1989 Fiscal Year Annual Research Report

複合系の構造化学的アプローチ

Research Project

Project/Area Number	01649006
Research Institution	Osaka University
Principal Investigator	三角荘一大阪大学, 産業化学研究所, 教授 (40029830)
Co-Investigator(Kenkyū-buntansha)	築部浩岡山大学, 教養部, 助教授 (00144725) 高木誠九州大学, 工学部, 教授 (90037739) 西郷和彦東京大学, 工学部, 助教授 (80016154) 加納航治同志社大学, 工学部, 教授 (60038031)
Keywords	分子認識 / イオン輸送 / ホスト・ゲスト相互作用 / 色素化クラウン / 環状・非環状オリゴ糖 / ポリアザシクロファン / ビスインターカレータDNA錯体 / 天然系ホスト.モネンシン
Research Abstract	本研究班は、生体分子認識系や光合成系など分子集合系の機能発現に、重要な因子として知られるホスト・ゲスト相互作用を利用して、分子認識、イオン輸送、多段階電子移動などの機能をもつ複合系の構築と構造相関について研究を行ってきた。以下に各班員の成果を記述する。三角は、アゾフェノール色素化クラウンによるアミン選択的捕捉呈色の研究を行い、Onー色素化クラウンではアミン級数と錯体安定度が環の大小で逆転すること、複数の色素化ホスト使用でアミン級数の判別をしうること、ジアミン類の選択的捕捉呈色を示すホストの合成を報告した。加納は、環状及び非環状オリゴ糖(γーシクロデキストン(CD)、CDx等)によるゲスト捕捉を、キラルピレンニ量体の場合にはCPFで、BINAPの不斉認識と黄疸細胞毒色素ビリルビンの対掌体選択錯形成ではCDスペクトル測定により不斉分子識別を観察した。西郷は、ポリアザシクロファンによるアルカリ金属イオン中のリチウムイオン選択的捕捉を以前に報告したが、その他置換フェノール及びアンモニウムイオンの錯形成を検討した結果、両系ともに立体障害の大きさが安定度定数に顕著な効果を及ぼすことを報告した。高木は、ポリエチレングリコール鎖をもつビスインターカレータ(IC)のDNAへの挿入による吸収スペクトル変化から、ICの結合はDNA中の金属イオンとの交換により進むとの結論を得た。またビスICとCu^<2+>を組み合せ用いてDNAへの結合とそれに伴うDNA鎖の切断反応におけるICの効果について詳細な検討結果を報告した。築部は、生体膜輸送を仲介する天然系ホストモネンシンのイオン認識機能の高次化を図る目的で、エステル等各種誘導体を合成した。例えば、メチルエステルは銀イオン輸送選択性の向上、フェニルグリシン誘導体などアンモニウムイオンに対する高い不斉認識能を観察報告した。

Research Products

(27 results)

All Other

All Publications (27 results)

