Carbon Fixation Reactions Modeling Iron/Nickel Enzymes Included in Acetyl CoA Pathway

• Project/Area Number: 25410066
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Nagoya University
• Principal Investigator: Matsumoto Tsuyoshi 名古屋大学, トランスフォーマティブ生命分子研究所, 准教授 (50311717)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: ニッケル酵素 / アセチルCoA合成酵素 / COデヒドロゲナーゼ / 炭素固定 / モデル研究

Outline of Final Research Achievements

Model studies of CO dehydrogenase (CODH) and acetyl CoA synthase (ACS) were conducted to elucidate the unrevealed mechanism of the carbon fixation process of acetyl CoA pathway in nature. As a CODH active site model, a novel [4Fe-5S-Ni] cluster was synthesized by utilizing our unique tridentate thiolate ligands. For our model studies of ACS, a series of dinuclear nickel complexes having tetra-anionic diamido-dithiolate ligand “mbea” modeling the plausible intermediates included in the ACS catalytic pathway was synthesized, and the thioester formation reaction modeling the ACS was accomplished. The results considerably contribute to elucidate the ACS reaction mechanism, and provide clues to the development of new carbon fixation reactions.

Research Products

• [Journal Article] “Supramolecular Porphyrin-Based Metal–Organic Frameworks with Fullerenes: Crystal Structures and Preferential Intercalation of C70” (2016)
  • Author(s): Mukae, Y.; Motegi, H.; Kajiya, S.; Yamamoto, M.; Senda, S.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Chem. Asian J. Volume: 11 Issue: 5 Pages: 700-704
  • DOI: 10.1002/asia.201501422
  • Peer Reviewed
• [Journal Article] Heterolytic Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Rutheni um-Germanium Dinuclear Complex. Theoretical Insights (2014)
  • Author(s): N. Ochi, T. Matsumoto, T. Dei, Y. Nakao, H. Sato, K. Tatsumi, S. Sakaki
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 2 Pages: 576-585
  • DOI: 10.1021/ic502463y
  • Peer Reviewed
• [Journal Article] [3:1] Site-Diffentiated [4Fe-4S] Clusters Having One Carboxylate and Three Thiolates. (2013)
  • Author(s): T. Terada, K. Hirabayashi, D. Liu, T. Nakamura, T. Wakimoto, T. Matsumoto, and K. Tatsumi
  • Journal Title: Inorg. Chem Volume: 52 Issue: 20 Pages: 11997-12004
  • DOI: 10.1021/ic4017596
  • Peer Reviewed
• [Presentation] ナフトエ酸銅(II)-銅(II)テトラピリジルポルフィン錯体の結晶構造とガス吸蔵 (2016)
  • Author(s): 大村 哲賜、臼杵 有光、向江 友佑、千駄 俊介、松本 剛、巽 和行
  • Organizer: 日本化学会第96春季年会 (2016)
  • Place of Presentation: 京田辺, 同志社大学
  • Year and Date: 2016-03-24
• [Presentation] Synthesis of Dithiolate-Bridged Iron(Carbonyl/Cyanide)-Nickel Complexes and their Reactions Modeling the [NiFe] Hydrogenase Active Site (2016)
  • Author(s): Moumita BOSE, Zilong LI, Yasuhiro OHKI, Tsuyoshi MATSUMOTO, and Kazuyuki TATSUMI
  • Organizer: The 5th International Conference on MEXT Project of Integrated Research on Chemical Synthesis
  • Place of Presentation: Nagoya
  • Year and Date: 2016-01-29
  • Int'l Joint Research
• [Presentation] An Optimal P-Cluster Model of Nitrogenase having Sterically Demanding Thiolates (2016)
  • Author(s): Golam MOULA, Ayaka NAGASAKI, Yasuhiro OHKI, Tsuyoshi MATSUMOTO, and Kazuyuki TATSUMI
  • Organizer: The 5th International Conference on MEXT Project of Integrated Research on Chemical Synthesis
  • Place of Presentation: Nagoya
  • Year and Date: 2016-01-29
  • Int'l Joint Research
• [Presentation] Synthesis of Dithiolato-Bridged (Carbonyl/Cyano)Iron-Nickel Complexes Bearing Hydride as a model of [Ni/Fe] hydrogenase active site (2016)
  • Author(s): Zilong Li, Yasuhiro OHKI, Tsuyoshi MATSUMOTO, and Kazuyuki TATSUMI
  • Organizer: The 5th International Conference on MEXT Project of Integrated Research on Chemical Synthesis
  • Place of Presentation: Nagoya
  • Year and Date: 2016-01-29
  • Int'l Joint Research
• [Presentation] Model Studies on Acetyl CoA Synthase catalyzing CO2 fixation in organisms (2015)
  • Author(s): Tsuyoshi Matsumoto
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of [8Fe-7S] Clusters Having Sterically Demanding Thiolates: An Optimal P-Cluster Model of Nitrogenase (2015)
  • Author(s): Golam Moula, Ayaka Nagasaki, Yasuhiro Ohki, Tsuyoshi Matsumoto, Kazuyuki Tatsumi
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] Synthesis and Reactions of Dithiolate-Bridged Heterobimetallic Iron(Carbonyl/Cyanide)-Nickel Complexes in Relevance to the Active Site of [NiFe] Hydrogenase (2015)
