Model Studies of Nickel Enzymes Included in Carbon Fixation Processes in Nature

• Project/Area Number: 22550059
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Nagoya University
• Principal Investigator: MATSUMOTO Tsuyoshi 名古屋大学, 理学研究科, 助教 (50311717)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2011: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2010: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: ニッケル酵素 / アセチル CoA合成酵素 / メチル CoM還元酵素 / チオラート / 炭素固定 / メタン生成 / アセチルCoA合成酵素 / メチルCoM還元酵素 / COデヒドロゲナーゼ / メタン菌

Research Abstract

Nickel complexes modeling acetyl CoA synthase (ACS) and methylCoM reductase (MCR) were synthesized in order to investigate their structures and reactions wereto obtain clues to the unrevealed reaction mechanisms. Synthesis of a series of dinuclear nickelcomplexes having tetra-anionic diamido-dithiolate ligand mbpa modeling the plausibleintermediates of the catalytic reaction was achieved. As for MCR model complexes, the nickel(II)cyclams coordinated by methyl CoM sulfonate as an inactive form model and the nickel(I) cyclamsmodeling the active reduced state were synthesized.

Research Products

• [Journal Article] Coordination of Methyl Coenzyme M and Coenzyme M at Divalent and Trivalent Nickel Cyclams: Model Studies of Methyl Coenzyme M Reductase Active Site (2012)
  • Author(s): Nishigaki, J.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Inorg. Chem. Volume: 51 Issue: 6 Pages: 3690-3697
  • DOI: 10.1021/ic202686x
  • Peer Reviewed
• [Journal Article] Tridentate Thiolate Ligands: Application to the Synthesis of the Site-Differentiated [4Fe-4S]Cluster having a Hydrosulfide Ligand at theUnique Iron Center (2012)
  • Author(s): Terada, T.; Wakimoto, T.; Nakamura, T.; Hirabayashi, K.; Tanaka, K.; Li, J.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Chem. Asian J. Volume: 7 Issue: 5 Pages: 920-929
  • DOI: 10.1002/asia.201200039
  • Peer Reviewed
• [Journal Article] Model Studies of Methyl CoM Reductase: Methane Formation via CH3.S Bond Cleavage of Ni(I) Tetraazacyclic ComplexesHaving Intramolecular Methyl Sulfide Pendants. (2012)
  • Author(s): Nishigaki, J.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Inorg. Chem. Volume: 51 Issue: 9 Pages: 5173-5187
  • DOI: 10.1021/ic300017k
  • Peer Reviewed
• [Journal Article] Dihydrogen Activation by Sulfido-Bridged Dinuclear Ru/Ge Complexes: Insight into the [NiFe] Hydrogenase Unready State (2011)
  • Author(s): Matsumoto, T.; Itakura, N.; Nakaya, Y.; Tatsumi, K.
  • Journal Title: Chem. Commun. Volume: 47 Issue: 3 Pages: 1030-1032
  • DOI: 10.1039/c0cc03391j
  • Peer Reviewed
• [Journal Article] Dihydrogen Activation by Sulfido-Bridged Dinuclear Ru/Ge Complexes : Insight into the [NiFe] Hydrogenase Unready State (2011)
  • Author(s): T.Matsumoto, N.Itakura, Y.Nakaya, K.Tatsumi
  • Journal Title: Chem.Commun. Volume: 47 Pages: 1030-1032
  • Peer Reviewed
• [Journal Article] Dodecanuclear Ellipse and Decanuclear Wheel Nickel(II) Thiolato Clusters with Efficient Femtosecond Nonlinear Absorption (2010)
  • Author(s): Zhang, C.; Matsumoto, T.; Samoc, M.; Petrie, S.; Meng, S.; Corkery, T. C.; Stranger.R.; Zhang, J.; Humphrey, M. G.; Tatsumi. K.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 49 Issue: 25 Pages: 4209-4212
  • DOI: 10.1002/anie.200907074
  • Peer Reviewed
• [Journal Article] Coordination of Coenzyme M and its Derivatives on Ni(II)(tetraazacycle)Complexes: A Model for the Acitive Site ofMethyl Coenzyme M Reductase (2010)
  • Author(s): Nishigaki, J.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2010 Issue: 31 Pages: 5011-5017
  • DOI: 10.1002/ejic.201000801
  • Peer Reviewed
• [Journal Article] Dodecannclear-Ellipse and Decanuclear-Wheel Nickel(II) Thiolato Clusters with Efficient Femtosecond Nonlinear Absorption (2010)
