1999 年度実績報告書

分子認識機能界面とセンシング

研究課題

研究課題/領域番号	09237106
研究機関	熊本大学
研究代表者	谷口功熊本大学, 工学部, 教授 (90112391)
研究分担者	末永智一東北大学, 大学院・工学研究科, 教授 (70173797) 佐々木陽一北海道大学, 大学院・理学研究科, 教授 (30004500) 山添昇九州大学, 大学院・総合理工学研究科, 教授 (40037817)
キーワード	分子認識 / センシング / 構造規制界面 / 電極反応 / 電子移動 / 無機・有機複合界面 / 生体機能界面 / 固体型センサ
研究概要	本研究では、新しいセンシング機能界面の創製を目指して、1)制御無機・有機複合化界面の創製、2)酵素モデル構造性金属錯体等を用いた生体機能界面の構築、3)無機固体界面を用いたガスセンサ機能界面の構築、などの研究を進め、以下のような研究成果を得た。 1.制御無機・有機複合化界面での分子認識機能の発現に関して、シトクロムcの電気化学応答に対する明確な界面構造依存性を2-、4-ピリジンチオール(2-PySH、4-PySH)、2-ピリミジンチオール(2-PymSH)等を用いて示し、その界面構造や吸着分子のピリジン窒素のpKaは変化などをSTM測定および表面赤外分光測定から明らかにした。4-PySHの金(100)面上での吸着構造やアントラキノン部位を持つアルキルチオールの金電極上へ吸着挙動を明らかにした。 2.生体機能界面の創製と応用において、ヘムエリトリン酵素機能を有する多電子移動型のルテニウムニ核錯体の電極上への固定化に成功し、その特性を明らかにした。また、2-PymSH修飾金電極上では銅タンパク質であるアズリンの速い電子移動反応を観測した。電気化学顕微鏡を用いて単一細胞および細胞膜の機能を明らかにすると共に自己集合的に電極上にパターニングした酵素等のイメージングに成功した。 3.高選択制・無機固体型センサ機能界面の創製に関して、半導体型ガスセンサの高感度化のため酸化スズゾル粒子の分散性を制御してメソポア構造の制御によりセンサ感度を一桁向上できた。また、100ppmレベルの二酸化炭素測定用の高耐湿性・低温動作機能を持つ固体電解質型ガスセンサを開発し選択性発現のための界面構造を明らかにすると共に高機能化のメカニズムを示した。これらの研究は、いずれも新しい機能材料・機能素子創出の基礎の確立に大きく寄与する世界をリードする研究である。

研究成果

(42件)

すべてその他

すべて文献書誌 (42件)

