1990 Fiscal Year Annual Research Report

酵素機能の化学的展開に関する研究

Research Project

Project/Area Number	01303007
Research Institution	Osaka University
Principal Investigator	大城芳樹大阪大学, 工学部, 教授 (70028984)
Co-Investigator(Kenkyū-buntansha)	木村栄一広島大学, 医学部, 教授 (30034010) 生越久靖京都大学, 工学部, 教授 (90026188) 大野惇吉京都大学, 化学研究所, 教授 (70027077) 井上祥平東京大学, 工学部, 教授 (20010762) 青山安宏長岡技術科学大学, 工学部, 教授 (00038093)
Keywords	酵素モデル / 補酵素モデル / 分子認識 / 細胞認識 / 金属錯体
Research Abstract	本年度は平成元年度の研究成果をさらに発展させ、酵素機能の化学的展開に関する研究をつぎのような観点から総合的に推進した。【1】酵素、補酵素機能の解明とその応用、【2】分子認識と選択的取り込み場の設計、【3】生体金属の機能と応用、【4】生体過程の調節物質の機能と応用。その結果、平成2年度においては以下に示したような成果が得られた。1.酸化還元酵素のモデルとして主に補酵素PQQやフラビンモデルを取り上げ、それらの機能解明およびそれらを用いた高効率的触媒反応を見いだした。2.グリセロ-ル脱水素酵素の反応系において基質の反応性と立体化学の間の興味深い関係を明らかにした。3.亜鉛酵素モデルとしてイミダゾ-ル基を有する機能性界面活性剤を合成し、エステル加水分解に対して大きな触媒効果を発揮することを見いだした。4.機能性合成二分子膜を用いた効率的な変換反応を確立した。5.ミクロ溶媒和による非選択的基質取り込み場を構築した。6.脂質二分子膜上での分子認識と選択的取り込み場の設計を行なった。7.新規なポルフィリン配位子の合成に成功した。8.ルテニウムポルフィリン錯体を用いた高効率酸素転移触媒反応を明らかにした。9.環状ポリアミン金属錯体を用いて生体金属の機能を解明した。10.モリブデンコファクタ-モデルとしてのモリブデン錯体の合成とその機能の解明に成功した。11.モリブデンおよびタングステンに配位した窒素分子の反応性を明らかにした。12.二核銅および鉄タンパクの構造および機能類似錯体の合成に成功した。さらに平成3年2月5日、研究報告会を開催し、研究者相互の研究成果に関して情報交換を行なうと共に、今後の研究展望について熱のこもった議論を交わした。

Research Products

(48 results)

All Other

All Publications (48 results)

