1989 Fiscal Year Annual Research Report

弱い配位系の動的解析

Research Project

Project/Area Number	01612005
Research Institution	Waseda University
Principal Investigator	土田英俊早稲田大学, 理工学部, 教授 (90063461)
Co-Investigator(Kenkyū-buntansha)	引地邦男北海道大学, 理学部, 教授 (30000805) 東村敏延京都大学, 工学部, 助教授 (20025860) 大矢博昭京都大学, 理学部, 教授 (00025389) 大瀧仁志岡崎国立共同機構, 分子化学研究所, 教授 (80022549) 堀江一之東京大学, 先端科技研センター, 助教授 (10013690)
Keywords	高分子錯体 / 弱い配位 / 動的解析 / 動的相互作用 / 動力学 / 歪錯体 / 大環状錯体
Research Abstract	高分子錯体に独特な弱い配位系を対象に、その相互作用を動的に把え、高分子錯体に関する基礎科学を確立することが目的である。錯体部周囲環境を構成するコンフォメ-ション変化に伴う弱い配位錯体系の動力学を、固相および溶液状態において理論と実験の両面から解析するとともに、ポルフィリン錯体、歪錯体、大環状錯体、π配位錯体、生体高分子錯体において、錯体部を標識とした動的スペクトル解析や反応解析に新しい方法を駆使して、高分子錯体に独特な動的相互作用を定量的かつ系統的に明らかにしようとした。第3年次として研究組織一体となって、次の成果を得た。 (1)高分子ポルフィリン錯体を対象に、歪構造と弱い配位現象をポルフィリン周囲の分子環境とマトリックスの動的構造に関連させて、高速分光法、ESRゆらぎ微細構造パラメ-タ、フォノンカップリング、メスバウアパラメ-タなどから動的に解析、相互作用を総合的に把握できた。 (2)ポリアミノ酸、多糖および対応するアミノ酸、糖錯体など、モデル高分子錯体の溶液中における局所微細構造の動的解析を進め、解析結果の相互比較とシュミレ-ションから、動的相互作用の因子を定量的に整理できた。 (3)π配位錯体、大環状ポリアミン錯体、不製ルテニウム錯体などに独特な、歪構造と弱い配位系を時間軸で測定した。特に動的相互作用を電子過程との相関から特徴づけ、化学反応過程における弱い配位の役割を実証できた。各班員間の直接の共同も含めて、高分子錯体の動的解析結果を相互比較し、高分子錯体の弱い配位系の実態について定量的議論を進め、基礎概念と具体的意義をまとめた。動的相互作用の理解に基づく新しい物質系「高分子錯体」の定量的把握に踏み込む成果が得られた。

Research Products
(38 results)

All Other

All Publications (38 results)