[文献書誌] Nishiyama,Katsuhiko: "Photochemical Reduction of NADP+ by Zinc Porphyrin Reconstituted Myoglobin as a Simple Model of Photosystem I"Chem.Lett.,. 357-358 (1999)
[文献書誌] Uemura,Shinobu: "In situ STM visualization of Fullerlene Epitaxial Adlayers on Au(111) Surfaces Prepared by the Transfer of Langmuir Films"Chem.Lett.,. 279-280 (1999)
[文献書誌] Nishiyama,Katsuhiko: "Phase Separation of an Unsymmetrical Disulfide SAM at an Evaporated Au(111) Electrode Monitored by Reductive Desorption and the Electrochemical Response of Cytochrome c"Chem.Lett.,. 753-754 (1999)
[文献書誌] Taniguchi,Isao: "Electroanalytical chemistry of myoglobin with modification of distal histidine by cyanated imidazole"J.Electroanal.Chem.,. 468,. 9-18 (1999)
[文献書誌] Yoshimoto,Soichiro: "Electorochemical study on competitive adsorption of pyridinethiol with sulfide onto Au(111) surfaces"J.Electroanal.Chem.,. 473,. 85-92 (1999)
[文献書誌] Azehara,Hiroaki: "Investigation of structure of self-assembled monolayers of asymmetrical disulfide on Au(111) electrodes by electrochemical desorption"J.Electroanal.Chem.,. 473,. 68-74 (1999)
[文献書誌] Akashi,Tetsuyuki: "Comparison of the Electrostatic Binding Sites on the Surface of Ferredoxin for Two Ferredoxin-dependent Enzymes,Ferredoxin-NADP+Reductase and Sulfate Reductase"J.Biol.Chem.,. 274,. 29399-29405 (1999)
[文献書誌] Ohira,Akihiro: "Self-organization of a-cyclodextrin on Au(111) surfaces induced by potential controlled adsorption"J.Electroanal.Chem.,. 472,. 163-167 (1999)
[文献書誌] Nishiyama,Katsuhiko: "Structural differences in self-assembled monolayers of anthraquinone derivatives of silver and gold electrodes studied by cyclic voltammmetry and in situ SERS spectroscoy"J.Electroanal.Chem.,. 478,. 83-91 (1999)
[文献書誌] Taniguchi,Isao: "Potential and pH Dependencies of Adsorbed Species of 2,4-Pyridinethiol and 2-Pyrimidinethiol on Au(111) Electrode"Electrochemistry,. 67(12),. 1197-1199 (1999)
[文献書誌] Azehara,Hiroaki: "Electrochemical Desorption of Binary Self-Assembled Monolayers of Butyl Hexadecayl Disulfide on Au(111) Electrodes"Electrochemistry,. 67(12),. 1227-1230 (1999)
[文献書誌] Yoshimoto,Soichiro: "STM and Voltammetric Studies on Structure of 4-Pyridinethiolate Monolayer Chemisorbed on Au(100)-(1x1) surface"Electrochemistry Communications,. 2(1),. 39-43 (2000)
[文献書誌] Ohira,Akihiro: "Formation of the "nanotube"structure of b-cyclodextrin on Au(111) surfaces induced by potential controlled adsorption"Colloids and Surfaces A:Physicochemical and Engineering Aspects,. (in press). (2000)
[文献書誌] Taniguchi,Isao: "Simple methods for preparation of a well-defined 4-pyridinethiol modified surface on Au(111) electrodes for cytochrome c electrochemistry"Electrochim.Acta,. (in press). (2000)
[文献書誌] Sawaguchi,Takahiro: "Voltammetric and In Situ STM Studies on Self-Assembled Monolayers of 4- and 2-Mercaptopyridines and Thiophenol on Au(111) Electrodes"Electrochim.Acta,. (in press). (2000)
[文献書誌] Mie,Yasuhiro: "Electrochemical analysis of heme functions of myogloblin using semi-artificial myoglobins"Bioelectrochemistry and Bioenergetics.,. (in press). (2000)
[文献書誌] Yoshimoto,Soichiro: "Direct Observation of Structurl Change Induced by Redox Reaction of Bis(2-Anthraquinyl)disulfide SAM on Au(100)-(1x1) by in situ High Resolution STM"Langmuir,. (in press). (2000)
[文献書誌] 谷口,功: "ポイントミューテーションによるタンパク質電子機能の改変"Electrochemistry(電気化学). 68(5)(印刷中). (2000)
[文献書誌] Shimanoe,K.: "Sensing Properties and Intergfacial Structure of Solid Electrolyte CO_2 Sensor Attached with Na_2CO_3-based Auxiliary Phase"Electrochemistry,. 67,. 1258-1261 (1999)