[Publications] Yoshiki Ohshiro: "Mechanism of Amine Oxidation by Coenzyme PQQ" Bioorganic Chemistry.
[Publications] Yoshiki Ohshiro: "Reaction of Trimethyl Ester of Coenzyme PQQ (PQQTME) and Amines in.Organic Media.Products and Mechanism" J.Org.Chem.
[Publications] Yasuhiro Aoyama: "TwoーPoint HydrogenーBonding Interaction:A Remarkable ChainーLength Selectivity in the Binding of Dicarboxylic Acids with ResorcinolーAldehyde Cyclotetramer." J.Am.Chem.Soc.112. 2807-2808 (1990)
[Publications] Yasuhiro Aoyama: "Simultaneus Hydrogen Bonding and Metal Coordination Interaction in the TwoーPoint Fixation of Amino Acids with a Bifunctional Metalloporphyrin Recepter." J.Am.Che.Soc.112. 3145-3151 (1990)
[Publications] Yasuhiro Aoyama: "Highly Stereoselective Glycosidation of Ribose Solubilized in Apolar Organic Media via HostーGuest Complexation" Tetrahedron Lett.31. 6193-6196 (1990)
[Publications] Shohei Inoue: "Reaction of Carbon Dioxide with (Porphyrinato)aluminum Thiolates." Chem.Lett.551-554 (1990)
[Publications] Shohei Inoue: "Stereoselective Formation of Aluminum Enolate on Capped porphyrin." Chem.Lett.1167-1170 (1990)
[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.69.Mechanism of Stereospecific(Net) Hydride Transfer Controlled by Electronic Effect." Bull.Chem.Soc.Jpn.63. 813-818 (1990)
[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.71.A Convenient Route to the Synthesis of Javavione." Bull.Chem.Soc.Jpn.63. 1255-1257 (1990)
[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.72.Isotope Effect to Prove the MultiーStep Mechanism in the Reduction with an NAD(P)H Analog" Bull.Chem.Soc.Jpn.63. 2682-2686 (1990)
[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.73.StructureーStereochemistry Relationship in the Reaction of NAD Analog." Bull.Chem.Soc.Jpn.64. 81-86 (1991)
[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.74.EntropyーControlled Kinetics,Stereochemistry,and Tunneling Effect." Bull.Chem.Soc.Jpn.64. 87-90 (1991)
[Publications] Hisanobu Ogoshi: "Novel 1:1 Complex of Rhodium(III)porphyrins with Nucleobases." Chem.Lett.51-54 (1990)
[Publications] Hisanobu Ogoshi: "Epoxidation Reaction Catalysed by Cyclodextrin Sandwiched Porphyrin in Aqueous Buffer Solution." J.Chem.Soc.,Chem.Commun.1594-1595 (1990)
[Publications] Hisanobu Ogoshi: "Regioselectivities and Stereoselectivities of Singlet Oxygen Generated by Cyclodextrin Sandwiched Porphyrin Sensitization.Lopoxygenaseーlike Activity." J.Am.Chem.Soc.
[Publications] Eiichi Kimura: "Isolation and Unusual Stability of a New Macrocyclic Polyamine Containing a Phthalimidine." J.Org.Chem.55. 764-766 (1990)
[Publications] Eiichi Kimura: "A Novel CyclamーNickel(II) Complex Appended with a trisー(2,2^′ーbipyridine)ーRuthenium(II) Complex." J.Chem.Soc.,Chem.Commun.,. 397-398 (1990)
[Publications] Eiichi Kimura: "A Zinc(II) Complex of 1,5,9ーTriazocyclododecane(12aneN3)as a Model for Carbonic Anhydrase." J.Am.Chem.Soc.112. 5805-5811 (1990)
[Publications] Eiichi Kimura: "Polarographic Study of the Rates of the Dissociation Reactions of the Eu(III)ーHAHA Complex and of the Eu(III)ーGd(III)ー,and Ho(III)ーPAPA Complexes." Bull.Chem.Soc.,Jpn.63. 2639-2645 (1990)
[Publications] Eiichi Kimura: "Momoー,Diー,and Tetrafluorinated Cyclams." J.Am.Chem.Soc.112. 9237-9245 (1990)
[Publications] Eiichi Kimura: "Acid Properties of Zinc(II) and Cadmium(II) in Complexation with Macrocyclic Oxopolyamine Ligands." Inorg.Chem.29. 4621-4929 (1990)
[Publications] Eiichi Kimura: "A Novel Cyclam Appended with 3ーHydroxypyridine.An Ambident Donor Ligand Comprising a Pyridyl N and A Pyridinolate O^ー Donors." Inorg.Chem.29. 4991-4996 (1990)
[Publications] Toyoki Kunitake: "Layered Arrangement of Oriented Myoglobins in Cast Films of a Phosphate Bilayer Membrane" J.Am.Chem.Soc.112. 6744-6745 (1990)
[Publications] Toyoki Kunitake: "Design of Spatial Disposition of Anionic Porphyrins in Matrices of Ammonium Bilayer Membrane" J.Am.Chem.Soc.113. 621-630 (1991)
