TOP > 研究報告検索 > オキシジェニクス(高分子錯体)

オキシジェニクス(高分子錯体)

研究報告コード R000000177
掲載日 2002年9月30日
研究者
  • 土田 英俊
研究者所属機関
  • 早稲田大学理工学部
研究機関
  • 早稲田大学理工学部
報告名称 オキシジェニクス(高分子錯体)
報告概要 酸素が関与する一段階多電子移動生起を利用する、「錯体部の配位活性制御と革新的化学反応の構築」についての研究を展開した。具体的には、
(1)配位酸素への電子移動の促進例として、複核錯体を介した一段階4電子移動が室温下で空気吹込みのみで容易に生起し、これが従来反応しないとされてきた化合物を活性化して、長鎖の巨大分子に成長させる酸化重合反応(μ-オキソ型複核金属錯体によるO2分子架橋錯体の形成と接触的に生起する酸素開裂の特徴を利用した酸化重合反応系、加えてスルホニウム基の親電子反応を利用する直鎖型長鎖ポリヘテロアセンの合成など)を見出している。この方法を普遍化すれば、高温高圧化の現行化学工業の生産過程は極めて簡単になり、省エネルギー過程としても社会貢献が期待できる。
(2)錯体構造を工夫して電子移動抑制の条件を附与すると、例えば生理塩水溶液に溶け込ませたキャリア分子(例えばリピドヘム)導入に依り空気から溶液に酸素のみを選択濃縮でき、濃度勾配を駆動力として配位酸素の着脱が可能となるため、生体組織の全細胞の呼吸と生存を保障できる酸素の高濃度輸送系の実現に繋がる利用に道を開くことができた。
(3)酸素促進輸送の原理を明らかにし、これを次世代の膜利用技術として定着させる可能性を明確にした。
研究分野
  • 巨大分子,高分子
  • 高分子の結晶構造
  • 無機化合物一般及び元素
  • 分子化合物
  • エネルギー消費,省エネルギー
関連発表論文 (1) Synthesis of Semicrystalline Aromatic Poly(thioether thioether ketone)s (PTTK and PTBTK) and Their Copolymers with Ether Analogues, Y Ding, A. R. Hlil, A. S. Hay, B. Tsuchida, K. Miyatake, Macromolecules, 32, 315-321(1999).
(2) Synthesis of a Novel Oligo(p-phenylene) Ladder by Sulfide and Sulfonio Groups, A. Haryono, K. Miyatake, J. Natori, E. Tsuchida, Macromolecules, 32, 3146-3149 (1999).
(3) A Novel Electroactive Polyelectrolyte with Alternating Seleno- and Selenoniophenylene Units, K. Miyatake, T. Ishikawa, E. Tsuchida, Macromolecules, 32, 4497-4499 (1999).
(4) Synthesis and Photochemical Reaction of Polyarylenesulfonium Salts, A. Haryono, K. Miyatake, E. Tsuchida, Macromol. Chem. Phys., 200, 1257-1267 (1999).
(5) Molecular Structure of a μ-Oxo Chromium-Iron Complex: Rare Example of a Crystallographi- cally Characterized μ-Oxo Heterometallic Porphyrin, K. Oyaizu, A. Haryono, Y. Nishimura, K. Yamamoto, E. Tsuchida, Bull. Chem. Soc. Jpn., 72, 1781-1784 (1999).
(6) Catalysis of the Electroreduction of O2 to H2O by Vanadium-Salen Complexes in Acidified Dichloromethane, E. Tsuchida, K. Oyaizu, E. L. Dewi, T. Imai, F. C. Anson, Inorg. Chem., 28, 3704-3708 (1999).
(7) Synthesis and Functionalization of Bromomethylated Poly(phenylene sulfide), K. Miyatake, H. Hara, E. Tsuchida, Macromol. Chem. Phys., 200, 1930-1934 (1999).
(8) Preparation and Properties of Polyaniline Doped with Poly(thiophenylenesulfonic acid), K. Miyatake, J.-S. Cho, S. Takeoka, E. Tsuchida, Macromol. Chem. Phys., 200, 2897-2601 (1999).
(9) Synthesis and Characterization of Nickel Dithiocarbamate Complexes Bearing Ferrocenyl Subunits, K. Oyaizu, K. Yamamoto, Y. Ishii, E. Tsuchida, Chem. Eur J., 5, 3 193-3201 (1999).
(10) Solubilization of Poly(phenylene sulfide) via Sulfonium Formation by Alkylation, K. Miyatake, K. Endo, E. Tsuchida, Macromolecules, 32, 8786-8790 (1999).
(11) Nonaqueous Proton Conduction in Poly(thiophenylenesulfonic acid)/Poly(oxyethylene) Composite, K. Miyatake, K. Fukushima, S. Takeoka, E. Tsuchida, Chem. Mater, 11, 1171-1173 (1999).