[Publications] Takahiaro Kaneda: "Chiral Azophenolic Acerands:Color Indicators to Judge the Absolute Configuration of Chiral Amines" J.Am.Chem.Soc.111. 742-743 (1989)
[Publications] Takahiro Kaneda: "Azophenolic Acerands:AmineーSelective Coloration and Crystal Structure of a Piperidinium Saltex" J.Am.Chem.Soc.111. 1881-1883 (1989)
[Publications] Soichi Misumi: "Cation Selective ComplexationーColoration with Chromophoric Crowns" J.Inclu.Phenom.7. 83-90 (1989)
[Publications] Kenichiro Nakashima: "Coloration Reaction of a Crowned 2,4ーDinitrophenylazophenol Barium(II)Complex with Amines and its Application to Flow Injection Spectrophotometry" Analyst. 114. 501-504 (1989)
[Publications] Yoshiteru Sakata: "Synthesis of Completely Fixed PorphyrinーQuinone Compounds and the mutual Orientation Effect on Electron Transfer" J.Am.Chem.Soc.111. 8979-8991 (1989)
[Publications] Soichi Misumi: "Amine Selective Coloration with Chromoacerands" Pure & Apple.Chem.62. 493-498 (1990)
[Publications] Koji Kano: "Monolayers of 1ーStearylpyreneー6ーsulfonate and 1ーStearylーpyreneー8ーsulfonate" Langmuir. 5. 927-932 (1989)
[Publications] Koji Kano: "Chiral Recognition of Binaphthyls by Permethylated βーCyclodextrin" J.Chem.Soc.,Chem.Commun.1278-1279 (1989)
[Publications] Koji Kano: "Molecular Recognition by Saccharides.Asymmetric Complexation between Bilirubin and Nucleosides" Chem.Lett.21-24 (1990)
[Publications] Koji Kano: "Molecular Complex of a Cationic Porphyrin and pーNitrophenol.Verificcation of the Porphyrin Dimeization" Bull.Chm.Soc.Jpn.63. 633-635 (1990)
[Publications] Koji Kano: "Cationic Porphyrins in water.^1HNMR and Fluorescence Studies on Dimer and Molicular Complex Formation" J.Phys.Chem.94. (1990)
[Publications] Nobuhiro Kihara: "Lithium Selective Complexation by a Novel Cyclophaneーtype Macricyclic Ligand" Chem.Lett.1289-1292 (1989)
[Publications] H.Kimoto: "The Potential Energy Calculation for Conglomerate Crystals" Chem.Lett.(1990)
[Publications] Akira Ohki: "Extraction of Organic Dianionic Species with Decationic Extractants and Their Application to Anion Selective Elecrode" Chem.Lett.95-98 (1989)
[Publications] Naotoshi Nakashima: "Potential Use of Synthetic Molecular Bilayer Films as Chemical Sensing Materials:Application to Humidity Sensors" J.Mater.Sci.Lett.8. 387-388 (1989)
[Publications] S.Ide: "Synergistic Extraction of Heavy Metal ions with 1,2ーBisー(octanesulfonamido)benzene in Chlorobenzene" Anal.Sci.5. 351-354 (1989)
[Publications] Makoto Takagi: "Crown Ethers as Sensory Materials in Chemical Measurements:Interfaces for Chemical Signal Transformation" Pure & Appl.Chem.61. 1605-1612 (1989)
[Publications] Akira Ohki: "Solvent Extraction of Dーand LーDibenzoyltartarate Anions with Dicationic IronーPair Extractions Featuring Chirality Recognition and Shape Recognition" Chem.Lett.1551-1554 (1989)
[Publications] Naotoshi Nakashima: "Detection of Phase Transition of Thin LangmuirーBlodgett Film Based on an Electrochemical Capacitance Measurement" J.Chem.Scot.,Chem.Commun.1441-1442 (1989)
[Publications] M.Maeda: "Gel Electrophoretic Demonstration of PseudoーGrafting of Polyacrylamide onto λ Phage DNA" Chem.Lett.1831-1834 (1989)
[Publications] S.Takenaka: "Intercalatorーinduced Gelーelectrophoretic Retardation of Synthetic Doubleーstranded Oligonucleotides and Comigration of Intercalators" Anal.Sci.6. (1990)
[Publications] Hiroshi Tukube: "Iron Selectivity Control in Esterーand Armed DiazaーCrown Ethers: SideーArm Effects in Cooperative Binding and Specific Transport" J.Chem.Soc.,Perkin I. 89-93 (1989)
[Publications] Hiroshi Tsukube: "AmideーArmed Azamacrocycles as a New Series of Synthetic Carriers for Alkali and Alkaline Earth Mental Cations" J.Chem.Soc.,Perkin Commun.1537-1538 (1989)
[Publications] Hiroshi Tsukube: "Triazamacrocycle Having PyridineーPendant Arms as a New Na^+IonーSelective Ionophore" Tetrahedron Lett.30. 3983-3986 (1989)
[Publications] Kazuhiro Maruyama: "New Chiral Host Molecules Derived form Naturally Occurring Monensin Ionophore" J.Chem.Soc.,Chem.Commun. 864-865 (1989)
[Publications] Hiroshi Tsukube: "Specific Ag^+ IonーTransport Properties of Functionalized Biological Monensin Ionophore" Inorg.Ch;m.Acta. 27-29 (1990)
[Publications] Hiroshi Tsukube: ""Cation Binding by Natural andーodifies Ionophore"in"Cation Binding by Macrocycles",ed.by Inoue and Gokel" Marcel Dekker, (1990)

1989 Fiscal Year Annual Research Report

複合系の構造化学的アプローチ

Principal Investigator

三角 荘一 大阪大学, 産業化学研究所, 教授 (40029830)

Research Products

[Publications] Takahiaro Kaneda: "Chiral Azophenolic Acerands:Color Indicators to Judge the Absolute Configuration of Chiral Amines" J.Am.Chem.Soc.111. 742-743 (1989)

[Publications] Takahiro Kaneda: "Azophenolic Acerands:AmineーSelective Coloration and Crystal Structure of a Piperidinium Saltex" J.Am.Chem.Soc.111. 1881-1883 (1989)

[Publications] Soichi Misumi: "Cation Selective ComplexationーColoration with Chromophoric Crowns" J.Inclu.Phenom.7. 83-90 (1989)

[Publications] Kenichiro Nakashima: "Coloration Reaction of a Crowned 2,4ーDinitrophenylazophenol Barium(II)Complex with Amines and its Application to Flow Injection Spectrophotometry" Analyst. 114. 501-504 (1989)