[Publications] Seiji Shinkai: "Coenzyme Models.52.Diastereoーdifferentiating Hydrogen Transfer in 5ーdeazaflavin Oxidation of Alcohols and Amines." J.Chem.Soc.,Perkin Trans I. 1075-1078 (1990)
[Publications] Junzo Sunamoto: "The Effect of Polysaccharide Adsorption on Surface Potential of Phospholipid Monolayers Spread at waterーAir Interface" Chem.Lett.299-302 (1990)
[Publications] Junzo Sunamoto: "Functinalized Liposomes in Medicine." BIOmedica. 5. 31-34 (1990)
[Publications] Waichiro Tagaki: "Metal IonーFacilitated Oxidations of Dihydropyridines with Molecular Oxygen and Hydrogen Peroxide" J.Chem.Soc.,Perkin Trans II. 1645-1650 (1990)
[Publications] Waichiro Tagaki: "RateEnhancing MultiーSite Interactions in Ester Hydrolysis Catalyzed by Cu^<2+>Complexes of Surfactant Imidazole Ligands in Nonーionic Micelles." Tetrahedron Lett.31. 7023-7026 (1990)
[Publications] Waichiro Tagaki: "Hydrolytic Metalloenzyme Models.Micellar Effects on the Activation of the Hydroxyl Groups of Alkylー2ーhydroxymethylimidazole Ligands by Cu^<2+> in the・・・・・・" Bull.Chem.Soc.Jpn.64. 74-80 (1991)
[Publications] Akira Nakamura: "Synthesis and Crystal Structure of a cisーDioxomolybdenum(VI) Complex with two Benzenedithiolato Ligands.(NEt_4)_2[Mo^<VI>O_2(1,2ーbenzenethiolato)_2]." Chem.Lett.1655-1656 (1990)
[Publications] Akira Nakamura: "Transition Metal Thiolates:Synthetic,Catalytic,and Biomimetic Aspects." Pure & Appl.Chem.62. 1011-1020 (1990)
[Publications] Akira Nakamura: "Oーatom Transfer Biomimetic Oxidation of Benzoin in the Presence of Monooxomolybdenum(VI) Thiolate Complexes." J.Mol.Cata.64. 247-256 (1991)
[Publications] Yoshio Hisaeda: "Hydrophobic Vitamin B_<12>.8.CarbonーSkeleton Rearrangement Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Bioorg.Chem.18. 49-62 (1990)
[Publications] Yoshio Hisaeda: "Preparation and Molecular Recognition Behavior of a Hexapus Azaparacyclophane" Tetrahedron Lett.31. 1027-1030 (1990)
[Publications] Yoshio Hisaeda: "Functionalized Bilayer Membranes as Artificial Tryptophan Synthase.Caracterization of Catalytic Efficiency Substrate Specificity,and Reaction Selectivity." Bull.Chem.Soc.Jpn.63. 2339-2345 (1990)
[Publications] Masanobu Hidai: "Novel Disilylation and Germylation of Coordinated Dinitrogen in cisー[W(N_2)_2(PMe_2Ph)_4]" Chem.Lett.1303-1306 (1990)
[Publications] Masanobu Hidai: "Regioselective Alkylation of Tungsten Diazoalkane Complexes via Alkenyldaizenido Complexes." J.Chem.Soc.,Chem.Commun.1569-1571 (1990)
[Publications] Masanobu Hidai: "Regioselective Monoー and DiーCーacylation of Tungsten Diazoalkane Complexes via Alkenyldiazzenido Complexes." Chem.Lett.
[Publications] Masaaki Hirobe: "Synthesis of a Highly Stable Porphinatoiron Coordinated by Thiolate Anion as a Model for Cytochrome Pー450 and Its Catalytic Activity in OーO Bond Cleavage." J.Am.Chem.Soc.112. 7051-7053 (1990)
[Publications] Masaaki Hirobe: "Sulfide Oxidation,Amine NーDemethylation,and Olefin Oxidation by HemeーUndecapeptide,Microperoxidaseー11,in the Presence of Hydrogen Peroxide." Tetrahedron Lett.31. 3163-3166 (1990)
[Publications] Masaaki Hirobe: "3ーHydroxycoumarins:First Direct Preparation from Coumarins using a Cu^<2+>ーAscorbic AcidーO_2 System,and Their Potent Bioactivities." Biochem.Biophys.Res.Commun.168. 169-175 (1990)
[Publications] Shunーichi Murahashi: "TungstenーCatalyzed Oxidation of Secondary Amines to Nitrones." J.Org.Chem.55. 1736-1744 (1990)
[Publications] Shunーichi Murahashi: "TungstenーCatalyzed Oxidation of Tetrahydroquinones with Hydrogen Peroxide:A Novel Method for theSynthesis of Cyclic Hydroximic Acids." J.Org.Chem.55. 1744-1749 (1990)
[Publications] Shunーichi Murahashi: "New Aspects of Oxypalladation of Alkenes." Acc.Chem.Res.23. 49-54 (1990)
[Publications] Yoshihiko Moroーoka: "Formation and Characterization of a Mononuclear(Acylperoxo)copper(II) Complex." Inorg.Chem.29. 357-358 (1990)
[Publications] Yoshihiko Moroーoka: "Fixation of Atmospheric CO_2 by a Copper(II) Complex." J.Chem.Soc.,Chem.Commun.1357-1358 (1990)
[Publications] Yoshihiko Morooka: "Reaction Aspects of a ーPeroxo Binuclear Copper(II)Complex." J.Am.Chem.Soc.112. 8833-8839 (1990)