[Publications] E.Tsuchida,H.Nishide,M.Yuasa,E.Hasegawa,K.Eshima,Y.Matsushita: ""Polymerized Liposome/LipidーHeme as an Oxygen Transporter under Phuysiological Condition"" Macromolecules. 22. 2103-2107 (1989)
[Publications] L.Wang,T.Takahashi,H.Ohno,E.Tsuchida: ""Porphnato Zinc Complexes Incorporated into the Bilayer Membrane of Lipid Liposomes"" J.Macromol.Sci.ーChem.A26. 481-493 (1989)
[Publications] L.Wang,H.Ohno,E.Tsuchida: ""Reversible Association of Porphyrin Derivative Incorporate into Hydrophobic Region of Phospholipid Bilayer"" Polymer J.21. 505-510 (1989)
[Publications] S.Takeoka,H.Sakai,L.Wang,H.Ohno,E.Tsuchida: ""Study on the Phase Transition Behavior of Polymerized Liposomes through the Interaction of DieneーGroups in Their Acyl Chains"" Polymer J.21. 641-648 (1989)
[Publications] K.Yamamoto,S,Yoshioka,H.Nishide,E.Tsuchida: ""Preparation of Poly(phenylene sulfide)s:Polymerization of Aromatic Disulfides with Sewis Acids"" Bull.Chem.Soc.Jpn.62. 3655-3660 (1989)
[Publications] E.Tsuchida,K.Yamamoto,,M.Jikei,H.Nishide: ""New Synthesis of Poly(phenylene suflide)s through O_2 Oxidative Polymerization of Diphenyl Disulfide with VO Catalyst"" Macromolecules. 22. 4138-4140 (1989)
[Publications] E.Tsuchida,E.Hasegawa,Y.Chika,T.Babe,H.Nishide: ""Oxygenation of Porphnatoiron(II)Complexes with ImidazoleーContaining GlycerophosphoーCholines in Phospholipid Bilayers"" Chem.Lett.1989. 1727-1730 (1989)
[Publications] E.Tsuchida,H.Ohno,N.Kobayashi,H.Ishizuka: ""Poly[(Wーcarboxyl)oxyethylene)methacrylate]as a New Type of Polymeric Solid Electrolyte for AlkaliーMetal Ion Transport"" Macromolecules. 22. 1771-1775 (1989)
[Publications] H.Ohno,E.Tsuchida: ""Design of Single Ionic Conduction in Polymeric Solid Electrolytes"" J.Macromol.Sci.ーChem.A26. 551-566 (1989)
[Publications] E.Hasegawa,M.Fukuzumi,H.Nishide,E.Tsuchida: ""Synthesis of a Negativelyーcharged Porphinatoiron(II) Having a Phosphoserine Groups and Oxygenation in Phospholipid"" Chem.Lett.1990. 123-126 (1990)
[Publications] I.Mita,K.Horie,K.Hirao: ""Photochemistry in Polymer Solids.9.Photoisomeriazation of Azobenzene in a Polycarbonate Film"" Macromolecules. 22. 558-563 (1989)
[Publications] A.Furusawa,I.Mita,K.Horie,K.Kuroki: ""Photochemical Hole Burning of Tetraphenylparphin in Phenoxy Resion at 4.2ー80K"" J.Appl.Phys.66. 6041-6047 (1989)
[Publications] A.Furusawa,K.Horie,I.Mita: ""Low Energy Excitation Modes of Amorphous Polymers Probed by Photochemical Hole Burning"" Chem.Phys.let.161. 227-231 (1989)
[Publications] L.Nagy,H.Ohtaki,T.Yamaguchi,H.Nomura: "“EXAFS Study of Iron(III)Complexes of Sugar一Type Ligands"" Inorg.Chim.Acta. 159. 201-207 (1989)
[Publications] T.Radnai,S.Shiguro,H.Ohtaki: ""Intramolecular and Liquid Structure of 2,2,2ーTraifluoroethanol by XーRay Diffraction." J.Solution Chem.18. 771-784 (1989)
[Publications] T.Radnai,S.Ishiguro,H.Ohtaki: ""Liquid Strucutre of 2,2,2ーTrifuroethanolーDimethyl Sulfoxide Mixtures as Studied by XーRay Diffraction" Chem.Phys.Lett.159. 532-537 (1989)
[Publications] K.Ozutsumi,T.Takamuku,S.Ishiguro,H.Ohtaki: ""An XーRay Diffraction Study on the Structure of Solvated Cadmium(II)Ion and Tetrathiocyanatocadmate(II)Complex in N,NーDimethl formide." Bull.Chem.Soc.Jpn.62. 1875-1879 (1989)
[Publications] K.Ozutsumi,M.Natsuhara,H.Ohtaki: ""An XーRay diffraction Study on the Structure of 18ーCrownー6 Ether Complexes with Alkali Metal Ions in Aqueous Solution."" Bull.Chem.Soc.Jpn.62. 2807-2818 (1989)
[Publications] T.Yamaguchi,S.Hayashi,H.Ohtaki: ""XーRay Diffraction Study of Calcium(II)Chloride Hydrate Melts:CaCl_2・RH_2O(r=4.0,5.6,6.0,and 8.6)"" Inorg.Chem.28. 2434-2439 (1989)
