1998 Fiscal Year Annual Research Report

金属酵素における生体系特殊反応場の構築と機能制御

Research Project

Project/Area Number	09440230
Research Institution	Nagoya Institute of Technology
Principal Investigator	増田秀樹名古屋工業大学, 工学部, 教授 (50209441)
Co-Investigator(Kenkyū-buntansha)	小澤智宏岡崎国立共同研究機構, 分子科学研究所, 助手 (70270999) 実川浩一郎名古屋工業大学, 工学部, 助教授 (50235793)
Keywords	部位特異的分子認識 / アミノ酸 / 酸素錯体 / 金属錯体 / 特殊反応場 / ATPase / ビタミンB6
Research Abstract	生体系に見られる金属酵素等の優れた基質特異性や高効率高反応性は全て水素結合、疎水結合、静電結合等の非共有結合性相互作用によって発現・制御されている。本研究では、そのような酵素機能の解明を目的として、以下の3つのテーマについて酵素類似機能を有する金属錯体分子の構築を行ってきた。 (1) 部位特異的分子認識能を有する金属錯体の構築と反応制御:アミノ酸、ペプチド、リン酸を認識する酵素類似機能錯体の開発研究遂行中、水中、リン酸エステルであるNPPとの反応においてピロリン酸の合成に初めて成功した。この反応は,ATPaseのモデル反応であり、きわめて重要な反応である。 (2) 新規ビタミンB6反応の開発:アミノ酸とピリドキサールよりなるシッフ塩基配位子のコバルト錯体を合成し、アミノ基転位反応を錯体上でモデル化した。その結果、ターピリジンとシッフ塩基との三元錯体において特異な水酸化やイミノ化が見つかり、そのメカニズムについて検討した。その結果、この反応はコバルト(II)種を経由せず、ラジカル的に進行することが明らかとなった。 (3) 酸素分子認識能力を付与した遷移金属錯体の合成:生体系で酸素の捕捉活性化に関わる銅および鉄酵素の機能発現を目指して、非共有結合性相互作用基を配した金属錯体を設計・合成的した。それらを用いて、過酸化水素との反応を試みたところ、いずれの場合にも金属にハイドロパーオキサイドが配位した錯体を生成した。これらはX線、Raman、UV-VIS、ESR、質量分析法等により、固体および溶液状態の両面からアプローチし構造確認に初めて成功した。

Research Products
(12 results)

All Other

All Publications (12 results)

[Publications] A.Wada: "Structural and Spectroscopic Characterization of Hydroperoxo Mononuclear Copper Complex with Tripodal Pyridylamine Ligands." Angew.Chem.,Int,Ed.Engl.37. 798-799 (1998)
[Publications] N.Sakurai: "Spectral Properties of Cytochrome c553 and a Membrane-bound Cytochrome b from Alcaligenes xylosxidans GIFU 1051." Bull.Chem.Soc.Jpn.71. 135-140 (1998)
[Publications] M.Harata: "Preparation,Structure and Physico-chemical Properties of Copper(II)Complex with New Tripodal Tetradentate Ligand,Bis{(6-pivaloylamino-2-pyridyl)methyl)}{5-carboxy-2-pyridyl)methyl}amine(BPCA),and Reaction of Its Cu(I)Complex with Dioxygen." J.Coord.Chem.44. 311-324 (1998)
[Publications] M.Harata: "Preparations,Structures and Properties of Cu(II)Complexes with Tripodal Tetradentate Ligand,Tris(6-pivaloylamino-2-pyridylmethyl)amine(TPPA),and Reaction of Its Cu(I)Complex with Dioxygen." Bull.Chem.Soc.Jpn.71. 637-645 (1998)
[Publications] M.Harata: "Preparations,Structures,and Properties of Cu(II)Complexes with a New Tripodal Tetradentate Ligand,N-(2-Pyridylmethyl)bis(6-pivalamido-2-pyridylmethyl)amine,and Reactivities of the Cu(I)Complex with Dioxygen." Bull.Chem.Soc.Jpn.71. 1031-1038 (1998)
[Publications] M.Mizutani: "Foramation of a Novel Diaqua Disodium Tetrakis(1-methyluracilato)palladium Complex with a Unique Supramolecular Channel Structure." Chem.Lett.663-664 (1998)
[Publications] T.Funabiki: "X-ray Crystallographic and Absorption Spectroscopic Analyses of Structures of Catecholato(pyridine)iron Chloride Complexes in Relevance to Functional Model Complexes for Catechol 1,2-Dioxygenases." Inorg.Chim.Acta. 275-276. 222-229 (1998)
[Publications] M.Mizutani: "An Infinite Chiral Single-helical Structure formed in Cu(II)-L-/D-glutamic Acid System." Inorg.Chim.Acta. 298. 105-110 (1998)
[Publications] H.Kumita: "Structures and Electrochemical Properties of the Co(III)Ternary Complexes containing the NO_3-Type Tripodal Tetradentate Ligands and Amino Acids.Effect of the Outer Coordination Sphere to exert the Reduction Potential." Inorg.Chim.Acta. 298. 160-166 (1998)
[Publications] S.Ogo: "Synthesis,Structure,and Spectroscopic Properties of [Fe^<III>(TNPA)(OH)(PhCOO)]ClO_4:A Plausible Model Complex for an Active Form of Soybean Lipoxygenase-1." Angw.Chem.Int.Ed.Engl.37. 2102-2104 (1998)
[Publications] M.Mizutani: "Nucleobase Stacking Evidenced on Ternary Metal(Palladium(II),Copper(II))Complexes with Nucleobase Amino Acids and Aromatic Diimines." Inorg.Chem.38. 420-421 (1999)
[Publications] A.Wada: "Synthesis and Characterization of Novel Alkylperoxo Mononuclear Iron(III)Complexes with a Tripodal Pyridylamine Ligand:A Model for Peroxo Intermediates in Reactions Catalyzed by Non-Heme Iron Enzymes." Inorg.Chem.(印刷中). (1999)