(12) Physicochemical Properties and O2-Coordination Structure of Human Serum Albumin Incorporating Tetrakis(o-pivalamido)phenylporphyrinatoiron(II) Derivatives, T. Komatsu, K. Hamamatsu, J. Wu, E. Tsuchida, Bioconjugate Chem., 10, 82-86 (1999).
(13) Self-Assembled Fibers Made of Lipidporphyrinato-Zinc(II) and -Iron(II) Complexes with an Intramolecular Coordinated Axial Imidazole, T. Komatsu, T. Yanagimoto, Y Furubayashi, J. Wu, E. Tsuchida, Langmuir, 15, 4427-4433 (1999).
(14) Human Serum Albumin Incorporating Tetrakis(o-pivalamido)phenylporphinatoiron(II) Derivative as a Totally Synthetic O2-Carrying Hemoprotein, E. Tsuchida, T. Komatsu, Y Matsukawa, K. Hamamatsu, J. Wu, Bioconjugate Chem., 10, 797-802 (1999). (15) Photoexcitation and Electron Transfer Reactions of Zinc-Lipidporphyrins in DMSO, T. Ohgushi, Z.-C. Li, F.-M. Li, T. Komatsu, S. Takeoka, B. Tsuchida, J. Porphyrins Phthalocyanines, 3, 53-59 (1999).
(16) 5,10,15,20-Tetrakis(α,α,α,α,-o-pivalamidophenyl)porphinatoiron(II) Bearing a Covalently Linked Axial Imidazole via m-Aminobenzoic Acid: Synthesis and Influence of Imidazole Basicity on O2-Binding Affinity, T. Komatsu, Y Furubayashi, H. Nishide, E. Tsuchida, Inorg. Chim. Acta., 295, 234-238 (1999).
(17) Cross-Linked Human Serum Albumin Dimers Incorporating Sixteen (Tetraphenylporphinato)- iron(II) Derivatives: Synthesis, Characterization, and O2-Binding Property, T. Komatsu, K. Hamamatsu, E. Tsuchida, Macromolecules, 32, 8388-8391 (1999).
(18) Microvascular Responses to Hemodilution with Hb Vesicles as Red Blood Cell Substitutes: Influence of O2 Affinity, H. Sakai, A. G. Tsai, R. J. Rohlfs, H. Hara, S. Takeoka, E. Tsuchida M. Intaglietta, Am. J. Physiol. Heart Circ. Physiol., 276, H553-H562 (1999).
(19) Changes in Resistance Vessels during Hemorrhagic Shock and Resuscitation in Conscious Hamster Model, H. Sakai, H. Hara, A. G. Tsai, E. Tsuchida, P. C. Johnson, M. Intaglietta, Am.J. Physiol. Heart Circ. Physiol., 276, H563-H571 (1999).
(20) Synthesis of Poly(4-imidazolylmethylstyrene)-Cobaltporphyrin Complex and Facilitated Oxygen Transport through its Membrane, A. Kato, H. Nishide, E. Tsuchida, Porphyrins, 8, 8-14 (1999).
(21) Oxygen-Carrying Cobaltporphyrin Complexed with Electroconductive Poly(3,4-azopyridylene), F. Ito, H. Nishide, E. Tsuchida, Chem. Lett., 1999, 1149-1150.
(22) Reversible Stretching of a Polymer-Supported Cobalt-Chelate Film in Response to Oxygen, H. Nishide, H. Mizuma, E. Tsuchida, J. McBreen, Bull. Chem. Soc. Jpn., 72, 1123-1127 (1999).
(23) Oxygen Permeability of Biodegradable Copolycaprolactones, S.-G. Wang, H. Nishide, E. Tsuchida, Polymers Adv. Tech., 10, 282-286 (1999).
(24) Reversible Oxygen-Releasing from the Composite of Picketfence-Porphyrinatocobalt and Carbon in Response to a 1.5 V-Application, H. Nishide, Y Suzuki, E. Tsuchida, Bull. Chem. Soc., Jpn., 72, 2791-2794 (1999).
(25) First Synthesis of High Molecular-Weight Poly(2,6-difluoro-1,4-phenylene oxide) by Oxidative Polymerization, K. Oyaizu, Y. Kumaki, K. Saito, E. Tsuchida, Macromolecules, 33, 5766-5769 (2000).
(26) Electroreduction of μ-Oxo Iron(III) Porphyrins Adsorbed on an Electrode Leading to a Cofacial Geometry for the Iron(II) Complex: Unexpected Active Site for the Catalytic Reduction of O2 to H2O, K. Oyaizu, A. Haryono, J. Natori, H. Shinoda, E. Tsuchida, Bull. Chem. Soc. Jpn., 73, 115 1-1161 (2000).
