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第4班 生体系複合場金属錯体による新反応系の構築

Research Project

Project/Area Number 04225107
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionOkazaki National Research Institutes

Principal Investigator

田中 晃二  岡崎国立共同研究機構, 分子科学研究所, 教授 (00029274)

Co-Investigator(Kenkyū-buntansha) 矢野 重信  奈良女子大学, 理学部, 教授 (60011186)
長野 哲雄  東京大学, 薬学部, 助教授 (20111552)
北島 信正  東京工業大学, 資源化学研究所, 助教授 (20177843)
大倉 一郎  東京工業大学, 生命理工学部, 教授 (90089821)
青山 安宏  長岡技術科学大学, 工学部, 教授 (00038093)
船引 卓三  京都大学, 工学部, 助教授 (70026061)
Project Period (FY) 1991 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥52,000,000 (Direct Cost: ¥52,000,000)
Fiscal Year 1993: ¥34,000,000 (Direct Cost: ¥34,000,000)
Fiscal Year 1992: ¥18,000,000 (Direct Cost: ¥18,000,000)
Keywords亜硝酸還元 / 分子認識 / 光誘起電子移動 / SOD / イオン認識錯体 / ヘモシアニンモデル / 酸素運搬 / 二酸化炭素固定 / α-ケト酸 / オキシヘモシアニン / オキシチロシナーゼ / オキシゲナーゼ / スーパーオキシド / 人工SOD / オリゴ糖錯体
Research Abstract

金属たん白質の機能を化学的に構築するために基質の認識能を有する機能性金属錯体を合成して金属たん白質を範とした新しい反応系を開発することを目的として,研究を行ない以下の知見を得た。
銅たん白による亜硝酸還元反応を化学的に解明するために,酸素配位(ニトリト錯体)と窒素配位(ニトロ錯体)の亜硝酸銅錯体を合成した。前者の錯体を経由して亜硝酸イオンが還元される際には,銅に結合した酸素あるいは末端酸素が還元脱水を受けるために,必然的にNO発生を伴ってN_2Oが生成することを明らかにした。モノ-オキシゲナーゼ反応中間体モデル錯体として銅および鉄単核ならびに2核錯体の単離に成功し,ラジカル機構でアルケン,アルキン類の酸素酸化反応が進行することを明らかにした。亜鉛ミオグロビンのアミノ酸残基中のリシンあるいはヒスジンを無水コハク酸で化学修飾を行ない,変異ミオグロビンからメチルビオローゲンへの光電子移動反応を測定し,修飾サイトの違いにより3倍程度の差が生じることを見いだし,反応中心付近の負電荷の増大が電子移動に大きな役割をもつ機構を提案した。新規ポリアミン鉄錯体が有する高いSOD活性はピリジル基の鉄原子へのon‐off機構が重要な因子であることを錯体の構造解析を含めた種々の物理化学的測定により明らかにした。トリス(2-アミノエチルアミン)(trm)とL-ラムノースを配位子として有する〔Co(L‐Rha_3‐tren)〕SO_43H_2OのX線構造解析により,SO_4^<2‐>イオンが分子間水素結合により取り込まれたDELTA-lambda3(lel)構造であることを明らかにした。一方,対イオンをSO_4^<2‐>イオンに代えてハロゲンイオンを使用すると,コットン効果が逆転してLAMBDA-lambda3(ob)構造に変化することを見いだした。これらの結果はSO_4^<2‐>イオンが錯体に接近すると分子内水素結合が破壊され,SO_4^<2‐>イオンとの水素結合により,大きな構造変化が引き起こされたものと解釈され,新たなイオン識別能を有するCo(II)配糖錯体の確立に成功した。

Report

(2 results)
  • 1993 Annual Research Report
  • 1992 Annual Research Report
  • Research Products

    (40 results)

All Other

All Publications (40 results)