1990 Fiscal Year Annual Research Report

酵素機能の化学的展開に関する研究

Principal Investigator

大城 芳樹 大阪大学, 工学部, 教授 (70028984)

Research Products

[Publications] Yoshiki Ohshiro: "Mechanism of Amine Oxidation by Coenzyme PQQ" Bioorganic Chemistry.

[Publications] Yoshiki Ohshiro: "Reaction of Trimethyl Ester of Coenzyme PQQ (PQQTME) and Amines in.Organic Media.Products and Mechanism" J.Org.Chem.

[Publications] Yasuhiro Aoyama: "TwoーPoint HydrogenーBonding Interaction:A Remarkable ChainーLength Selectivity in the Binding of Dicarboxylic Acids with ResorcinolーAldehyde Cyclotetramer." J.Am.Chem.Soc.112. 2807-2808 (1990)

[Publications] Yasuhiro Aoyama: "Simultaneus Hydrogen Bonding and Metal Coordination Interaction in the TwoーPoint Fixation of Amino Acids with a Bifunctional Metalloporphyrin Recepter." J.Am.Che.Soc.112. 3145-3151 (1990)

[Publications] Yasuhiro Aoyama: "Highly Stereoselective Glycosidation of Ribose Solubilized in Apolar Organic Media via HostーGuest Complexation" Tetrahedron Lett.31. 6193-6196 (1990)

[Publications] Shohei Inoue: "Reaction of Carbon Dioxide with (Porphyrinato)aluminum Thiolates." Chem.Lett.551-554 (1990)

[Publications] Shohei Inoue: "Stereoselective Formation of Aluminum Enolate on Capped porphyrin." Chem.Lett.1167-1170 (1990)

[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.69.Mechanism of Stereospecific(Net) Hydride Transfer Controlled by Electronic Effect." Bull.Chem.Soc.Jpn.63. 813-818 (1990)

[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.71.A Convenient Route to the Synthesis of Javavione." Bull.Chem.Soc.Jpn.63. 1255-1257 (1990)

[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.72.Isotope Effect to Prove the MultiーStep Mechanism in the Reduction with an NAD(P)H Analog" Bull.Chem.Soc.Jpn.63. 2682-2686 (1990)

[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.73.StructureーStereochemistry Relationship in the Reaction of NAD Analog." Bull.Chem.Soc.Jpn.64. 81-86 (1991)

[Publications] Atsuyoshi Ohno: "NAD(P)^+ーNAD(P)H Models.74.EntropyーControlled Kinetics,Stereochemistry,and Tunneling Effect." Bull.Chem.Soc.Jpn.64. 87-90 (1991)

[Publications] Hisanobu Ogoshi: "Novel 1:1 Complex of Rhodium(III)porphyrins with Nucleobases." Chem.Lett.51-54 (1990)

[Publications] Hisanobu Ogoshi: "Epoxidation Reaction Catalysed by Cyclodextrin Sandwiched Porphyrin in Aqueous Buffer Solution." J.Chem.Soc.,Chem.Commun.1594-1595 (1990)

[Publications] Hisanobu Ogoshi: "Regioselectivities and Stereoselectivities of Singlet Oxygen Generated by Cyclodextrin Sandwiched Porphyrin Sensitization.Lopoxygenaseーlike Activity." J.Am.Chem.Soc.

