連続ポテンシャル場の構築

1989 Fiscal Year Annual Research Report

• Project/Area Number: 01612002
• Research Institution: The University of Tokyo
• Principal Investigator: 戸嶋 直樹 東京大学, 工学部, 助教授 (50011010)
• Co-Investigator(Kenkyū-buntansha): 阿部 康次 信州大学, 繊維学部, 助教授 (00126658) ; 山本 隆一 東京工業大学, 資源化学研究所, 教授 (10016743) ; 竹本 喜一 大阪大学, 工学部, 教授 (50029170) ; 金子 正夫 理化学研究所, 副主任研究員 (90109794) ; 白井 汪芳 信州大学, 繊維学部, 教授 (80021153)
• Keywords: 連続ポテンシャル場 / 高分子金属錯体 / 金属クラスター / ギャドサイクル系 / 生体系高分子 / 相互作用 / 多電子移動 / 触媒作用

Research Abstract

1.金属クラスター錯体内における連続ポテンシャル場の構築ーー高分子包埋PtーPdバイメリッククラスターでは、Pt/Pd=1/4のとき白金原子を核とする二層構造となり高い触媒活性を示すことを明らかにした。αーピロリドンを配位子とする4核の白金ブルー錯体を用いて多電子移動反応に成功した。これらはいずれもクラスター内連続ポテンシャル場の構築に基づくものである。
2.高分子金属錯体によるギャドサイクル系の構造ーー生体内酸化酵素モデルとして高分子固定化コバルト(II)および鉄(III)フタロシアニン誘導体を用い酸化還元ギャドサイクル系を組立てて、メルカプトエタノールの空気酸化の高効率化に成功し、悪息消除に応用した。また、多核ルテニウム錯やマンガン錯体を用いて光合成モデルのギャドサイクル系を構成させ、水の4電子酸化に成功した。
3.生体系高分子錯体の相互作用と連続ポテンシャル場ーー水溶性核酸アナログを合成し、高分子間相互作用を明らかにした。また高分子金属錯体の相互作用を利用して、核酸の合成および分解のモデル反応系を構成することに成功した。さらにアミノ酸類や糖質を含む金属錯体による分子認識を利用した新規機能素子へと発展を目ざしている。これらは、いずれも分子間相互作用と連続ポテンシャル場の概念を巧みに用いて成功したものである。
4.高分子金属錯体の連続ポテンシャル場と多電子移動ーー複素共役系高分子の新規合成法を開発し、この高分子を用いて、金属塩を配位させることにより高効率の多電子移動に成功した。また、ポリアクリルニトリルなどのポリマーとCuS、CdSなどの金属硫化物とを含む新しいオルガノゾルの電気伝導性を見出した。さらに、高分子電解質錯体を用いて電導度に及ぼすミクロ環境の効果を明らかにした。

Research Products

• [Publications] 戸嶋直樹: "金属超微粒子分散系の合成とその機能" 塗装工学. 24. 71-78 (1989)
• [Publications] 戸嶋直樹: "ますます高まる高分子錯体の重要性(連続ポテンシャル場)" 化学. 44. 172-173 (1989)
• [Publications] Naoki Toshima: "Transient Spectroscopy of the Redox Reactions of the Prussian Blue Membrane Having Electronic State Gradient" Chemistry Lett.1989. 1099-1102 (1989)
• [Publications] Wataru Mizutani: "Measurements of Copper Phthalocyanine Ultrathin Films by Scaning Tunneling Microscopy and Spectroscopy" Japanese J.Applied Physics. 28. Ll460-Ll463 (1989)
• [Publications] 趙斌: "ポリ(N2ビニルー2ーピロリドン)に保護されたロジウム及びパラジウム超微粒子分散系触媒による1,3ーシクロオクタジエンの水素化" 高分子論文集. 46. 551-558 (1989)
• [Publications] Naoki Toshima: "Colloidal Dispersions of Palladium-Platinum Bimetallic Clusters Protected by Polymers.Preparation and Application to Catalysis" Chemistry Lett.1989. 1769-1772 (1989)
• [Publications] 戸嶋直樹: "分子線蒸着法による配向性有機超薄膜の作製" 化学工学. 40. 959-964 (1989)
• [Publications] 戸嶋直樹: "規制された構造の分子集合体に保持された金属超微粒子の合成と機能" 旭硝子工業技術奨励会研究報告. 54. 145-156 (1989)
• [Publications] Satoshi Tanishima: "Effect of Film Thickness Upon Molecular Orientation in Copper(II)Phthalocyanine Ultrathin Films Prepared by Molecular Beam Deposition" Chem.Express. 1990. (1990)
• [Publications] Naoki Toshima: "A New Preparation Method of Electrochromic Prossian Blue Films by Casting a Solution and Their Electrochemical Properties" Chemistry Lett.1990. (1990)
