2000 年度実績報告書

水素一電子相互作用系

研究課題

研究課題/領域番号	10146103
研究機関	大阪大学
研究代表者	中筋一弘大阪大学, 大学院・理学研究科, 教授 (60028230)
研究分担者	三浦洌熊本大学, 医学部, 教授 (70093466) 坂田祥光大阪大学, 産業科学研究所, 教授 (60029874) 三谷忠興北陸先端科学技術大学院大学, 材料科学研究科, 教授 (50010939) 金藤敬一九州工業大学, 情報工学部, 教授 (70124766) 田所誠大阪市立大学, 大学院・理学研究科, 助教授 (60249951)
キーワード	水素結合 / プロトン / 非局在電子系 / 水素-電子相互作用系 / 電子移動 / 電荷移動
研究概要	"水素-電子相互作用系"においては,プロトン移動と電子移動が連動する分子システムを開発し,連動または複合により,単独では発現しない新しい機能を作り出すことが重要課題である.このような研究の学術的特色は,1)新しい概念を学際的に探索すること,2)生体機能の本質を有機化学的に抽出すること,3)非局在電子系を物性科学的観点から応用的側面を重視すること,および合成・物性グループが互いに連携して特異な水素-電子相互作用系の創出を目指ことにある.これまでの成果を以下にまとめる。(1)a)プロトンー電子連動を活用した新システムの開発では,温度上昇により水素結合が融解し,金属的電導性を与える電荷移動錯体を開発した(中筋,三谷),b)プロトンダイナミックスによる機能性分子システムの構築(菅原),c)水素結合と配位結合を用いた自己組織体の開発においては,水素結合と配位結合による二重螺旋構造の構築に成功した(田所).(2)a)人工光合成を目指したパイ電子複合系の構築(坂田),b)フラビン酵素における電子移動反応場の作動原理の分子レベルの解明では,フラビン酵素D-アミノ酸オキシダーゼ(DAO)の紫色中間状態のX線結晶構造解析に初めて成功した。(3)a)導電性高分子、ポリ(3-アルキルチオフェン)のキャリアー移動度は、側鎖が短く立体規則性が高い程移動度は大きいことが分かった。(金藤),b)電子-プロトン相互作用に基づく新規素子機能の探索では,電解還元により水素ドーピングができることを見出した.

研究成果
(34件)

すべてその他

すべて文献書誌 (34件)