[Publications] Yoshiteru Sakata: "Synthesis of Completely Fixed PorphyrinーQuinone Compounds and the mutual Orientation Effect on Electron Transfer" J.Am.Chem.Soc.111. 8979-8991 (1989)

[Publications] Soichi Misumi: "Amine Selective Coloration with Chromoacerands" Pure & Apple.Chem.62. 493-498 (1990)

[Publications] Koji Kano: "Monolayers of 1ーStearylpyreneー6ーsulfonate and 1ーStearylーpyreneー8ーsulfonate" Langmuir. 5. 927-932 (1989)

[Publications] Koji Kano: "Chiral Recognition of Binaphthyls by Permethylated βーCyclodextrin" J.Chem.Soc.,Chem.Commun.1278-1279 (1989)

[Publications] Koji Kano: "Molecular Recognition by Saccharides.Asymmetric Complexation between Bilirubin and Nucleosides" Chem.Lett.21-24 (1990)

[Publications] Koji Kano: "Molecular Complex of a Cationic Porphyrin and pーNitrophenol.Verificcation of the Porphyrin Dimeization" Bull.Chm.Soc.Jpn.63. 633-635 (1990)

[Publications] Koji Kano: "Cationic Porphyrins in water.^1HNMR and Fluorescence Studies on Dimer and Molicular Complex Formation" J.Phys.Chem.94. (1990)

[Publications] Nobuhiro Kihara: "Lithium Selective Complexation by a Novel Cyclophaneーtype Macricyclic Ligand" Chem.Lett.1289-1292 (1989)

[Publications] H.Kimoto: "The Potential Energy Calculation for Conglomerate Crystals" Chem.Lett.(1990)

[Publications] Akira Ohki: "Extraction of Organic Dianionic Species with Decationic Extractants and Their Application to Anion Selective Elecrode" Chem.Lett.95-98 (1989)

[Publications] Naotoshi Nakashima: "Potential Use of Synthetic Molecular Bilayer Films as Chemical Sensing Materials:Application to Humidity Sensors" J.Mater.Sci.Lett.8. 387-388 (1989)

[Publications] S.Ide: "Synergistic Extraction of Heavy Metal ions with 1,2ーBisー(octanesulfonamido)benzene in Chlorobenzene" Anal.Sci.5. 351-354 (1989)

[Publications] Makoto Takagi: "Crown Ethers as Sensory Materials in Chemical Measurements:Interfaces for Chemical Signal Transformation" Pure & Appl.Chem.61. 1605-1612 (1989)

[Publications] Akira Ohki: "Solvent Extraction of Dーand LーDibenzoyltartarate Anions with Dicationic IronーPair Extractions Featuring Chirality Recognition and Shape Recognition" Chem.Lett.1551-1554 (1989)

[Publications] Naotoshi Nakashima: "Detection of Phase Transition of Thin LangmuirーBlodgett Film Based on an Electrochemical Capacitance Measurement" J.Chem.Scot.,Chem.Commun.1441-1442 (1989)

[Publications] M.Maeda: "Gel Electrophoretic Demonstration of PseudoーGrafting of Polyacrylamide onto λ Phage DNA" Chem.Lett.1831-1834 (1989)

[Publications] S.Takenaka: "Intercalatorーinduced Gelーelectrophoretic Retardation of Synthetic Doubleーstranded Oligonucleotides and Comigration of Intercalators" Anal.Sci.6. (1990)

[Publications] Hiroshi Tukube: "Iron Selectivity Control in Esterーand Armed DiazaーCrown Ethers: SideーArm Effects in Cooperative Binding and Specific Transport" J.Chem.Soc.,Perkin I. 89-93 (1989)

[Publications] Hiroshi Tsukube: "AmideーArmed Azamacrocycles as a New Series of Synthetic Carriers for Alkali and Alkaline Earth Mental Cations" J.Chem.Soc.,Perkin Commun.1537-1538 (1989)

[Publications] Hiroshi Tsukube: "Triazamacrocycle Having PyridineーPendant Arms as a New Na^+IonーSelective Ionophore" Tetrahedron Lett.30. 3983-3986 (1989)

[Publications] Kazuhiro Maruyama: "New Chiral Host Molecules Derived form Naturally Occurring Monensin Ionophore" J.Chem.Soc.,Chem.Commun. 864-865 (1989)

[Publications] Hiroshi Tsukube: "Specific Ag^+ IonーTransport Properties of Functionalized Biological Monensin Ionophore" Inorg.Ch;m.Acta. 27-29 (1990)

[Publications] Hiroshi Tsukube: ""Cation Binding by Natural andーodifies Ionophore"in"Cation Binding by Macrocycles",ed.by Inoue and Gokel" Marcel Dekker, (1990)

三角荘一大阪大学, 産業化学研究所, 教授 (40029830)