place of Presentation: 名古屋市立大学
  • Year and Date: 2012-11-17
• [Presentation] TypeIII 銅蛋白質の二核銅中心構造を模倣したモデル錯体の性質 (2012)
  • Author(s): 舩橋靖博
  • Organizer: 生物物質科学フォーラム
  • Place of Presentation: 北陸先端科学技術大学院大学
  • Year and Date: 2012-03-10
• [Presentation] Phenolate-binding Dicopper Complex System as a Model of Tyrosinase (2011)
  • Author(s): 舩橋靖博、城田剛志、外山智章、和佐田祐子、猪股智彦、小澤智宏、 久保稔、山口悟、小倉尚志、 増田秀樹
  • Organizer: International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation (ADHOC2011)
  • Place of Presentation: Bankoku Shinryokan, Okinawa
  • Year and Date: 2011-07-04
• [Presentation] 二核銅-酸素錯体の形成とチロシナーゼの反応機構との関連 (2011)
  • Author(s): 舩橋靖博、城田剛志、外山智章、西川知秀、和佐田祐子、梶田裕二、猪股智彦、小澤智宏、増田秀樹
  • Organizer: 第38回生体分子科学討論会
  • Place of Presentation: 筑波大学
  • Year and Date: 2011-06-23
• [Presentation] O_2-Activation on Di/Tricopper Complexes as Biomimetic Model Systems (2011)
  • Author(s): 舩橋靖博
  • Organizer: 日本化学会第91 春季年会Asian International Symposium for Young Scientists (Division of Coordination Chemistry and Organometallic Chemistry)
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-28
• [Presentation] Synthetic Approaches to Dicopper and Tricopper Centers for Constructing Biomimetic Model Compounds of Multicopper Proteins (2010)
  • Author(s): 舩橋靖博、外山智章、永田光知郎、吉井孝太郎、西川知秀、福井健祐、梶田裕二、和佐田祐子、猪股智彦、小澤智宏、増田秀樹
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-17
• [Presentation] 分子状酸素の活性化能を有する多核銅中心の電子構造 (2010)
  • Author(s): 舩橋靖博
  • Organizer: 第4回東北大学G-COE 研究会「金属錯体の固体物性科学最前線-錯体化学と固体物性物理と生物物性の連携新領域創成をめざして-」
  • Place of Presentation: 東北大学
  • Year and Date: 2010-12-03
• [Presentation] チロシナーゼ反応メカニズム解明を目指した二核銅スパルテイン錯体におけるフェノラーゼ活性 (2010)
  • Author(s): 外山智章、吉井孝太郎、西川知秀、和佐田祐子、梶田裕二、猪股智彦、小澤智宏、増田秀樹、舩橋靖博
  • Organizer: 第43回酸化反応討論会
  • Place of Presentation: 東京大学
  • Year and Date: 2010-11-12
• [Presentation] 蛋白質内で酸素に関わる二核銅中心の立体構造と電子構造 (2010)
  • Author(s): 舩橋靖博
  • Organizer: 生物物質科学フォーラム
  • Place of Presentation: 北陸先端大東京サテライトキャンパス
  • Year and Date: 2010-05-26