• [Publications] Michitaka Ohtaki: "Photoreduction of Rhdium3(III)Ion in Water with Ultraviolet Light Aiming to Prepare the Dispersions of Ultrafine Particle" Chemistry Lett.1990. (1990)
• [Publications] 戸嶋直樹: "機能性高分子錯体" 高分子加工. 38. (1990)
• [Publications] Naoki Toshima: "Polymer-Protected Bimetallic Clusters.Preparation and Application to Catalysis" J.Macromol.Sci.-Chem.(1990)
• [Publications] H.Ito: "Biaxially Orientated Langmuir-Blodgett Films of Substituted Metallophthalocyanine" J.Chem.Soc.,Dalton Trans.1989. 1543-1546 (1989)
• [Publications] H.Ito: "Thermally Stable Metallophthalocyanine Formaldehyde Condensation Resins" J.Polym.Sci.,Polym.Chem.Ed.27. 2531-2537 (1989)
• [Publications] Hirofusa Shirai: "Kinetics and Mechanism of the Biomimetic Oxidation of Thiol by Oxygen Catalyzed by Homogeneous Polycarboxyphthalocyaninato Metals" J.Phys.Chem.(1990)
• [Publications] Hirofusa Shirai: "Kinetics and Mechanism of the Biomimetic Decomposition of Hydrogen Peroxide Catalyzed by Heterogeneous Octacarboxyphthalocyaninato Iron(III)Supported or Amorphous Enriched Rayon Staple Fiber" J.Phys.Chem.(1990)
• [Publications] H.Tsuiki: "The Biomimetic Oxidation of Thiol with Oxygen Catalyzed by Hetero-geneous Octacarboxyphthalocyaninato Iron(III)and cobalt(II)Supported on Amorphous Enriched Rayon Staple Fiber" Textile Res.J.(1990)
• [Publications] H.Tsuiki: "Kinetics and Mechanism of the Biomimetic Oxidation of Hydrogen Sulfide by Oxygen Catalyzed by Homogeneous Metallophthalocyanine Polycarboxylic Acids" J.Mol.Catal.(1990)
• [Publications] Masao Kaneko: "Efficient Water Cleavage with Visible Light by a System Mimicking Photosystem II" J.Chem.Soc.,chem.commun.1989. 1338-1339 (1989)
• [Publications] Masao Kaneko: "Photochargeable Multilayer Membrane Device Composed of CdS Film and Prussian blue Battery" Electrochim.Acta. 35. 291-293 (1990)
• [Publications] 山田和伸: "ビオロゲン型ポリシロキサン膜とフタロシアニン膜から成る光電応答機能電極" 電気化学および工業物理化学. 57. 1129-1132 (1989)
• [Publications] Kazunobu Yamada: "Syntheses of Viologen-pendant Polysiloxanes and their Characteristic Behavior of Aggregation and Deposition Observed in Electron Transfer" Makromol.Chem.(1990)
• [Publications] 金子正夫: "高分子金属錯体の機能と応用の新展開" 高分子加工. 38. 2-7 (1989)
• [Publications] Tekehiko Wada: "Synthesis and Interaction Studies on Water Soluble Nucleic Acid Analogs:Polyethyleneimine Derivatives Containing Cytosine and Hypoxanthine" Polymer J.21. 11-18 (1989)
• [Publications] Tekehiko Wada: "Synthesis and Interaction studies on Water Soluble Nucleic Acid Analogs:Polyethleneimine Derivatives Containing Uracil and 5-Fluorouracil" J.Bioactive and Compatible Polymers. 4. 25-41 (1989)
• [Publications] Suguru Nagae: "Specific Interaction of Nucleic Acid Analogs in High Performance Liquid Chromatography System" Polymer J.21. 425-432 (1989)