(27) Crystal Structure of Dimeric Manganese(III) Complexes of Tetradentate Schiff-Base Ligands with Ancillary Axial Donors, K. Oyaizu, T. Nakagawa, E. Tsuchida, Inorg. Chim. Acta, 305, 184-188 (2000).
(28) Copper-Catalyzed Oxidative Coupling of 2,4,6-Trimethylphenol with Oxygen, K. Oyaizu, K. Saito, E. Tsuchida, Chem. Lett., 2000, 1318-1319.
(29) Proton-Conduction in Poly(alkylenecarbonate)/Poly(thiophenylenesulfonic acid) Composites, J.-S. Cho, Y. Hayashino, K. Miyatake, S. Takeoka, E. Tsuchida, Polymers Adv. Tech., 11, 548-552 (2000).
(30) Proton-Conduction of Perfluorooctanesulfonic Acid with Polypropylene-Carbonate Composite, J.-S. Cho, Y Hayashino, K. Miyatake, S. Takeoka, E. Tsuchida, Chem. Lett., 2000, 44-45 (2000).
(31) Photoreduction of Self-Assembled Lipidporphyrinatoiron(III) Chloride with Hyaluronic Acid under Semi-Physiological Conditions, T. Komatsu, T. Yanagimoto, A. Nakagawa, E. Tsuchida, Chem. Lett., 2000, 84-85.
(32) Exchange Transfusion of Albumin-Heme as an Artificial O2-Inffision into Anesthetized Rats: Physiological Responses, O2-Delivery and Reduction of the Oxidized Hemin Sites by Red Blood Cells, E. Tsuchida., T. Komatsu, K. Hamamatsu, Y Matsukawa, A. Tajima, A. Yoshizu, Y Izumi, K. Kobayashi, Bioconjugate Chem., 11, 46-50 (2000).
(33) Molecular Environment Effect on O2-Binding to Lipidporphyrinatoiron(II) Complexes in Aqueous Media, E. Tsuchida, T. Komatsu, T. Yanagimoto,J. Porphyrins Phthalocyanines, 4, 81-87 (2000).
(34) Photoinduced Elecron Transfer between Lipidporphyrinato-Zinc(II) and -Iron(III) Complexes in Phospholipid Vesicular Membrane, T. Yanagimoto, T. Komatsu, E. Tsuchida, Inorg. Chim. Acta., 305, 26-31(2000).
(35) Nitrosyl Iron(II) Copmlex of meso-Tetrakis(α,α,α,α-o-pivalamidophenyl)porphyrin with a Covalently Linked 2-Methylimidazolylalkyl Group, T. Komatsu, Y Matsukawa, E. Tsuchida, Chem. Lett., 2000, 1060-106 1.
(36) Kinetics of CO- and O2-Binding to Human Serum Albumin-Heme Hybrid, T. Komatsu, Y Matsukawa, E. Tsuchida, Bioconjugate Chem., 11, 772-776 (2000).
(37) Redox Behavior of Human Serum Albumin-Heme Hybrid on Graphite Electrode Modified with Didodecyldimethylammonium Bromide, Y. Wu, T. Komatsu, E. Tsuchida, Chem. Lett., 2000, 1194-1195.
(38) Poly(ethyleneglycol)-Conjugation and Deoxygenation Enable Long Term Preservation of Hemoglobin Vesicles as Oxygen Carriers, H. Sakai, K. Tomiyama, K. Sou, S. Takeoka, E. Tsuchida, Bioconjugate Chem., 11, 425-432 (2000).
(39) Constriction of Resistance Arteries Determines L-NAME Induced Hypertention, H. Sakai, H. Hara, A. G. Tsai, E. Tsuchida, M. Intaglietta, Microvasc. Res., 60, 21-27 (2000).
(40) Molecular Dimensions of Hb-Based O2 Carriers Determine Constriction of Resistance Arteries and Hypertension in Conscious Hamster Model, H. Sakai, H. Hara, M. Yuasa, A. G. Tsai, S. Takeoka, E. Tsuchida, M. Intaglietta, Am. J. Physiol. Heart Circ. Physiol., 279, 908-915 (2000).
(41) Synthesis and Physicochemical Characterization of a Series of Hemoglobin-Based Oxygen Carriers: Objective Comparison between Cellular and Acellular Types, H. Sakai, M. Yuasa, H. Onuma, S. Takeoka, E. Tsuchida, Bioconjugate Chem., 11, 56-64 (2000).
(42) Poly(ethylene glycol)-Modification of the Phospholipid Vesicles by using the Spontaneous Incorporation of Poly(ethylene glycol)-Lipid into the Vesicles, K Sou, T. Endo, S. Takeoka, E. Tsuchida, Bioconjugate Chem., 11, 372-379 (2000).