[文献書誌] Y.Morita: "New Persistent Radicals : Synthesis and Electronic Spin Structure of 2,5-Di-t-Butyl-6-Oxophenalenoxyl Derivatives."J.Am.Chem.Soc. 122. 4825-4826 (2000)
[文献書誌] M.Tadokoro: "Hydrogen Bonded 2.2'-Biimidazolate Transition Metal Complexes as a Tool of Crystal Engineering."Cord.Chem.Rev.. 198. 205-218 (2000)
[文献書誌] K.Fukui: "ESR/ENDOR (TRIPLE) Studies on Generation and Decay Process of a Triangulene Derivative, the First Non-Kekule Polynuclear Aromatic Hydrocarbon."Magnetic Resonance and Related Phenomena. 311-314 (2000)
[文献書誌] K.Fukui: "Electron-Nuclear Multiple Resonance Studies on Novel Persistent Neutral Radical with 1,3-Diazaphenalene Skeleton."Magnetic Resonance and Related Phenomena. 351-354 (2000)
[文献書誌] T.Shigeta: "Theoretical Study on Dependency of Conductivity on Structure of the Proton-and Electron-Coupled System."Int.J.Quantum Chem. 80. 882-891 (2000)
[文献書誌] M.Nishizawa: "Evidence for the Breakdown of Simple Classical Pictures of Organic Molecule-Based Ferrimagnetics : Low-Temperature Crystal Structure and Single-Crystal ESR Studies of an Organic Heterospin System."J.Phys.Chem., B. 104. 503-509 (2000)
[文献書誌] G.Ono: "One-Dimensional Double Chain Composed of Carbamoylmethylthio-Substituted TTF-Based Donor in Ion Radical Salt."J.Mater.Chem.,. 10. 2277-2282 (2000)
[文献書誌] A Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor : Thianthrene bis (nitronyl nitroxide)."J.Am.Chem.Soc.. 122. 3234-3235 (2000)
[文献書誌] H.Sakurai: "Design, Preparation and Electronic Structure of High-Spin Cation Diradicals Derived from Amine-Based Spin-Polarized Donors."J.Am.Chem.Soc.. 122. 9723-9734 (2000)
[文献書誌] T.Mochida: "Tetra-n-butylammonium bis (1,2-dimercaptoethene-1,2-dicarbonitrilato-S,S') nickel (III)."Acta Cryst., C. 56. 1183-1184 (2000)
[文献書誌] K Nishi: "Coupling between the Internal Rotation of the Methyl Group and Proton/deuteron Transfer in Jet-Cooled 5-Metyl-9-hydroxyphenalenone (OH) and 5-Metyl-9-hydroxyphenalenone (OD) : Tunneling Rate Dependence of Coupling Potential."J.Chem.Phys.. 112. 5002-5011 (2000)
[文献書誌] I.Tamura: "X-ray diffraction studies on the lock-in phase transition of intramolecular hydrogen-bonded compound d-BrHPLN."J.Phys. : Condens.Matter. 12. 8345-8356 (2000)
[文献書誌] J.Mizuguchi: "Correlation between crystal and electronic structures in diketopyrrolopyrrole pigments as viewed from exciton coupling effects"J.Phys.Chem.A. 104. 1817-1821 (2000)
[文献書誌] J.Mizuguchi: "Correlation between crystal and electronic structures in diketopyrrolopyrrole pigments as viewed from exciton coupling effects"J.Phys.Chem.A. 104. 1817-1821 (2000)
[文献書誌] S.Matsumoto: "Structure of magnesiumphthalocyanine complexes"Z.Krist. 215. 182-186 (2000)
[文献書誌] H.Mizutani: "Three-dimensional structure of the purple intermediate of porcine kidney D-amino acid oxidase. Optimization of the oxidative half-reaction through alignment of the product with reduced flavin"J.Biochem. 128. 73-81 (2000)
[文献書誌] Y.Nishina: "Substrate recognition and activation mechanism of D-amino acid oxidase A study using substrate analogs."J.Biochem. 128. 213-223 (2000)
[文献書誌] R.Miura: "Porcine kidney D-amino acid oxidase : The three-dimensional structure and its catalytic mechanism based on the enzyme-substrate complex model."J.Mol.Catalysis.B, Enzymatic. 12. 43-52 (2001)
[文献書誌] R.Miura: "Versatility and specificity of flavoenzymes : Control mechanism of flavin reactivity."The Chemical Record. 1(in press). (2001)
[文献書誌] Wee Y.Lim: "Dependencies of Field Effect Mobility on Regioregularity and Side Chain Length in Poly (alkylthiophene) Films"IEICE Transactions onElectronics. E-83-C. 1071-1075 (2000)
[文献書誌] Shyam S.Pandey: "Effect of Synthetic Impurities on Photocarrier Transport in Poly (3-hexylthiophene)"IEICE Transations on Electronics. E-83-C. 1088-1093 (2000)
[文献書誌] Y.Ando: "Multiwalled carbon nanotubes prepared by hydrogen arc"Diamondand Related Materials. 9. 845-851 (2000)
[文献書誌] Shyam S.Pandey: "Role of Processing Solvents in Photocarrier Transport of Polyanilines"Jpn.J.Appl.Phys. 39. 4045-4050 (2000)
[文献書誌] K.Kaneto: "Alkyl Chain Length Dependence of Field-Effect Mobilities in Regioregular Poly (3-Alkylthiophene) Films"Jpn.J.Appl.Phys. 39. L872-L874 (2000)
[文献書誌] K.Keiichi: "Direct measurement and Mechanism of electrochemomechanical Expansion and Contraction in Polypyrrole Films"Jpn.J.Appl.Phys.. 39. 5918-5922 (2000)
[文献書誌] M.Kaneko: "Polym.Deformation of poly (o-methoxyaniline) Film Induced by polymer Conformation on Electrochemical Oxidation"Journal, Jan.. 33. 104-107 (2001)
[文献書誌] Shyam S.Pandey: "Mechanism of Photocarrier Generation and Transport in Poly (3-alkylthiophene) films"Jpn.J.Appl.Phys.. 37. 6309-6313 (2000)
[文献書誌] H.Onodera: "Photophysical and Photochemical Behavior of Triplet Excited State of C60 in Unimer Micelle"Chem.Lett.. 426-427 (2000)
[文献書誌] D.Hirayama: "Preparation and Photoelectrochemical Properties of Gold Electrodes Modified with [60] Fullerene-Linked Oligothiophenes"Chem.Lett.. 570-571 (2000)
[文献書誌] H.Imahoari: "Photoinduced Energy Transfer in Mixed Self-Assembled Monolayeres of Pyrene and Porphyrin"Chem.Commun. 661-662 (2000)
[文献書誌] K.Sugiura: "A Porphyrin Square : Synthesis of a Square-Shaped p-Conjugated Porphyrin Tetramer Connected by Diacetylene Linkages"Chem.Commun. 1105-1106 (2000)
[文献書誌] H.Imahori: "Chain Length Effect on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayeres of Porphyrins on Gold Electrodes"J.Phys.Chem.B. 104. 1253-1260 (2000)
[文献書誌] H.Imahori: "Vectorial Multistep Electron Transfer at the Gold Electrodes Modified with Self-Assembled Monolayeres of Ferrocence-Porphyrin-Fullerene Triads"J.Phys.Chem.B. 104. 2099-2108 (2000)
[文献書誌] H.Tsue: "Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin-Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring"J.Am.Chem.Soc.. 122. 2279-2288 (2000)