  • Author(s): C.Zhang, T.Matsumoto, 他
  • Journal Title: Angew.Chem.Int.Ed. Volume: 49 Pages: 4209-4212
  • Peer Reviewed
• [Journal Article] Coordination of Coenzyme M and Its Derivatives on Ni^<II>(tetraazacycle) Complexes : A Model for the Active Site of Methyl Coenzyme M Reductase (2010)
  • Author(s): J.Nishigaki, T.Matsumoto, K.Tatsumi
  • Journal Title: Eur.J.Inorg.Chem. Volume: 30 Pages: 5011-5017
  • Peer Reviewed
• [Presentation] アセチルCoA合成酵素活性部位のモデル構築：ジアミドジチオラート配位子mbeaをもつ二核ニッケル錯体の合成と反応 (2013)
  • Author(s): 大須理恵・小澤由佳・松本剛・巽和行
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 草津、滋賀
• [Presentation] [3:1] Site-differentiated [4Fe-4S] Clusters: Structure and Spectroscopic Analysis (2012)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi, G. Kehr, G. Erker
  • Organizer: The 14th Joint Seminar University of Munster Nagoya University
  • Place of Presentation: Nagoya
• [Presentation] Synthesis of [3:1] Site-differentiated [4Fe-4S]^+ Cluster Having Tridentate Thiolate TefpS_3^3- by the Reduction of [4Fe-4S]^2+ Cluster with NaBH_4 (2012)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 2ndInternational Conference on MEXT Projectof Integrated Research on Chemical Synthesis "Molecular Functions in Complex Systems"
  • Place of Presentation: Nagoya
• [Presentation] Synthesis of [4Fe-4S]^2+ and [4Fe-4S]^+ Clusters Carrying a Tridentate Thiolate Ligand and a Carboxylate (2012)
  • Author(s): T. Nakamura, T. Terada, T. Matsumoto,K. Tatsumi
  • Organizer: The 2nd International Conference on MEXT Project of Integrated Research on ChemicalSynthesis "Molecular Functions in Complex Systems"
  • Place of Presentation: Nagoya
• [Presentation] Synthesis and Reactions of [3Fe-4S] Clusters Having Tridentate Thiolate: A Model Study of CODehydrogenase Active Site (2012)
  • Author(s): K. Tanaka, T. Nakamura, T. Terada, T.Matsumoto, K. Tatsumi
  • Organizer: The 2nd International Conference on MEXT Projectof Integrated Research on Chemical Synthesis "Molecular Functions in Complex Systems"
  • Place of Presentation: Nagoya
• [Presentation] Dinuclear nickel complexes having diamido-dithiolatembea: Models studies of acetyl CoA synthase (2012)
  • Author(s): R. Osu, Y. Ozawa, A. Oana, T. Matsumoto, and K. Tatsumi
  • Organizer: The 2nd International Conference on MEXT Project of IntegratedResearch on Chemical Synthesis "Molecular Functions in ComplexSystems"
  • Place of Presentation: Nagoya
• [Presentation] 三座チオラート配位子を導入した[4Fe-4S]クラスターと水素化ホウ素ナトリウムの反応 (2012)
  • Author(s): 寺田玲季・松本剛・巽和行
  • Organizer: 錯体化学会第62回討論会
  • Place of Presentation: 富山
• [Presentation] 三座チオラート配位子と1つのカルボキシラートが配位した[1:3]不均等配位 [4Fe-4S]^2+および[4Fe-4S]^1+クラスターの合成 (2012)
  • Author(s): 中村友彦・寺田玲季・松本剛・巽和行
  • Organizer: 錯体化学会第62回討論会
  • Place of Presentation: 富山
• [Presentation] COデヒドロゲナーゼ活性中心のモデル錯体をめざした三座チオラート配位[3Fe-4S]クラスターの合成と反応 (2012)
  • 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62回討論会
  • Place of Presentation: 富山
• [Presentation] [3:1] Site-differentiated [4Fe-4S] Clusters: Structure and Spectroscopic Analysis (2012)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi, G. Kehr, G. Erker
  • Organizer: The 14th Joint Seminar University of M&#252;nster &#8211; Nagoya University
  • Place of Presentation: 名古屋
• [Presentation] Synthesis of [3:1] Site-differentiated [4Fe-4S]+ Cluster Having Tridentate Thiolate TefpS33– by the Reduction of [4Fe-4S]2+ Cluster with NaBH4 (2012)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 2nd International Conference on MEXT Project of Integrated Research on Chemical Synthesis “Molecular Functions in Complex Systems”
  • Place of Presentation: 名古屋
• [Presentation] Synthesis of [4Fe-4S]2+ and [4Fe-4S]+ Clusters Carrying a Tridentate Thiolate Ligand and a Carboxylate (2012)