[文献書誌] Kida,T: "Interfacial structure of NASICON-based sensor attached with Li_2CO_3-CaCO_3 auxiliary phase for detection of CO_2"Solid State Ionics,. (in press). (2000)
[文献書誌] Baik,N.-S: "Hydrothermal treatment oftin oxide sol solution for preperation of thin-film sensor with enhanced thermal stability and gas sensitivity"Sensors and Actuators B,. (in press). (2000)
[文献書誌] Baik,N.-S: "Hydrothermally treated sol solution of tin oxide for thin-film gas sensor"Sensors and Actuators B,. (in press). (2000)
[文献書誌] Yamazoe,N: "Solid State Gas Sensor Design Using Froeign Receptors"Electrochemistry,. 67,. 224-231 (1999)
[文献書誌] 山添,昇: "酸素を測る"化学と教育. 47巻,10号. 660-664 (1999)
[文献書誌] Xu,L: "[Ru(CO)(O^2CMe)(tpa)]ClO_4・C_6H_5Me(tpa=tris(2-pyridylmethyle)amine),the First Ruthenium Carbonyl Complex of tpa"Inorg.Chem.Commun.,. 2(4),. 121-123 (1999)
[文献書誌] Inomata,T: "Interaction of Some Lewis Acids with the Oxo-bridge of(μ-Oxo)di(μ-acetato)diruthenium(III,III)Complexes and Their Electrochemical Consequence"Electorochem.,. 67(5),. 427-430 (1999)
[文献書誌] Yoshimura,T.: "Hexarhenium(III) Clusters [Re_6(μ_3-S)_8X_6]^<2->(X=Cl.Br,I)are Luminescent at Room Temperature"Chem.Lett.,. (7),. 697-698 (1999)
[文献書誌] Xu,L: "Syntheses and Characterization of a Series of Carbonylruthenium(I) and (II) Complexes Containing Pyridyl Ligands"J.Organomet.Chem.,. 585(2),. 246-252 (1999)
[文献書誌] Abe,M: "Synthesis and Electochemical Characterization of Self-Assembled Monolayers of Redox-Active Oxide-Bridged Trirruthenium(III) Clusters on Au(111)"J.Electroanal,Chem.,. 473(1-2),. 93-98 (1999)
[文献書誌] Inomata,T: "Self-Assembled Monlayers of Non-Heme Diiron(III) Model Complexes on Au(111) Electrode:Synthesis and Proton-Coupled Redox Behavior in Water"Chem.Lett.,. (10),. 1097-1098 (1999)
[文献書誌] Yoshimura,T.: "Unusual Capping Chalcogenide Dependence of the Luminescense Quantum Yield of the Hexarhenium(III) Cyano Complexes[Re_6(μ_3-E)_8(CN)_6]^<4->,E^2=Se^2>S^2>Te^2"Chem.Lett.,. (10),. 1121-1122 (1999)
[文献書誌] Yoshimura,T.: "Synthesis,Structures and Redox Properties of Octa(μ_3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands"Inorg.Chem.,. 38(24),. 5557-5564 (1999)
[文献書誌] Abe,M: "Electrochemical and Infrared Spectroelectrochemical Characterization of self-Assembled Monolayers of a Carbonyl-Coordinated Trinuclear Ruthenium Complex on a Gold Electrode"Electorochem.,. 67(12),. 1162-1164 (1999)
[文献書誌] Yoshimura,T.: "Emission and Metal-and Ligand-Centered-Redox Characteristics of the Hexarhenium(III) Clusters trans-and-cis-[Re_6(μ_3-S)_8Cl_4(L)_4],Where L Is a Pyridine Derivative or Pyrazine"Inorg.Chem.,. (in press). (2000)
[文献書誌] Zhou,H: "Imaging the Activity of Immobilized Horse Radish Peroxidase with Scannnig Electrochemical/chemiluminescence Microscopy"Electorochemistry,. 67,. 1135-1137 (1999)
[文献書誌] Kasai,S: "Chemiluminescensce Imaging of Localized Enzymes by Scanning Chemical Reaction Microscopy"Chem.Lett.,. (in press). (2000)
[文献書誌] Yasukawa,T: "Imaging of Diaphorase Activity Micropatterned at Gold Arrays with Scanning Electrochemical Microscopy"Chem.Lett.. (in press). (2000)
[文献書誌] 末永,智一: "マイクロ電極システムを用いた生体材料の局所機能探索と応用"表面技術. 50巻. 705-709 (1999)
[文献書誌] 珠玖,仁: "微小空間の生物電気化学.走査型電気化学顕微鏡による生体分子機能表面の構築と評価"化学. 54巻,11号. 72-73 (1999)
[文献書誌] 珠玖,仁: "電気化学顕微鏡の基礎と応用"表面技術. 51巻,. 46-52 (2000)
[文献書誌] Hawkridge,F.M.: "Electrochemistry of Heme Proteins in The Porphyrin Handbook(eds.)K.M.Kadish and K.M.Smith Vol.8(Electron Transfer),"Academic Press,. 200 (1999)
[文献書誌] 谷口,功: "電気化学便覧(第9章生物電気化学:生体内の電気化学反応)"丸善(印刷中). (2000)