2000 年度 実績報告書

水素一電子相互作用系

研究代表者

中筋 一弘 大阪大学, 大学院・理学研究科, 教授 (60028230)

研究成果

[文献書誌] Y.Morita: "New Persistent Radicals : Synthesis and Electronic Spin Structure of 2,5-Di-t-Butyl-6-Oxophenalenoxyl Derivatives."J.Am.Chem.Soc. 122. 4825-4826 (2000)

[文献書誌] M.Tadokoro: "Hydrogen Bonded 2.2'-Biimidazolate Transition Metal Complexes as a Tool of Crystal Engineering."Cord.Chem.Rev.. 198. 205-218 (2000)

[文献書誌] K.Fukui: "ESR/ENDOR (TRIPLE) Studies on Generation and Decay Process of a Triangulene Derivative, the First Non-Kekule Polynuclear Aromatic Hydrocarbon."Magnetic Resonance and Related Phenomena. 311-314 (2000)

[文献書誌] K.Fukui: "Electron-Nuclear Multiple Resonance Studies on Novel Persistent Neutral Radical with 1,3-Diazaphenalene Skeleton."Magnetic Resonance and Related Phenomena. 351-354 (2000)

[文献書誌] T.Shigeta: "Theoretical Study on Dependency of Conductivity on Structure of the Proton-and Electron-Coupled System."Int.J.Quantum Chem. 80. 882-891 (2000)

[文献書誌] M.Nishizawa: "Evidence for the Breakdown of Simple Classical Pictures of Organic Molecule-Based Ferrimagnetics : Low-Temperature Crystal Structure and Single-Crystal ESR Studies of an Organic Heterospin System."J.Phys.Chem., B. 104. 503-509 (2000)

[文献書誌] G.Ono: "One-Dimensional Double Chain Composed of Carbamoylmethylthio-Substituted TTF-Based Donor in Ion Radical Salt."J.Mater.Chem.,. 10. 2277-2282 (2000)

[文献書誌] A Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor : Thianthrene bis (nitronyl nitroxide)."J.Am.Chem.Soc.. 122. 3234-3235 (2000)

[文献書誌] H.Sakurai: "Design, Preparation and Electronic Structure of High-Spin Cation Diradicals Derived from Amine-Based Spin-Polarized Donors."J.Am.Chem.Soc.. 122. 9723-9734 (2000)

[文献書誌] T.Mochida: "Tetra-n-butylammonium bis (1,2-dimercaptoethene-1,2-dicarbonitrilato-S,S') nickel (III)."Acta Cryst., C. 56. 1183-1184 (2000)

[文献書誌] K Nishi: "Coupling between the Internal Rotation of the Methyl Group and Proton/deuteron Transfer in Jet-Cooled 5-Metyl-9-hydroxyphenalenone (OH) and 5-Metyl-9-hydroxyphenalenone (OD) : Tunneling Rate Dependence of Coupling Potential."J.Chem.Phys.. 112. 5002-5011 (2000)

[文献書誌] I.Tamura: "X-ray diffraction studies on the lock-in phase transition of intramolecular hydrogen-bonded compound d-BrHPLN."J.Phys. : Condens.Matter. 12. 8345-8356 (2000)

[文献書誌] J.Mizuguchi: "Correlation between crystal and electronic structures in diketopyrrolopyrrole pigments as viewed from exciton coupling effects"J.Phys.Chem.A. 104. 1817-1821 (2000)