1998 Fiscal Year Annual Research Report

金属酵素における生体系特殊反応場の構築と機能制御

Principal Investigator

増田 秀樹 名古屋工業大学, 工学部, 教授 (50209441)

Research Products

[Publications] A.Wada: "Structural and Spectroscopic Characterization of Hydroperoxo Mononuclear Copper Complex with Tripodal Pyridylamine Ligands." Angew.Chem.,Int,Ed.Engl.37. 798-799 (1998)

[Publications] N.Sakurai: "Spectral Properties of Cytochrome c553 and a Membrane-bound Cytochrome b from Alcaligenes xylosxidans GIFU 1051." Bull.Chem.Soc.Jpn.71. 135-140 (1998)

[Publications] M.Harata: "Preparation,Structure and Physico-chemical Properties of Copper(II)Complex with New Tripodal Tetradentate Ligand,Bis{(6-pivaloylamino-2-pyridyl)methyl)}{5-carboxy-2-pyridyl)methyl}amine(BPCA),and Reaction of Its Cu(I)Complex with Dioxygen." J.Coord.Chem.44. 311-324 (1998)

[Publications] M.Harata: "Preparations,Structures and Properties of Cu(II)Complexes with Tripodal Tetradentate Ligand,Tris(6-pivaloylamino-2-pyridylmethyl)amine(TPPA),and Reaction of Its Cu(I)Complex with Dioxygen." Bull.Chem.Soc.Jpn.71. 637-645 (1998)

[Publications] M.Harata: "Preparations,Structures,and Properties of Cu(II)Complexes with a New Tripodal Tetradentate Ligand,N-(2-Pyridylmethyl)bis(6-pivalamido-2-pyridylmethyl)amine,and Reactivities of the Cu(I)Complex with Dioxygen." Bull.Chem.Soc.Jpn.71. 1031-1038 (1998)

[Publications] M.Mizutani: "Foramation of a Novel Diaqua Disodium Tetrakis(1-methyluracilato)palladium Complex with a Unique Supramolecular Channel Structure." Chem.Lett.663-664 (1998)

[Publications] T.Funabiki: "X-ray Crystallographic and Absorption Spectroscopic Analyses of Structures of Catecholato(pyridine)iron Chloride Complexes in Relevance to Functional Model Complexes for Catechol 1,2-Dioxygenases." Inorg.Chim.Acta. 275-276. 222-229 (1998)

[Publications] M.Mizutani: "An Infinite Chiral Single-helical Structure formed in Cu(II)-L-/D-glutamic Acid System." Inorg.Chim.Acta. 298. 105-110 (1998)

[Publications] H.Kumita: "Structures and Electrochemical Properties of the Co(III)Ternary Complexes containing the NO_3-Type Tripodal Tetradentate Ligands and Amino Acids.Effect of the Outer Coordination Sphere to exert the Reduction Potential." Inorg.Chim.Acta. 298. 160-166 (1998)

[Publications] S.Ogo: "Synthesis,Structure,and Spectroscopic Properties of [Fe^<III>(TNPA)(OH)(PhCOO)]ClO_4:A Plausible Model Complex for an Active Form of Soybean Lipoxygenase-1." Angw.Chem.Int.Ed.Engl.37. 2102-2104 (1998)

[Publications] M.Mizutani: "Nucleobase Stacking Evidenced on Ternary Metal(Palladium(II),Copper(II))Complexes with Nucleobase Amino Acids and Aromatic Diimines." Inorg.Chem.38. 420-421 (1999)

[Publications] A.Wada: "Synthesis and Characterization of Novel Alkylperoxo Mononuclear Iron(III)Complexes with a Tripodal Pyridylamine Ligand:A Model for Peroxo Intermediates in Reactions Catalyzed by Non-Heme Iron Enzymes." Inorg.Chem.(印刷中). (1999)

増田秀樹名古屋工業大学, 工学部, 教授 (50209441)