  • Author(s): Moumita Bose, Zilong Li, Yasuhiro Ohki, Tsuyoshi Matsumoto, Kazuyuki Tatsumi
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] Dithiolato-Bridged (Carbonyl/Cyano)Iron-Nickel Complexes Bearing Hydride as a Model of [NiFe]Hydrogenase Active Site (2015)
  • Author(s): 李 子龍・大木 靖弘・松本 剛 ・巽 和行
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] 酢酸銅(II)-テトラピリジルポルフィン錯体の C70 分子認識能 (2015)
  • Author(s): 大村 哲賜・臼杵 有光・千駄 俊介・松本 剛・巽 和行
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] Model Studies on Acetyl CoA Synthase (2015)
  • Author(s): Tsuyoshi Matsumoto
  • Organizer: 6th International IMBG Meeting, Chemistry & Biology of Iron-Sulfur Clusters
  • Place of Presentation: Villard de Lans, France
  • Year and Date: 2015-09-15
  • Int'l Joint Research / Invited
• [Presentation] Model Studies on Acetyl CoA Synthase: Structures and Reaction Mechanism (2015)
  • Author(s): T. Matsumoto
  • Organizer: UC Irvine Bioinorganic Lecture Series
  • Place of Presentation: Irvine, CA, USA
  • Year and Date: 2015-02-12
  • Invited
• [Presentation] アセチルCoA合成酵素の反応中間体モデルとなるジアミドジチオラート型mbea配位子をもつ二核ニッケル錯体の合成と反応 (2014)
  • Author(s): 大須 理恵・大木 靖弘・唯 美津木・巽 和行・松本 剛
  • Organizer: 錯体化学会 第64回討論会
  • Place of Presentation: 東京
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] かさ高いterphenyl 基をリン上に導入したジホスフィン配位子を有する単核ニッケル錯体の合成と反応 (2014)
  • Author(s): 鈴木 宏徳・唯 美津木・大木 靖弘・松本 剛
  • Organizer: 錯体化学会 第64回討論会
  • Place of Presentation: 東京
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] Synthesis and Reaction of Dinuclear Nickel Complexes Modeling Intermediates in the Enzymatic Cycle of Acetyl CoA Synthase (2014)
  • Author(s): R. Osu, Y. Ozawa, Y. Ohki, T. Matsumoto, K. Tatsumi
  • Organizer: XXXVI International Conference on Organometallic Chemistry (ICOMC 2014)
  • Place of Presentation: 札幌
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Synthesis of [3:1] Site-Differentiated [4Fe-4S] Clusters Functioning in Biological System (2014)
  • Author(s): T. Matsumoto
  • Organizer: Bioinogranic Group Seminar, University of Freiburg
  • Place of Presentation: Freiburg, Germany
  • Year and Date: 2014-07-04
  • Invited
• [Presentation] Model Studies on Nickel Enzymes Playing Key Roles in Autotrophic Carbon Fixation (2014)
  • Author(s): T. Matsumoto
  • Organizer: EMTECH, Universiti Putra Malaysia (UPM) – University Of Hyogo (UH), Japan Joint Colloquium 2014
  • Place of Presentation: Putra, Malaysia
  • Year and Date: 2014-05-26 – 2014-05-27
  • Invited
• [Presentation] My Career Path (2014)
  • Author(s): T. Matsumoto
  • Organizer: SOKENDAI Physical Science Student Seminar AY2013
  • Place of Presentation: Okazaki
  • Invited
• [Presentation] 三座チオラート配位子をもつ鉄硫黄クラスターへのニッケル錯体の導入:COデヒドロゲナーゼ活性中心モデルの構築 (2014)
  • Author(s): 田中香帆、寺田玲季、松本剛、巽和行
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] アセチルCoA合成酵素の中間体モデルとなるジアミドジチオラート型mbea配位子を持つ二核ニッケル錯体 (2014)
  • Author(s): 大須理恵、小澤由佳、唯美津木、大木靖弘、巽和行、松本剛
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] Model Studies on Nickel Enzymes Relevant to Autotrophic Carbon Fixation (2013)
  • Author(s): T. Matsumoto
  • Organizer: The 15th Joint Semiar University of Münster-Nagoya University
  • Place of Presentation: Nagoya
  • Invited
• [Presentation] Synthesis of [Ni-Ni] and [Ni-S-Fe4S4] Complexes Modeling Acetyl CoA Synthase Active Site (2013)
  • Author(s): T. Matsumoto, R. Osu, Y. Ozawa, T. Terada, K. Tanaka, K. Tatsumi
  • Organizer: 16th International Conference on Biological Inorganic Chemistry (ICBIC16)
  • Place of Presentation: Grenoble, France
• [Presentation] 嫌気性生物の炭素固定に関わる金属酵素のモデル研究 (2013)
  • Author(s): 松本 剛
  • Organizer: 錯体化学若手の会夏の学校2013
  • Place of Presentation: 札幌
  • Invited
• [Presentation] アセチルCoA 合成酵素の反応中間体モデルとなるメチル基とチオラートを併せもつ二核ニッケル錯体 (2013)
  • Author(s): 大須理恵、小澤由佳、松本剛、巽和行
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 沖縄
• [Presentation] 三座チオラート配位子を導入した[1:3]不均等配位[4Fe-4S]クラスターおよびCOデヒドロゲナーゼ活性中心モデルの合成 (2013)
  • Author(s): 田中香帆、中村友彦、寺田玲季、松本剛、巽和行
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 沖縄
• [Presentation] 三座チオラート配位子とクロリドが配位した[4Fe-4S]2+クラスターと水素化ホウ素ナトリウムの反応 (2013)
  • Author(s): 寺田玲季、松本剛、巽和行
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 沖縄
• [Book] 科学の健全な発展のために (2015)
  • Author(s): 日本学術振興会「科学の健全な発展のために」編集委員会
  • Total Pages: 141
  • Publisher: 丸善出版