[Publications] Eiichi Kimura: "Isolation and Unusual Stability of a New Macrocyclic Polyamine Containing a Phthalimidine." J.Org.Chem.55. 764-766 (1990)

[Publications] Eiichi Kimura: "A Novel CyclamーNickel(II) Complex Appended with a trisー(2,2^′ーbipyridine)ーRuthenium(II) Complex." J.Chem.Soc.,Chem.Commun.,. 397-398 (1990)

[Publications] Eiichi Kimura: "A Zinc(II) Complex of 1,5,9ーTriazocyclododecane(12aneN3)as a Model for Carbonic Anhydrase." J.Am.Chem.Soc.112. 5805-5811 (1990)

[Publications] Eiichi Kimura: "Polarographic Study of the Rates of the Dissociation Reactions of the Eu(III)ーHAHA Complex and of the Eu(III)ーGd(III)ー,and Ho(III)ーPAPA Complexes." Bull.Chem.Soc.,Jpn.63. 2639-2645 (1990)

[Publications] Eiichi Kimura: "Momoー,Diー,and Tetrafluorinated Cyclams." J.Am.Chem.Soc.112. 9237-9245 (1990)

[Publications] Eiichi Kimura: "Acid Properties of Zinc(II) and Cadmium(II) in Complexation with Macrocyclic Oxopolyamine Ligands." Inorg.Chem.29. 4621-4929 (1990)

[Publications] Eiichi Kimura: "A Novel Cyclam Appended with 3ーHydroxypyridine.An Ambident Donor Ligand Comprising a Pyridyl N and A Pyridinolate O^ー Donors." Inorg.Chem.29. 4991-4996 (1990)

[Publications] Toyoki Kunitake: "Layered Arrangement of Oriented Myoglobins in Cast Films of a Phosphate Bilayer Membrane" J.Am.Chem.Soc.112. 6744-6745 (1990)

[Publications] Toyoki Kunitake: "Design of Spatial Disposition of Anionic Porphyrins in Matrices of Ammonium Bilayer Membrane" J.Am.Chem.Soc.113. 621-630 (1991)

[Publications] Seiji Shinkai: "Coenzyme Models.52.Diastereoーdifferentiating Hydrogen Transfer in 5ーdeazaflavin Oxidation of Alcohols and Amines." J.Chem.Soc.,Perkin Trans I. 1075-1078 (1990)

[Publications] Junzo Sunamoto: "The Effect of Polysaccharide Adsorption on Surface Potential of Phospholipid Monolayers Spread at waterーAir Interface" Chem.Lett.299-302 (1990)

[Publications] Junzo Sunamoto: "Functinalized Liposomes in Medicine." BIOmedica. 5. 31-34 (1990)

[Publications] Waichiro Tagaki: "Metal IonーFacilitated Oxidations of Dihydropyridines with Molecular Oxygen and Hydrogen Peroxide" J.Chem.Soc.,Perkin Trans II. 1645-1650 (1990)

[Publications] Waichiro Tagaki: "RateEnhancing MultiーSite Interactions in Ester Hydrolysis Catalyzed by Cu^<2+>Complexes of Surfactant Imidazole Ligands in Nonーionic Micelles." Tetrahedron Lett.31. 7023-7026 (1990)

[Publications] Waichiro Tagaki: "Hydrolytic Metalloenzyme Models.Micellar Effects on the Activation of the Hydroxyl Groups of Alkylー2ーhydroxymethylimidazole Ligands by Cu^<2+> in the・・・・・・" Bull.Chem.Soc.Jpn.64. 74-80 (1991)