  • [Publications] H.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2]PF_6[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and[Ru(bpy)_2(CO)(eta^1‐CO_2)]・3H_2O(bpy=2,2′‐bipyridyl)" Inorg.Chem.32. 1508-1512 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Komeda: "Molecular Structure of Copper Nitrito Complex as the Reaction lntermediate of Dissimilatory Reduction of NO_2^‐" Chem.Lett.1521-1524 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Kobayashi: "CHpi Interaction as an Important Driving Force of Host‐Guest Complexation in Apolar Organic Media.Binding of Monools and Acetylated Compounds to Resoricinol Cyclic Tetramer As Studiedby 1H NMR and Circular Dichroism Spectroscopy" J.Am.Chem.Soc.115. 2648-2654 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Kobayashi: "Binding of Amino Acids in water to a Highly Electron‐Rich Aromatic Cavity of Pyrogallol or Resoricinol Cyclic Tetramer As pi‐Base" Tetrahedron Lett.34. 5121-5124 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kitajima: "mu‐eta2:eta2‐Peroxide in Biological Systems" J.Chem.Soc.,Dalton Trans.2665-2671 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kitajima: "Synthesis,Molecular Structure,and Reaction of(Alkylperoxo)copper(II)Complex" J.Am.Chem.Soc.115. 7872-7873 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kitajima: "A Reaction Mimic of Tyrosine Hydroxylase:Hydroxylation of a Phenoxo Ferric Complex to a Catecholate Complex with mCPBA" J.Am.Chem.Soc.115. 9335-9336 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] S.Aono: "Photoinduced Electron Transter between Zinc Proloporphyline Reconstituted Myoglobin and Methylviologen" Bull.Chem.Soc.Jpn.65. 591-593 (1992)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Yahiro: "Regulation of the Ligand Field Strength of a Cobalt(III)Complex by Methyl Substitutions on a Tetraamine Ligand:An Important Factor for the Dissociation of a Generally Inert Chelated Amino Acidate Ligand form a Cobalt(III)Complex" Inorg.Chem.32. 4166-4167 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Tanase: "Inversion of Configuration around the Seven‐Coordinated Cobalt Center Induced by an Interaction between Sugars and Tetrahedral Oxoanions" Inorg.Chem.33. 5-6 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Tanase: "Synthesis and Characterization of Nicke(II)Complexes containing Ligands derived from Disaccharides and 1,3‐Diaminopropane." J.Chem.Soc.,Dalton Trans.2645-2652 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Tanaka: "Synthesis and Characterization of Bis(2,2'-bipyridine)nitrocarbonylruthenium(II)Hexsafluorophoshate." Inorg.Chem.31. 1971-1973 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Crystal Structure of cis-(Carbon monoxide)(η1-carbon dioxide)bis(2,2'-bipyridine)ruthenium,an Active Speciesin Catalytic CO_2 Reduction Affording CO and HCOO^-." Organometallics. 11. 1450-1451 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Structure and Bonding of cis-[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN(bpy=2,2'-bipyridine)" Organometallics. 11. 3171-3172 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->." J.Am.Chem.Soc.114. 3625-3630 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Kambayashi: "(Ph_4As)_2[Fe_4S_4(SAd)_4]and Stabilization of [Fe_4S_4(SAd)_4]^- Site in Aqueous Media." Chem.Lett.919-922 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Comparative Study on Crystal Structures of [Ru(bpy)_2(CO)_2]PF_6,[Ru(bpy)_2(CO)(C(O)OCH_3)]B(C_6H_5)_4・CH_3CN,and [Ru(bpy)_2(CO)(η^1-CO_2)]・3H_2O(bpy=2,2'-bipyridyl)" Inorg.chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Tanaka: "Evaluation of Acidity of CO_2 in Protic Media.Carboxylation of Reduced Quinone." Chem.Lett.