(43) Conjugation of Von Willebrand Factor-Binding Domain of Platelet Glycoprotein Ib to Size-Controlled Albumin Microspheres, S. Takeoka, Y Teramura, H. Ohkawa, Y Ikeda, E. Tsuchida, Biomacromolecules, 1, 290-295 (2000).
(44) Assemblies of Multiacyl Poly(ethyleneglycol) Lipids and Co-Assemblies with Phospholipid Vesicles, S. Takeoka, K. Mon, H. Ohkawa, K. Sou, E. Tsuchida, J. Am. Chem. Soc., 122, 7927-7935 (2000).
(45) Photoreduction of Methemoglobin by Irradiation in Near-Ultraviolet Region, H. Sakai, H. Onuma, M. Umeyama, S. Takeoka, E. Tsuchida, Biochemistry, 39, 14595-14602 (2000).
(46) Synthesis of Multiacyl Poly(ethylene glycol) for the Conjugation of Cytochrome c to Phospholipid Vesicle, H. Ohkawa, Y Teramura, S. Takeoka, E. Tsuchida, Bioconjugate Chem., 11, 815-821 (2000).
(47) Membranes of the Picket Fence Cobalt Porphyrin Complexed with Poly(vinyl-imidazole and -pyridine)s: Selective Optical Response to Oxygen, Y Suzuki, H. Nishide, E. Tsuchida, Macromolecules, 33, 2530-2534 (2000).
(48) High Oxygen-Binding Affinity of Poly(4-vinylimidazole-co-octylmethacrylate)Cobalt-porphyrin Complex: Effect of Hydrogen-Bond at the Imidazole Residue, H. Nishide, A. Kato, E. Tsuchida, Mol. Cryst. Liq. Cryst., 342, 249-254 (2000).
(49) Polysulfonium As a New Electrode-Modifying Polyclectrolyte, K. Oyaizu, H. Nakano, J. Natori, E. Tsuchida, J. Electroanal. Chem., 498, 232-236 (2001).
(50) Structure and Redox Properties of a Novel Decavanadium Cluster [(V=O)10(μ2-O)9(μ3-O)3(C5H7O2)6] in Dichioromethane, K. Oyaizu, E. L. Dewi, E. Tsuchida, J. Electroanal. Chem., 498, 136-141 (2001).
(51) Oxidative Polymerization of Pyrrole Promoted by Four-Electron Transfer to O2: Catalysis of O2-Oxidation by μ-Oxo Dinuclear Complexes with Macrocyclic Ligands, K. Oyaizu, A. Haryono, H. Shinoda, E. Tsuchida, Macromol. Chem. Phys., 202, (2001). In press
(52) Polymeization of Methyl Phenyl Sulfoxide under Acidic Conditions: Synthesis and X-Ray Structure Analysis of a Phenylene Sulfonium Polymer, K. Miyatake, K. Oyaizu, Y Nishimura, E. Tsuchida, Macromolecules, 34, 1172-1179 (2001).
(53) Copper(II) Complexes Resulting from the Oxygenation of (2,9-Dimethyl-1,10-phenanthroline)copper(I) Chloride in the Presence of Dimethylformamide, K. Oyaizu, M. Ueno, H. Li, E. Tsuchida, Bull. Chem. Soc. Jpn., 74, 869-870 (2001).
(54) Synthesis and Properties of Novel Sulfonated Arylene Ether / Fluorinated Alkane Copolymers, Kenji Miyatake, Kenichi Oyaizu, Eishun Tsuchida, Allan S. Hay, Macromolecules, 34, 2065-2071(2001).
(55) Reaction of Nitric Oxide with Synthetic Hemoprotein, Human Serum Albumin Incorporating Tetraphenylporphinatoiron(II) Derivatives, T. Komatsu, Y. Matsukawa, E. Tsuchida, Bioconjugate Chem., 12, 7 1-75 (2001).
(56) Photoreduction of Autooxidized Albumin-Heme Hybrid in Saline Solution; Revival of Its O2-Binding Ability, A. Nakagawa, T. Komatsu, E. Tsuchida, Bioconjugate Chem., 12, (2001). In press.
研究制度
  • 戦略的基礎研究推進事業、研究領域「単一分子・原子レベルの反応制御」研究代表者 土田 英俊(早稲田大学理工学部)/科学技術振興事業団
研究報告資料
  • 土田 英俊. 単一分子・原子レベルの反応制御 オキシジェニクス(高分子錯体). 戦略的基礎研究推進事業 平成11年度 研究年報.科学技術振興事業団, 2000. p.371 - 375.

PAGE TOP