1999 年度 実績報告書

分子認識機能界面とセンシング

研究代表者

谷口 功 熊本大学, 工学部, 教授 (90112391)

研究成果

[文献書誌] Nishiyama,Katsuhiko: "Photochemical Reduction of NADP+ by Zinc Porphyrin Reconstituted Myoglobin as a Simple Model of Photosystem I"Chem.Lett.,. 357-358 (1999)

[文献書誌] Uemura,Shinobu: "In situ STM visualization of Fullerlene Epitaxial Adlayers on Au(111) Surfaces Prepared by the Transfer of Langmuir Films"Chem.Lett.,. 279-280 (1999)

[文献書誌] Nishiyama,Katsuhiko: "Phase Separation of an Unsymmetrical Disulfide SAM at an Evaporated Au(111) Electrode Monitored by Reductive Desorption and the Electrochemical Response of Cytochrome c"Chem.Lett.,. 753-754 (1999)

[文献書誌] Taniguchi,Isao: "Electroanalytical chemistry of myoglobin with modification of distal histidine by cyanated imidazole"J.Electroanal.Chem.,. 468,. 9-18 (1999)

[文献書誌] Yoshimoto,Soichiro: "Electorochemical study on competitive adsorption of pyridinethiol with sulfide onto Au(111) surfaces"J.Electroanal.Chem.,. 473,. 85-92 (1999)

[文献書誌] Azehara,Hiroaki: "Investigation of structure of self-assembled monolayers of asymmetrical disulfide on Au(111) electrodes by electrochemical desorption"J.Electroanal.Chem.,. 473,. 68-74 (1999)

[文献書誌] Akashi,Tetsuyuki: "Comparison of the Electrostatic Binding Sites on the Surface of Ferredoxin for Two Ferredoxin-dependent Enzymes,Ferredoxin-NADP+Reductase and Sulfate Reductase"J.Biol.Chem.,. 274,. 29399-29405 (1999)

[文献書誌] Ohira,Akihiro: "Self-organization of a-cyclodextrin on Au(111) surfaces induced by potential controlled adsorption"J.Electroanal.Chem.,. 472,. 163-167 (1999)

[文献書誌] Nishiyama,Katsuhiko: "Structural differences in self-assembled monolayers of anthraquinone derivatives of silver and gold electrodes studied by cyclic voltammmetry and in situ SERS spectroscoy"J.Electroanal.Chem.,. 478,. 83-91 (1999)

[文献書誌] Taniguchi,Isao: "Potential and pH Dependencies of Adsorbed Species of 2,4-Pyridinethiol and 2-Pyrimidinethiol on Au(111) Electrode"Electrochemistry,. 67(12),. 1197-1199 (1999)

[文献書誌] Azehara,Hiroaki: "Electrochemical Desorption of Binary Self-Assembled Monolayers of Butyl Hexadecayl Disulfide on Au(111) Electrodes"Electrochemistry,. 67(12),. 1227-1230 (1999)

[文献書誌] Yoshimoto,Soichiro: "STM and Voltammetric Studies on Structure of 4-Pyridinethiolate Monolayer Chemisorbed on Au(100)-(1x1) surface"Electrochemistry Communications,. 2(1),. 39-43 (2000)

[文献書誌] Ohira,Akihiro: "Formation of the "nanotube"structure of b-cyclodextrin on Au(111) surfaces induced by potential controlled adsorption"Colloids and Surfaces A:Physicochemical and Engineering Aspects,. (in press). (2000)

[文献書誌] Taniguchi,Isao: "Simple methods for preparation of a well-defined 4-pyridinethiol modified surface on Au(111) electrodes for cytochrome c electrochemistry"Electrochim.Acta,. (in press). (2000)

[文献書誌] Sawaguchi,Takahiro: "Voltammetric and In Situ STM Studies on Self-Assembled Monolayers of 4- and 2-Mercaptopyridines and Thiophenol on Au(111) Electrodes"Electrochim.Acta,. (in press). (2000)

[文献書誌] Mie,Yasuhiro: "Electrochemical analysis of heme functions of myogloblin using semi-artificial myoglobins"Bioelectrochemistry and Bioenergetics.,. (in press). (2000)

[文献書誌] Yoshimoto,Soichiro: "Direct Observation of Structurl Change Induced by Redox Reaction of Bis(2-Anthraquinyl)disulfide SAM on Au(100)-(1x1) by in situ High Resolution STM"Langmuir,. (in press). (2000)

[文献書誌] 谷口,功: "ポイントミューテーションによるタンパク質電子機能の改変"Electrochemistry(電気化学). 68(5)(印刷中). (2000)

[文献書誌] Shimanoe,K.: "Sensing Properties and Intergfacial Structure of Solid Electrolyte CO_2 Sensor Attached with Na_2CO_3-based Auxiliary Phase"Electrochemistry,. 67,. 1258-1261 (1999)

[文献書誌] Kida,T: "Interfacial structure of NASICON-based sensor attached with Li_2CO_3-CaCO_3 auxiliary phase for detection of CO_2"Solid State Ionics,. (in press). (2000)

[文献書誌] Baik,N.-S: "Hydrothermal treatment oftin oxide sol solution for preperation of thin-film sensor with enhanced thermal stability and gas sensitivity"Sensors and Actuators B,. (in press). (2000)

[文献書誌] Baik,N.-S: "Hydrothermally treated sol solution of tin oxide for thin-film gas sensor"Sensors and Actuators B,. (in press). (2000)

[文献書誌] Yamazoe,N: "Solid State Gas Sensor Design Using Froeign Receptors"Electrochemistry,. 67,. 224-231 (1999)

[文献書誌] 山添,昇: "酸素を測る"化学と教育. 47巻,10号. 660-664 (1999)