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Tanase: "A Spontaneous Fixation of Carbon Dioxide in Air by a Nickel Diamine Complex:Synthesis and Characterization of a Trinuclear Nichel(II)Complex with a Novel Hydrogen Bonding System around Carbonate Ligand." Inorg.chem.31. 1058-1062 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Tanase: "C-2 Epimerization of Aldoses Promoted by Cobalt(II)-N-Alkylated Diamine Complexes,Involving a Stereospecific Rearrangement of the Carbon Skeleton." J.Chem.Res.252-253 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Murata: "Synthesis of Mixed-Metal Sulfido Clusters with Cuboidal Mo_3PdS_4Core which Coordinate Alkene to the Unique Pd Site Surrounded by Sulfide Ligands." J.Am.Chem.Soc.8287-8288 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Abe: "High Dioxygen Uptake by Hetero-Metal Binuclear Co(II)-Fe(II)-schiff Base Complexes Systems in Dimethyl Sulfoxide." Chem.Lett.897-900 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Kojima: "Observation of Radical intermediates for Unusual C-N Bond Formation of α-Aminomalonate to Give α-Diamine Linkage.ESR Studies on Electron Transfer Reactionsin Co(III)-Polyamine Complexes." Inorg.Chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Yano: "Stereochemistry of Sugar Units Contained in N-Glycoside Ligands of Octahedral Ni(II)Complexes Derived form[Ni(tn)_3]^<2+> and Natural Aldohexoses." J.Chem.Soc.,Dalton Trans.

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structure of the μ-η^2:η^2 Peroxo Dinuclear Copper(II)Complexes,[Cu(HB(3,5-R_2pz)_3]_2(O_2)(R=iPrandPh)" J.Am.Chem.Soc.114. 1277-1291 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Hikichi: "Phosphate Ester Cleavage with a Zinc Hydroxide Complex.Formation and Crystal Structure of a Dineclear Zinc Complex Bridged with a Phosphate Monoester." J.Chem.Soc.,Chem.Commun.814-815 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthesis and Molecular Structure of Diferrous Complexes Containing a Bis(hydroxo)or a Hydroxo Carboxylato Bridge." Inorg.Chem.31. 3342-3343 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthesis and Characterization of Copper Complexes with Hindered Tris(pyrazolyl)borate Ligands as Models for the Active Sites of Copper Proteins." J.Inorg.Biochem.,. 47. 17 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthetic Approach to the Dioxygen Binding Sites in Metalloproteins." J.Mol Catal.,. 74. 143-151 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "X-Ray Structure of Thiolate Copper(II)Complexes Bearing Close Spectroscopic Similarities to Blue Copper Proteins." J.Am.Chem.Soc.114. 9232-9233 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.J.Baldwin: "Spectroscopic Studies of Side-on Peroxo-Bridged Binuclear Copper(II)Model Complexes of Relevance to Oxyhemocyanin and Oxytyrosinase." J.Am.Chem.Soc.114. 10421-10431 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthesis and Molecular Structure of an Unsymmetric Dimanganese(II)Carboxylato Complex." J.Chem.Soc.,Chem.Commun.

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthetic Approach to the Structures and Functions of Copper Proteins." Inorg.Chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] N.Kitajima: "Synthesis,Structure and Properties of μ-μ_2:μ_2 Peroxo Dinuclear Copper Complex.Modeling the Active Site of Oxyhemocyanin and Oxytyrosinase." Bioinorganic Chemistry of Copper.

    • Related Report
      1992 Annual Research Report
  • [Publications] 北島 信正: "銅蛋白質の活性部位の合成モデル錯体" 季刊化学総説、生物無機化学の新展開.

    • Related Report
      1992 Annual Research Report
  • [Publications] 船引 卓三: "非ヘム鉄タンパク質の合成モデル" 季刊化学総説、生物無機化学の新展開.

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Funabiki: "Chracteristic Effect of Pyridine on the NIH Shift and Selectivity in the Monoxygenation of Aromatic Compounds Catalyzed by a Nonheme Iron Complex/Hydroquinones/O2 System." Chem.Lett.1279-1282 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Funabiki: "Controlled Monoxygenation of n-and Isoalkanes with Molecular Oxygen Catalyzed in Nonheme Iron Complex/hydroquinones Systems." Chem.Lett.2303-2306 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 長野 哲雄: "人工SODーその開発的前線ー" SODの基礎と臨床. 62-67 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 長野 哲雄: "Superoxide dismutase mimicsの分子設計" フリーラジカルと病態:疾患モデルからベッザサイドへ. 717-728 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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