  • Author(s): T. Nakamura, T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 2nd International Conference on MEXT Project of Integrated Research on Chemical Synthesis “Molecular Functions in Complex Systems”
  • Place of Presentation: 名古屋
• [Presentation] Dinuclear Ni(II)-Ni(II/I/0) ComplexesCoordinated by Diaminedithiolate (dadtEt)2. and Diamidodithiolate (mbpa)4.: Active Site Models of Acetyl CoA Synthase (2011)
  • Author(s): A.Oana, T. Matsumoto, S. Arae, M. Ito, K. Tatsumi
  • Organizer: International Symposium on Chemistry of Reductases IV
  • Place of Presentation: 名古屋
• [Presentation] CH_3-S Bond Cleavage of Ni(I) Cyclam Complexes Having MethylthioetherPendants: A Model Reaction of Methyl Coenzyme M Reductase (2011)
  • Author(s): J. Nishigaki, T. Matsumoto, K. Tatsumi
  • Organizer: The 1st International Conference on MEXT Projectof Integrated Research on Chemical Synthesis
  • Place of Presentation: 札幌
• [Presentation] Dinuclear nickel complexes having diamidodithiolate ligand mbpa: model studies of acetyl CoA synthase (2011)
  • Author(s): T. Matsumoto
  • Organizer: 15th International Conference on Biological Inorganic Chemistry (ICBIC15)
  • Place of Presentation: Vancouver, Canada
• [Presentation] アセチルCoA合成酵素のモデルとなるジアミドジチオラート配位ニッケル (2011)
  • Author(s): 二核錯体, 松本剛・小穴彩香・小澤由佳・巽和行
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋
• [Presentation] 分子内チオエーテルを持つニッケル (I)サイクラム錯体:温度変化による4配位から5配位への可逆的構造変化 (2011)
  • Author(s): 西垣潤一・松本剛・巽和行
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山
• [Presentation] 嫌気性生物の炭素固定に関連する金属酵素のモデル研究.アセチル CoA合成酵素の反応機構解明 (2011)
  • Author(s): 松本剛
  • Organizer: 統合物質創製化学推進事業第2回統合物質シンポジウム「化学合成力と機能創出」
  • Place of Presentation: 名古屋
• [Presentation] 生体内に存在する不均等配位 [4Fe.4S]クラスターのモデル構築 (2011)
  • Author(s): 松本剛・寺田玲季・中村友彦・巽和行
  • Organizer: 第38回有機典型元素化学討論会
  • Place of Presentation: 金沢
• [Presentation] Dinuclear nickel complexes having diamidodithiolate ligand mbpa : model studies of acetyl CoA synthase (2011)
  • Author(s): Tsuyoshi Matsumoto
  • Organizer: 15th International Conference on Biological Inorganic Chemistry (ICBIC15)
  • Place of Presentation: Vancouver, Canada(招待講演)
• [Presentation] アセチルCoA合成酵素のモデルとなるジアミドジチオラート配位ニッケル二核錯体 (2011)
  • Author(s): 松本剛・小穴彩香・小澤由佳・巽和行
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋
• [Presentation] 分子内チオエーテルを持つニッケル(I)サイクラム錯体:温度変化による4配位から5配位への可逆的構造変化 (2011)
  • Author(s): 西垣潤一・松本剛・巽和行
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山
• [Presentation] 嫌気性生物の炭素固定に関連する金属酵素のモデル研究-アセチルCoA合成酵素の反応機構解明 (2011)
  • Author(s): 松本剛
  • Organizer: 統合物質創製化学推進事業第2回統合物質シンポジウム「化学合成力と機能創出」
  • Place of Presentation: 名古屋(招待講演)
• [Presentation] 生体内に存在する不均等配位[4Fe-4S]クラスターのモデル構築 (2011)
  • Author(s): 松本剛・寺田玲季・中村友彦・巽和行
  • Organizer: 第38回有機典型元素化学討論会
  • Place of Presentation: 金沢
• [Presentation] Dinuclear Ni(II)-Ni(II/I/0)Complexes Coordinated by Diaminedithiolate (dadt^<Et>)^<2-> and Diamidodithiolate (mbpa)^<4-> : Active Site Models of Acetyl CoA Synthase (2011)
  • Author(s): A.Oana, T.Matsumoto, S.Arae, M.Ito, K.Tatsumi
  • Organizer: International Symposium on Chemistry of Reductases IV
  • Place of Presentation: 名古屋
• [Presentation] CH_<3->S Bond Cleavage of Ni(I) Cyclam Complexes Having Methylthioether Pendants : A Model Reaction of Methyl Coenzyme M Reductase (2011)
  • Author(s): J.Nishigaki, T.Matsumoto, K.Tatsumi
  • Organizer: The 1^<st> International Conference on MEXT Project of Integrated Research on Chemical Synthesis
  • Place of Presentation: 札幌
• [Presentation] Ligand Substitution Reactions of the Chloride-Coordinated [3:1] Site-Differentiated [4Fe-4S] Clusters (2010)
  • Author(s): D. Liu, T.Matsumoto, K. Tatsumi
  • Organizer: Nagoya University 3rd Global COE in Chemistry Annual Symposium
  • Place of Presentation: 名古屋
  • Year and Date: 2010-06-16