[Publications] Akira Nakamura: "Synthesis and Crystal Structure of a cisーDioxomolybdenum(VI) Complex with two Benzenedithiolato Ligands.(NEt_4)_2[Mo^<VI>O_2(1,2ーbenzenethiolato)_2]." Chem.Lett.1655-1656 (1990)

[Publications] Akira Nakamura: "Transition Metal Thiolates:Synthetic,Catalytic,and Biomimetic Aspects." Pure & Appl.Chem.62. 1011-1020 (1990)

[Publications] Akira Nakamura: "Oーatom Transfer Biomimetic Oxidation of Benzoin in the Presence of Monooxomolybdenum(VI) Thiolate Complexes." J.Mol.Cata.64. 247-256 (1991)

[Publications] Yoshio Hisaeda: "Hydrophobic Vitamin B_<12>.8.CarbonーSkeleton Rearrangement Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Bioorg.Chem.18. 49-62 (1990)

[Publications] Yoshio Hisaeda: "Preparation and Molecular Recognition Behavior of a Hexapus Azaparacyclophane" Tetrahedron Lett.31. 1027-1030 (1990)

[Publications] Yoshio Hisaeda: "Functionalized Bilayer Membranes as Artificial Tryptophan Synthase.Caracterization of Catalytic Efficiency Substrate Specificity,and Reaction Selectivity." Bull.Chem.Soc.Jpn.63. 2339-2345 (1990)

[Publications] Masanobu Hidai: "Novel Disilylation and Germylation of Coordinated Dinitrogen in cisー[W(N_2)_2(PMe_2Ph)_4]" Chem.Lett.1303-1306 (1990)

[Publications] Masanobu Hidai: "Regioselective Alkylation of Tungsten Diazoalkane Complexes via Alkenyldaizenido Complexes." J.Chem.Soc.,Chem.Commun.1569-1571 (1990)

[Publications] Masanobu Hidai: "Regioselective Monoー and DiーCーacylation of Tungsten Diazoalkane Complexes via Alkenyldiazzenido Complexes." Chem.Lett.

[Publications] Masaaki Hirobe: "Synthesis of a Highly Stable Porphinatoiron Coordinated by Thiolate Anion as a Model for Cytochrome Pー450 and Its Catalytic Activity in OーO Bond Cleavage." J.Am.Chem.Soc.112. 7051-7053 (1990)

[Publications] Masaaki Hirobe: "Sulfide Oxidation,Amine NーDemethylation,and Olefin Oxidation by HemeーUndecapeptide,Microperoxidaseー11,in the Presence of Hydrogen Peroxide." Tetrahedron Lett.31. 3163-3166 (1990)

[Publications] Masaaki Hirobe: "3ーHydroxycoumarins:First Direct Preparation from Coumarins using a Cu^<2+>ーAscorbic AcidーO_2 System,and Their Potent Bioactivities." Biochem.Biophys.Res.Commun.168. 169-175 (1990)

[Publications] Shunーichi Murahashi: "TungstenーCatalyzed Oxidation of Secondary Amines to Nitrones." J.Org.Chem.55. 1736-1744 (1990)

[Publications] Shunーichi Murahashi: "TungstenーCatalyzed Oxidation of Tetrahydroquinones with Hydrogen Peroxide:A Novel Method for theSynthesis of Cyclic Hydroximic Acids." J.Org.Chem.55. 1744-1749 (1990)

[Publications] Shunーichi Murahashi: "New Aspects of Oxypalladation of Alkenes." Acc.Chem.Res.23. 49-54 (1990)

[Publications] Yoshihiko Moroーoka: "Formation and Characterization of a Mononuclear(Acylperoxo)copper(II) Complex." Inorg.Chem.29. 357-358 (1990)

[Publications] Yoshihiko Moroーoka: "Fixation of Atmospheric CO_2 by a Copper(II) Complex." J.Chem.Soc.,Chem.Commun.1357-1358 (1990)

[Publications] Yoshihiko Morooka: "Reaction Aspects of a ーPeroxo Binuclear Copper(II)Complex." J.Am.Chem.Soc.112. 8833-8839 (1990)

大城芳樹大阪大学, 工学部, 教授 (70028984)