• [Publications] Suguru Nagae: "Application of Nucleic Acid Base Containing Polymers to High Performance Liquid Chromatography" J.Polym.Sci.,Polym.Chem.27. 2593-2609 (1989)
• [Publications] Takakazu Yamamoto: "Electrically Conducting,thermaly Stable and Mechanically Strong CuS-Poly(Parabanic Acid)composite Films and Their Shielding Effect of Electromagnetic Wave" Colloid Polym.Sci.267. 546-548 (1989)
• [Publications] Takakazu Yamamoto: "Alkaline Metal Secondary Batteries Using Poly(2,5-pyridinediyl)as an Active Electrode Material" Jpn.J.Appl.Phys.28. L875-L876 (1989)
• [Publications] Takakazu Yamamoto: "Polymers and Oligomers with Substituted 2,5-Thienylene Units.Preparation and Electrical Conducting Properties" Makromol.Chem.190. 1649-1655 (1989)
• [Publications] Takakazu Yamamoto: "Polarizing Film Prepared by Using Linear Poly(2,5-pyridinediyl)" Chemistry Lett.1989. 1951-1952 (1989)
• [Publications] Takakazu Yamamoto: "Conductive Polymer Materials" MRS Meeting Report. 1. (1989)
• [Publications] Takakazu Yamamoto: "New Method for Preparation of Poly(2,5-thienylene),Poly(p-phenylene)and Related Polymers" Polymer J.22. 187 (1990)
• [Publications] Ken-ichi Sanechika: "Mossbauer Spectroscopic Study of FeCl_3 Complexes of Poly(N-methyl-2,5-pyrrolylene),Poly(2,5-thienylene),Poly(3-methyl-2,5-thienylene)Prepared by Ni-catalyzed Polycondensation" J.Macromol.Sci.-Chem.(1990)
• [Publications] Kazuhiko Seki: "UV Photoelectron Spectroscopy of Poly(2,2'-ferrocenylene)" Chem.Phys.Lett.(1990)
• [Publications] Yoshihiro Itoh: "Fluorescence Study of Polyelectrolyte Complex Formation I.Complexation of Anthracene-loaded Poly(methacrylic acid)with Polycations" Polym.Adv.Technol.2. (1990)
• [Publications] Yoshihiro Itoh: "Fluorescence Study of Polyelectrolyte Complex Formation II.Effect of Acidity on Complexation" Macromolecules. (1990)
• [Publications] Y.Ishikawa: "Structure of the Organic Superconductor,(DMET)_2Aul_2" Acta Crystallogr.C45. 572-575 (1989)
• [Publications] K.Kanoda: "Anomalous Spin Dyanmics of Conduction Electrons in the Organic Conductor,[dimethyl(ethylenedithio)diselenadithiafulvalene]_2AuBr_2" Solid State Commun.68. 415-418 (1989)
• [Publications] K.Kanoda: "EPR Studies of a New Family of Organic Conductors:The dimethyl-(ethylenedithio)diselenadithiafulvalene Compounds,(DMET)_2×[×=PF_6,BF_4,Au(CN)_2,I_3and AuBr_2]" Phys.Rev.B39. 3396-4003 (1989)
• [Publications] K.Saito: "Phase Transition on(DMET)_2Au(CN)_2 at 180K" J.Phys.:condensed Matt.1. 8823-8829 (1989)
• [Publications] K.Saito: "First Unsymmetrical Donor Which Gives Organic Superconductors:DMET" Acta Crystallogr.C45. 1403-1405 (1989)
• [Publications] K.Saito: "Thermoelectric Power and an Order-Parameter Associated with the Phase Transition at 180K of the Organic Metal,(DMET)_2Au(CN)_2" J.Phys.Soc.Jpn.58. 4093-4097 (1989)