• [Presentation] [4Fe-4S] Clusters Coordinated by the Tridentate Thiolate TempS33. and a Monodentate Thiolate/Carboxylate Ligand (2010)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: Nagoya University Global COE in Chemistry 3rd Annual Symposium
  • Place of Presentation: 名古屋
  • Year and Date: 2010-06-16
• [Presentation] Ligand Substitution Reactions of the Chloride-Coordinated [3:1]Site-Differentiated [4Fe4S] Clusters (2010)
  • Author(s): D.Liu, T.Matsumoto, K.Tatsumi
  • Organizer: Nagoya University Global COE in Chemistry 3^<rd> Annual Symposium
  • Place of Presentation: 名古屋
  • Year and Date: 2010-06-16
• [Presentation] [4Fe-4S] Clusters Coordinated by the Tridentate Thiolate TempS_3^<3-> and a Monodentate Thiolate/Carboxylate Ligand (2010)
  • Author(s): T.Terada, T.Matsumoto, K.Tatsumi
  • Organizer: Nagoya University Global COE in Chemistry 3^<rd> Annual Symposium
  • Place of Presentation: 名古屋
  • Year and Date: 2010-06-16
• [Presentation] 1:3 Site-Differentiated [4Fe-4S] ClustersCarrying a Tridentate Thiolate Ligand anda Carboxylate (2010)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 9th Joint Seminar University of Munster and Nagoya University
  • Place of Presentation: 名古屋
• [Presentation] メチルCoM還元酵素のモデルとなる Ni(I)サイクラム錯体 (2010)
  • Author(s): 松本剛、西垣潤一、巽和行
  • Organizer: 第37回有機典型元素化学討論会
  • Place of Presentation: 東室蘭
• [Presentation] A Model Reaction of Methyl Coenzyme Mreductase: Methane Formation via CH3-S Bond Activation of Ni(I) CyclamComplexes Having Methylthio-Substituted Pendant Chains (2010)
  • Author(s): J. Nishigaki, T. Matsumoto, K., Tatsumi
  • Organizer: The 2010 International Chemical Congress of PacificBasin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] Synthesis and Redox Properties of [1:3] Site Differentiated [4Fe-4S] Clusters Coordinated by Carboxylates and Imidazoles (2010)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 2010 International ChemicalCongress of Pacific Basin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] Dinuclear Nickel Complexes Modeling ofthe Active Site of Acetyl CoA Synthase: AMechanistic Insight (2010)
  • Author(s): T. Matsumoto, M. Ito, K. Tatsumi
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] 1:3 Site-Differentiated [4Fe-4S] Clusters Carrying a Tridentate Thiolate Ligandand a Carboxylate (2010)
  • Author(s): T.Terada, T.Matsumoto, K.Tatsumi
  • Organizer: The 9^<th> Joint Seminar-University of Munster and Nagoya University
  • Place of Presentation: 名古屋
• [Presentation] メチルCoM還元酵素のモデルとなるNi(I)サイクラム錯体 (2010)
  • Author(s): 松本剛、西垣潤一、巽和行
  • Organizer: 第37回有機典型元素化学討論会
  • Place of Presentation: 東室蘭
• [Presentation] A Model Reaction of Methyl Coenzyme M Reductase : Methane Formation via CH_3-S Bond Activation of Ni(I) Cyclam Complexes Having Methylthio-Substituted Pendant Chains (2010)
  • Author(s): J.Nishigaki, T.Matsumoto, K.Tatsumi
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] Synthesis and Redox Properties of [1:3] Site Differentiated [4Fe-4S] Clusters Coordinated by Carboxylates and Imidazoles (2010)
  • Author(s): T.Terada, T.Matsumoto, K.Tatsumi
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] Dinuclear Nickel Complexes Modeling of the Active Site of Acetyl CoA Synthase : A Mechanistic Insight (2010)
  • Author(s): T.Matsumoto, M.Ito, K.Tatsumi
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、ハワイ
• [Presentation] Model Studies of NiFe-Hydrogenase and Acetyl CoA Synthase
  • Author(s): T. Matsumoto
  • Organizer: Organimetallic Seminar, University of Rochester
  • Place of Presentation: Rochester, NY
  • Invited
• [Remarks] Angew. Chem. Int. Ed. 2010, 49,4209-4212の中表紙 成果は論文誌の表紙等に取り上げられた
• [Remarks] Chem. Asian J. 2012, 7, 920-929の中表紙 成果は論文誌の表紙等に取り上げられた
• [Remarks] Inorg. Chem. 2012, 51, 5173-5187の表紙 成果は論文誌の表紙等に取り上げられた