[文献書誌] J.Mizuguchi: "Correlation between crystal and electronic structures in diketopyrrolopyrrole pigments as viewed from exciton coupling effects"J.Phys.Chem.A. 104. 1817-1821 (2000)

[文献書誌] S.Matsumoto: "Structure of magnesiumphthalocyanine complexes"Z.Krist. 215. 182-186 (2000)

[文献書誌] H.Mizutani: "Three-dimensional structure of the purple intermediate of porcine kidney D-amino acid oxidase. Optimization of the oxidative half-reaction through alignment of the product with reduced flavin"J.Biochem. 128. 73-81 (2000)

[文献書誌] Y.Nishina: "Substrate recognition and activation mechanism of D-amino acid oxidase A study using substrate analogs."J.Biochem. 128. 213-223 (2000)

[文献書誌] R.Miura: "Porcine kidney D-amino acid oxidase : The three-dimensional structure and its catalytic mechanism based on the enzyme-substrate complex model."J.Mol.Catalysis.B, Enzymatic. 12. 43-52 (2001)

[文献書誌] R.Miura: "Versatility and specificity of flavoenzymes : Control mechanism of flavin reactivity."The Chemical Record. 1(in press). (2001)

[文献書誌] Wee Y.Lim: "Dependencies of Field Effect Mobility on Regioregularity and Side Chain Length in Poly (alkylthiophene) Films"IEICE Transactions onElectronics. E-83-C. 1071-1075 (2000)

[文献書誌] Shyam S.Pandey: "Effect of Synthetic Impurities on Photocarrier Transport in Poly (3-hexylthiophene)"IEICE Transations on Electronics. E-83-C. 1088-1093 (2000)

[文献書誌] Y.Ando: "Multiwalled carbon nanotubes prepared by hydrogen arc"Diamondand Related Materials. 9. 845-851 (2000)

[文献書誌] Shyam S.Pandey: "Role of Processing Solvents in Photocarrier Transport of Polyanilines"Jpn.J.Appl.Phys. 39. 4045-4050 (2000)

[文献書誌] K.Kaneto: "Alkyl Chain Length Dependence of Field-Effect Mobilities in Regioregular Poly (3-Alkylthiophene) Films"Jpn.J.Appl.Phys. 39. L872-L874 (2000)

[文献書誌] K.Keiichi: "Direct measurement and Mechanism of electrochemomechanical Expansion and Contraction in Polypyrrole Films"Jpn.J.Appl.Phys.. 39. 5918-5922 (2000)

[文献書誌] M.Kaneko: "Polym.Deformation of poly (o-methoxyaniline) Film Induced by polymer Conformation on Electrochemical Oxidation"Journal, Jan.. 33. 104-107 (2001)

[文献書誌] Shyam S.Pandey: "Mechanism of Photocarrier Generation and Transport in Poly (3-alkylthiophene) films"Jpn.J.Appl.Phys.. 37. 6309-6313 (2000)

[文献書誌] H.Onodera: "Photophysical and Photochemical Behavior of Triplet Excited State of C60 in Unimer Micelle"Chem.Lett.. 426-427 (2000)

[文献書誌] D.Hirayama: "Preparation and Photoelectrochemical Properties of Gold Electrodes Modified with [60] Fullerene-Linked Oligothiophenes"Chem.Lett.. 570-571 (2000)

[文献書誌] H.Imahoari: "Photoinduced Energy Transfer in Mixed Self-Assembled Monolayeres of Pyrene and Porphyrin"Chem.Commun. 661-662 (2000)

[文献書誌] K.Sugiura: "A Porphyrin Square : Synthesis of a Square-Shaped p-Conjugated Porphyrin Tetramer Connected by Diacetylene Linkages"Chem.Commun. 1105-1106 (2000)

[文献書誌] H.Imahori: "Chain Length Effect on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayeres of Porphyrins on Gold Electrodes"J.Phys.Chem.B. 104. 1253-1260 (2000)

[文献書誌] H.Imahori: "Vectorial Multistep Electron Transfer at the Gold Electrodes Modified with Self-Assembled Monolayeres of Ferrocence-Porphyrin-Fullerene Triads"J.Phys.Chem.B. 104. 2099-2108 (2000)

[文献書誌] H.Tsue: "Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin-Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring"J.Am.Chem.Soc.. 122. 2279-2288 (2000)

2000 年度実績報告書

中筋一弘大阪大学, 大学院・理学研究科, 教授 (60028230)