[Publications] S.Ishiguro,K.Ozutsumi,M.Miyauchi,H.Ohtaki: ""Formation of Binary and Ternary Complexes of Cadmium(II)with Halide Ions and 2,2'ーBipyridine in N,NーDimethylーformamide."" Inorg.Chem.28. 3258-3263 (1989)
[Publications] S.Ishiguro,K.Ozustumi,L.Nagy,H.Ohtaki: ""Spectrophotometric and Calorimetric Studies on the Formation of Binary(2,2'ーBipyridine)nickel(II)and Ternary(2,2'ーBipyridine)chloronickel(II)Complexes in N,NーDimethyl Formamide"" J.Chem.Soc.,Dalton Trans.61. 655-659 (1989)
[Publications] T.Radnai,S.Ishiguro,H.Ohtaki: ""Intramolecular and Lipuid Satructure of 2,2,2ーTrifluroethanol by XーRay Diffraction"" J.Solution Chem.18. 771-784 (1989)
[Publications] H.Suzuki,S.Ishiguro,H.Ohtaki: ""Solvation and Complexation of Copper(II)and Chloride Ions in 2,2,2ーTrifluoroethanolーDimethyl Solfoxide Mixtures"" J.Chem.Soc.Faraday Trans.85. 2587-2596 (1989)
[Publications] H.OhyaーNishiguchi: ""Sensitive ESR Observation by Using a Programmable Spectrum Analyzer"" J.Mag.Res.82. 1-11 (1989)
[Publications] K.Tajima,J.Jinno,K.Ishizu,H.Sakurai,H.OhyaーNishiguci: ""Direct Evidence of Heme ーtertーButyl Peroxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements"" Inorg.Chem.28. 709-715 (1989)
[Publications] T.Masuda,T.Yoshimura,T.Higashimura: ""Living Polymerization of 1ーChloroー1ーalkynes by MoOCl_4ーnーBu_4SnーEtOH Catalyst"" Macromolecules. 22. 3804-3806 (1989)
[Publications] K.Hikichi,H.Tanaka,A.Konno: ""Nuclear Magnetic Resonance Study of Poly(ーーglutamic acid)ーCu(II)and Mn(II)Complexes"" Polymer J.22. 103-109 (1990)
[Publications] S.Tokura,Y.Uraki,K.Ohmiya,A.Tsutumi,H.Sashiwa: ""Preparation of Alchol Soluble Chitin Derivatives and Redical Induction by Photo-Irradiation"" Charbohydr.Polym.
[Publications] S.Tokura,S.Baba,Y.Uraki,Y.Miura,N.Nishi,O.Hasegawa: ""Carboxymethylーchitin as a Drug Carrier of Sustained Release"" Carbohydr.Polym.
[Publications] E.Kimura,Y.Kurogi,S.Wada,M.Shioya: ""A NeW Tetradentate(N^ー)_2S_2Macrocyclic Ligand which is Highly Selective for Platinum(!!)Palladium(!!)"" J.Chem.Soc.Chem.Commun.1989. 781-783 (1989)
[Publications] H.Inoue,T.Nakazawa,T.Mitsuhashi,T.Shirai: "Characterization of Prussian Blue and Its Thermal Decomposition Products." Hyp.Int.46. 725-731 (1989)
[Publications] H.Nishide,N.Yoshioka,H.Inoue: "Coordination Structure and Magnetic Properties of Poly(pyridilenemethylidenenitriloiron)s." J.Plym.Sci.27. 497-505 (1989)
[Publications] H.Inoue,T.Kuroiwa,T.Shirai,E.Fluck: "Preparation and Spectroscopic Characterization of transーFe(Co)_3L^1L^2(L^1L^2=Phosphine or Phosphite)." Z.Naturforsch.44b. 541-546 (1989)
[Publications] K.Furuya,H.Hatano,H.Inoue,T.Shirai: "Separation and Determination of Nitrate Ion by Affinity Chromatography with Cyano(pheophytinato a)cobalt(III)Charged Column." Chromatographia. 27. 461-464 (1989)
[Publications] H.Hori,K.Kadono,H.Inoue,T.Shirai,E.Fluck: "Mossbauer Spectroscopic and Magnetic Properties of Iron(III)Pheophytins." J.Radioanal.Nucl.Chem.Let.136. 159-168 (1989)
[Publications] H.Hori,K.Kadono,K.Fukuda,H.Inoue,T.Shirai,E.Fluck: "Mossbauer Study of Iron(III)Pyropheophytins." J.Radioanal.Nucl.Chem.Let.137. 227-286 (1989)
[Publications] Y.Shiro,T.Iizuka,R.Makino,Y.Ishimura,I.Marishima: ""^<15>N NMR Study on Cyanide(C^<15>N^ー)Complex of Cytochrome Pー450 Effects of dーCamphor and Putidaredoxin on the IronーLigand Structure"" J.Am.Chem.Soc.111. 7707-7711 (1989)
[Publications] Y.Nakamura,K.Tokubo,A.Yamagishi,S.Matsumoto,: ""HighーPerformance Liquid Chromatography for Optical Persolution on a colum of an IonーExchange Adduct of Spherically Shared Synthetic Hectorite and Optically Active Metal Complexes"" J.Chromatography. 482. 165-173 (1989)