[文献書誌] Xu,L: "[Ru(CO)(O^2CMe)(tpa)]ClO_4・C_6H_5Me(tpa=tris(2-pyridylmethyle)amine),the First Ruthenium Carbonyl Complex of tpa"Inorg.Chem.Commun.,. 2(4),. 121-123 (1999)

[文献書誌] Inomata,T: "Interaction of Some Lewis Acids with the Oxo-bridge of(μ-Oxo)di(μ-acetato)diruthenium(III,III)Complexes and Their Electrochemical Consequence"Electorochem.,. 67(5),. 427-430 (1999)

[文献書誌] Yoshimura,T.: "Hexarhenium(III) Clusters [Re_6(μ_3-S)_8X_6]^<2->(X=Cl.Br,I)are Luminescent at Room Temperature"Chem.Lett.,. (7),. 697-698 (1999)

[文献書誌] Xu,L: "Syntheses and Characterization of a Series of Carbonylruthenium(I) and (II) Complexes Containing Pyridyl Ligands"J.Organomet.Chem.,. 585(2),. 246-252 (1999)

[文献書誌] Abe,M: "Synthesis and Electochemical Characterization of Self-Assembled Monolayers of Redox-Active Oxide-Bridged Trirruthenium(III) Clusters on Au(111)"J.Electroanal,Chem.,. 473(1-2),. 93-98 (1999)

[文献書誌] Inomata,T: "Self-Assembled Monlayers of Non-Heme Diiron(III) Model Complexes on Au(111) Electrode:Synthesis and Proton-Coupled Redox Behavior in Water"Chem.Lett.,. (10),. 1097-1098 (1999)

[文献書誌] Yoshimura,T.: "Unusual Capping Chalcogenide Dependence of the Luminescense Quantum Yield of the Hexarhenium(III) Cyano Complexes[Re_6(μ_3-E)_8(CN)_6]^<4->,E^2=Se^2>S^2>Te^2"Chem.Lett.,. (10),. 1121-1122 (1999)

[文献書誌] Yoshimura,T.: "Synthesis,Structures and Redox Properties of Octa(μ_3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands"Inorg.Chem.,. 38(24),. 5557-5564 (1999)

[文献書誌] Abe,M: "Electrochemical and Infrared Spectroelectrochemical Characterization of self-Assembled Monolayers of a Carbonyl-Coordinated Trinuclear Ruthenium Complex on a Gold Electrode"Electorochem.,. 67(12),. 1162-1164 (1999)

[文献書誌] Yoshimura,T.: "Emission and Metal-and Ligand-Centered-Redox Characteristics of the Hexarhenium(III) Clusters trans-and-cis-[Re_6(μ_3-S)_8Cl_4(L)_4],Where L Is a Pyridine Derivative or Pyrazine"Inorg.Chem.,. (in press). (2000)

[文献書誌] Zhou,H: "Imaging the Activity of Immobilized Horse Radish Peroxidase with Scannnig Electrochemical/chemiluminescence Microscopy"Electorochemistry,. 67,. 1135-1137 (1999)

[文献書誌] Kasai,S: "Chemiluminescensce Imaging of Localized Enzymes by Scanning Chemical Reaction Microscopy"Chem.Lett.,. (in press). (2000)

[文献書誌] Yasukawa,T: "Imaging of Diaphorase Activity Micropatterned at Gold Arrays with Scanning Electrochemical Microscopy"Chem.Lett.. (in press). (2000)

[文献書誌] 末永,智一: "マイクロ電極システムを用いた生体材料の局所機能探索と応用"表面技術. 50巻. 705-709 (1999)

[文献書誌] 珠玖,仁: "微小空間の生物電気化学.走査型電気化学顕微鏡による生体分子機能表面の構築と評価"化学. 54巻,11号. 72-73 (1999)

[文献書誌] 珠玖,仁: "電気化学顕微鏡の基礎と応用"表面技術. 51巻,. 46-52 (2000)

[文献書誌] Hawkridge,F.M.: "Electrochemistry of Heme Proteins in The Porphyrin Handbook(eds.)K.M.Kadish and K.M.Smith Vol.8(Electron Transfer),"Academic Press,. 200 (1999)

[文献書誌] 谷口,功: "電気化学便覧(第9章 生物電気化学:生体内の電気化学反応)"丸善(印刷中). (2000)

1999 年度実績報告書

谷口功熊本大学, 工学部, 教授 (90112391)

[文献書誌] 谷口,功: "電気化学便覧(第9章生物電気化学:生体内の電気化学反応)"丸善(印刷中). (2000)