• [Publications] Y.Honda: "Phase Diagram of Superconductivity and Spin Density Wave in (DMET)_2Au(CN)_2" Solid State Commun.71. 1087-1092 (1989)
• [Publications] Hiroaki Sawai: "Uranyl Ion as a Highly Efficient Catalyst for the Internucleotide Bond Formation" Bull.Chem.Soc.Jpn.62. 2018-2023 (1989)
• [Publications] M.Shimazu: "Facile Synthesis of Nucleotide Containing Polyphosphate by Mn(II)and Cd(II)Ion Catalyzed Pyrophosphate Bond Formation" Tetrahedron Lett.31. 235-238 (1990)
• [Publications] Hiroaki Sawai: "Effect of Azoles As a Nucleotide Activating Group on Uranyl-Ion Catalyzed Synthesis of Oligoadenylates in Aqueous Solution" Bull.Chem.Soc.63. (1990)
• [Publications] Ken Sakai: "Mixed-Valent Octanuclear Platinum Acetamide Complex,[Pt_8(NH_3)_<16>(C_2H_4NO)_8]^<10+>" J.Am.Chem.Soc.111. 3074-3075 (1989)
• [Publications] Kazuko Matsumoto: "Crystal Structure and ^<13>C and ^<195>Pt NMR Spectra of an alpha-Pyrrolidonate-Bridged Binuclear Platinum(II)Complex,[Pt_2(NH_3)_4(C_4H_6NO)_2]_2(PF_6)_3(NO_3)・H_2O" Inorg.Chem.28. 2959-2964 (1989)
• [Publications] Takeya Abe: "Crystal Structure and ^<13>C NMR of alpha-Pyrrolidonato-Bridged [Pt(III)_2(NH_3)_4(C_4H_6NO)_2(NO_2)(NO_3)](NO_3)_2・H_2O and Conversion of the Binuclear into Tetranuclear Complex on Electrochemical Redox Reaction" Chemistry Lett.1989. 1857-1860 (1989)
• [Publications] Katsuhiko Suzuki: "synthesis and Crystal Structure of Head-to-Head Bis(μ-2-pyridonato-N,O)bis[(ethylenediamine)palladium]Nitrate,[Pb_2(en)_2-(C_5H_4NO)_2](NO_3)_2" Chemistry Lett.1989. 317-320 (1989)
• [Publications] Kazuko Matsumoto: "Crystal Structure of Head-to-Head Bis(μ-α-Pyridonato-N,O)bis-[ethylenediamine)palladium]Nitrate[Pd_2(en)_2(C_5H_4NO)_2](NO_3)_2,and^<13>C and ^1H-^<13>C COSY NMR Study of Head-to-Head to Head-to Tail Isomerization in Solution" Inorg.Chem.(1990)
• [Publications] 矢野重信: "金属イオンとアミンの協同効果による糖質の集積と変換" 日本化学会誌. 5. 769-783 (1989)
• [Publications] Shigenobu Yano: "Optical Resolution of a Co(III) Complex of 2-Hydroxy-1,3-Propane-diamine-N,N,N^1,N^1-tetraacetic Acid: Crystal Structure of (+)-Strychnine(2-Hydroxy-1,3-propanediamine-N,N,N^1,N^1-tetraacetato)-cobaltate(III)Sesquihydrate,(+)-(STC)[Co(dhpta)]・1.5 H_2O" Bull.Chem.Soc.Jpn.62. 3932-3938 (1989)
• [Publications] Takahiko Kojima: "Synthesis and Characterization of Cobalt(III)Complexes Containing α-Diamine and Carbinolamine Derived from α-Aminomalonate and Ethylenediamine" Inorg.Chem.(1990)
• [Publications] 戸嶋直樹: "高分子錯体材料(高分子新素材ワンポイントシリーズ)" 共立出版, (1990)
• [Publications] 工業技術会: "最新の消臭剤と消臭技術" 工業技術会, 362 (1989)
• [Publications] 金子正夫: "光エネルギー変換有機材料" 冬樹社(新素材100シリーズ), 80 (1989)
• [Publications] 山本隆一: "ポリマーバッテリー" 共立出版, (1990)