1989 Fiscal Year Annual Research Report

弱い配位系の動的解析

Principal Investigator

土田 英俊 早稲田大学, 理工学部, 教授 (90063461)

Research Products

[Publications] E.Tsuchida,H.Nishide,M.Yuasa,E.Hasegawa,K.Eshima,Y.Matsushita: ""Polymerized Liposome/LipidーHeme as an Oxygen Transporter under Phuysiological Condition"" Macromolecules. 22. 2103-2107 (1989)

[Publications] L.Wang,T.Takahashi,H.Ohno,E.Tsuchida: ""Porphnato Zinc Complexes Incorporated into the Bilayer Membrane of Lipid Liposomes"" J.Macromol.Sci.ーChem.A26. 481-493 (1989)

[Publications] L.Wang,H.Ohno,E.Tsuchida: ""Reversible Association of Porphyrin Derivative Incorporate into Hydrophobic Region of Phospholipid Bilayer"" Polymer J.21. 505-510 (1989)

[Publications] S.Takeoka,H.Sakai,L.Wang,H.Ohno,E.Tsuchida: ""Study on the Phase Transition Behavior of Polymerized Liposomes through the Interaction of DieneーGroups in Their Acyl Chains"" Polymer J.21. 641-648 (1989)

[Publications] K.Yamamoto,S,Yoshioka,H.Nishide,E.Tsuchida: ""Preparation of Poly(phenylene sulfide)s:Polymerization of Aromatic Disulfides with Sewis Acids"" Bull.Chem.Soc.Jpn.62. 3655-3660 (1989)

[Publications] E.Tsuchida,K.Yamamoto,,M.Jikei,H.Nishide: ""New Synthesis of Poly(phenylene suflide)s through O_2 Oxidative Polymerization of Diphenyl Disulfide with VO Catalyst"" Macromolecules. 22. 4138-4140 (1989)

[Publications] E.Tsuchida,E.Hasegawa,Y.Chika,T.Babe,H.Nishide: ""Oxygenation of Porphnatoiron(II)Complexes with ImidazoleーContaining GlycerophosphoーCholines in Phospholipid Bilayers"" Chem.Lett.1989. 1727-1730 (1989)

[Publications] E.Tsuchida,H.Ohno,N.Kobayashi,H.Ishizuka: ""Poly[(Wーcarboxyl)oxyethylene)methacrylate]as a New Type of Polymeric Solid Electrolyte for AlkaliーMetal Ion Transport"" Macromolecules. 22. 1771-1775 (1989)

[Publications] H.Ohno,E.Tsuchida: ""Design of Single Ionic Conduction in Polymeric Solid Electrolytes"" J.Macromol.Sci.ーChem.A26. 551-566 (1989)

[Publications] E.Hasegawa,M.Fukuzumi,H.Nishide,E.Tsuchida: ""Synthesis of a Negativelyーcharged Porphinatoiron(II) Having a Phosphoserine Groups and Oxygenation in Phospholipid"" Chem.Lett.1990. 123-126 (1990)

[Publications] I.Mita,K.Horie,K.Hirao: ""Photochemistry in Polymer Solids.9.Photoisomeriazation of Azobenzene in a Polycarbonate Film"" Macromolecules. 22. 558-563 (1989)

[Publications] A.Furusawa,I.Mita,K.Horie,K.Kuroki: ""Photochemical Hole Burning of Tetraphenylparphin in Phenoxy Resion at 4.2ー80K"" J.Appl.Phys.66. 6041-6047 (1989)

[Publications] A.Furusawa,K.Horie,I.Mita: ""Low Energy Excitation Modes of Amorphous Polymers Probed by Photochemical Hole Burning"" Chem.Phys.let.161. 227-231 (1989)

[Publications] L.Nagy,H.Ohtaki,T.Yamaguchi,H.Nomura: "“EXAFS Study of Iron(III)Complexes of Sugar一Type Ligands"" Inorg.Chim.Acta. 159. 201-207 (1989)

[Publications] T.Radnai,S.Shiguro,H.Ohtaki: ""Intramolecular and Liquid Structure of 2,2,2ーTraifluoroethanol by XーRay Diffraction." J.Solution Chem.18. 771-784 (1989)

[Publications] T.Radnai,S.Ishiguro,H.Ohtaki: ""Liquid Strucutre of 2,2,2ーTrifuroethanolーDimethyl Sulfoxide Mixtures as Studied by XーRay Diffraction" Chem.Phys.Lett.159. 532-537 (1989)

[Publications] K.Ozutsumi,T.Takamuku,S.Ishiguro,H.Ohtaki: ""An XーRay Diffraction Study on the Structure of Solvated Cadmium(II)Ion and Tetrathiocyanatocadmate(II)Complex in N,NーDimethl formide." Bull.Chem.Soc.Jpn.62. 1875-1879 (1989)

[Publications] K.Ozutsumi,M.Natsuhara,H.Ohtaki: ""An XーRay diffraction Study on the Structure of 18ーCrownー6 Ether Complexes with Alkali Metal Ions in Aqueous Solution."" Bull.Chem.Soc.Jpn.62. 2807-2818 (1989)

[Publications] T.Yamaguchi,S.Hayashi,H.Ohtaki: ""XーRay Diffraction Study of Calcium(II)Chloride Hydrate Melts:CaCl_2・RH_2O(r=4.0,5.6,6.0,and 8.6)"" Inorg.Chem.28. 2434-2439 (1989)

[Publications] S.Ishiguro,K.Ozutsumi,M.Miyauchi,H.Ohtaki: ""Formation of Binary and Ternary Complexes of Cadmium(II)with Halide Ions and 2,2'ーBipyridine in N,NーDimethylーformamide."" Inorg.Chem.28. 3258-3263 (1989)

[Publications] S.Ishiguro,K.Ozustumi,L.Nagy,H.Ohtaki: ""Spectrophotometric and Calorimetric Studies on the Formation of Binary(2,2'ーBipyridine)nickel(II)and Ternary(2,2'ーBipyridine)chloronickel(II)Complexes in N,NーDimethyl Formamide"" J.Chem.Soc.,Dalton Trans.61. 655-659 (1989)

[Publications] T.Radnai,S.Ishiguro,H.Ohtaki: ""Intramolecular and Lipuid Satructure of 2,2,2ーTrifluroethanol by XーRay Diffraction"" J.Solution Chem.18. 771-784 (1989)

[Publications] H.Suzuki,S.Ishiguro,H.Ohtaki: ""Solvation and Complexation of Copper(II)and Chloride Ions in 2,2,2ーTrifluoroethanolーDimethyl Solfoxide Mixtures"" J.Chem.Soc.Faraday Trans.85. 2587-2596 (1989)

[Publications] H.OhyaーNishiguchi: ""Sensitive ESR Observation by Using a Programmable Spectrum Analyzer"" J.Mag.Res.82. 1-11 (1989)

[Publications] K.Tajima,J.Jinno,K.Ishizu,H.Sakurai,H.OhyaーNishiguci: ""Direct Evidence of Heme ーtertーButyl Peroxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements"" Inorg.Chem.28. 709-715 (1989)

[Publications] T.Masuda,T.Yoshimura,T.Higashimura: ""Living Polymerization of 1ーChloroー1ーalkynes by MoOCl_4ーnーBu_4SnーEtOH Catalyst"" Macromolecules. 22. 3804-3806 (1989)

[Publications] K.Hikichi,H.Tanaka,A.Konno: ""Nuclear Magnetic Resonance Study of Poly(ーーglutamic acid)ーCu(II)and Mn(II)Complexes"" Polymer J.22. 103-109 (1990)

[Publications] S.Tokura,Y.Uraki,K.Ohmiya,A.Tsutumi,H.Sashiwa: ""Preparation of Alchol Soluble Chitin Derivatives and Redical Induction by Photo-Irradiation"" Charbohydr.Polym.

[Publications] S.Tokura,S.Baba,Y.Uraki,Y.Miura,N.Nishi,O.Hasegawa: ""Carboxymethylーchitin as a Drug Carrier of Sustained Release"" Carbohydr.Polym.

[Publications] E.Kimura,Y.Kurogi,S.Wada,M.Shioya: ""A NeW Tetradentate(N^ー)_2S_2Macrocyclic Ligand which is Highly Selective for Platinum(!!)Palladium(!!)"" J.Chem.Soc.Chem.Commun.1989. 781-783 (1989)

[Publications] H.Inoue,T.Nakazawa,T.Mitsuhashi,T.Shirai: "Characterization of Prussian Blue and Its Thermal Decomposition Products." Hyp.Int.46. 725-731 (1989)

[Publications] H.Nishide,N.Yoshioka,H.Inoue: "Coordination Structure and Magnetic Properties of Poly(pyridilenemethylidenenitriloiron)s." J.Plym.Sci.27. 497-505 (1989)

[Publications] H.Inoue,T.Kuroiwa,T.Shirai,E.Fluck: "Preparation and Spectroscopic Characterization of transーFe(Co)_3L^1L^2(L^1L^2=Phosphine or Phosphite)." Z.Naturforsch.44b. 541-546 (1989)

[Publications] K.Furuya,H.Hatano,H.Inoue,T.Shirai: "Separation and Determination of Nitrate Ion by Affinity Chromatography with Cyano(pheophytinato a)cobalt(III)Charged Column." Chromatographia. 27. 461-464 (1989)

[Publications] H.Hori,K.Kadono,H.Inoue,T.Shirai,E.Fluck: "Mossbauer Spectroscopic and Magnetic Properties of Iron(III)Pheophytins." J.Radioanal.Nucl.Chem.Let.136. 159-168 (1989)

[Publications] H.Hori,K.Kadono,K.Fukuda,H.Inoue,T.Shirai,E.Fluck: "Mossbauer Study of Iron(III)Pyropheophytins." J.Radioanal.Nucl.Chem.Let.137. 227-286 (1989)

[Publications] Y.Shiro,T.Iizuka,R.Makino,Y.Ishimura,I.Marishima: ""^<15>N NMR Study on Cyanide(C^<15>N^ー)Complex of Cytochrome Pー450 Effects of dーCamphor and Putidaredoxin on the IronーLigand Structure"" J.Am.Chem.Soc.111. 7707-7711 (1989)

[Publications] Y.Nakamura,K.Tokubo,A.Yamagishi,S.Matsumoto,: ""HighーPerformance Liquid Chromatography for Optical Persolution on a colum of an IonーExchange Adduct of Spherically Shared Synthetic Hectorite and Optically Active Metal Complexes"" J.Chromatography. 482. 165-173 (1989)

土田英俊早稲田大学, 理工学部, 教授 (90063461)