1989 Fiscal Year Annual Research Report

分子認識場の設計

Research Project

Project/Area Number	01648006
Research Institution	Kyushu University
Principal Investigator	新海征治九州大学, 工学部, 教授 (20038045)
Co-Investigator(Kenkyū-buntansha)	戸田芙三夫愛媛大学, 工学部, 教授 (50036232) 古賀憲司東京大学, 薬学部, 教授 (10012600) 笠井暢民大阪大学, 工学部, 教授 (50028958) 岡原光男大阪大学, 工学部, 教授 (70028992) 稲津孝彦九州大学, 理学部, 教授 (60037207)
Keywords	カリックスアレーン / デオキシコール酸 / クラウンエーテル / シクロファン / 分子認識 / 光学分割 / 結晶構造 / イオン輸送
Research Abstract	本年度は混合物系より特定の化合物を認識し、その目標化合物に対してのみ選択的に作用する機能をもつ「高度認識素子」の開発を中心に研究した。水溶性の新規環状化合物・カリックスアレーンが合成され、水溶液中における分子包接作用がNMR、X線結晶解析を駆使して詳細に調べられた(新海)。その結果、空孔のサイズと対応するゲスト分子が認識されることが明らかとなった。胆汁酸の一つであるデオキシコール酸を基本単位とする環状物が高収率で合成された(稲津)。この化合物はステロイド構造に基く特異な空孔を持つことがスペクトル的研究より明らかとされた。溶液系および結晶系で数種の有機分子が空孔内に包接されることが判明した。クラウンエーテルはアルカリ金属イオンを選択的に結合する機能をもつことが知られているが、Nーピボット型ラリアートエーテルやビシクロ環にすることにより空孔を精微に設計すれば、高いイオン識別能が実現できることが明らかになった(岡原)。クラウン化アゾフェノール色素とアミンの錯体をX線結晶解析した結果、アミンの錯化によりクラウン環の形が大きく変化し、“inducedーfit"型の性質をもつことが明らかとなった(笠井)。特に、ピペラジンとの錯体はクラウン環がゲストを包接する形状をとることが判明した。シクロファンは人工ホスト化合物の中でも分子認識の高いもののひとつであるが、アニオン性基およびカチオン性基を導入し、静電的相互作用を利用することにより、高精度の分子認識が起ることが明らかとなった(古賀)。さらに、ジヒドロキシアセチレン系包接化合物が結晶状態で形成する空孔を認識サイトとして使用することにより、構造異性体や光学異性体が分割できることが見い出された(戸田)。以上の結果より、分子が形成する空孔を巧みに設計することにより、分子認識の精密化をする新しい方法論が確立した。

Research Products
(39 results)

All Other

All Publications (39 results)

[Publications] S.Shinkai: "Autoaccelarative Diazo Coupling with Clix〔4〕arene:Unusual Coーoperativity of the Calixarene Hydroxy Groups" J.Chem.Soc.,Perkin Trans.1. 195-196 (1989)
[Publications] K.Airaki: "Actvation Parameters for Calixcarene Ring Inversion As Determined by Computer-Assisted Spectrum Simulation" Chem.Lett.581-584 (1989)
[Publications] T.Arimura: "Formation of SolventーSeparated Ion Pairs in Calixarene EsterーAlkali Picrate Complexes" Bull.Chem.Soc.Jpn.62. 1674-1676 (1989)
[Publications] S.Shinkai: "New WaterーSoluble Calixarenes Bearing the Sulphonate Groups on the“Lower Rim":Relations between the Calixarene Shape and the Binding Ability" J.Chem.Soc.,Perkin Trans.1. 1073-1074 (1989)
[Publications] S.Shinkai: "DiazoーCoupling Reactions with Calix〔4〕arenes.pK_a Determination with Chromophoric Azocalix〔4〕arenes" Chem.Lett.931-934 (1989)
[Publications] S.Shinkai: "Ion Permeation through Polymerーsupported Steroidal Crown Membranes" J.Polym.Sci.,Polym.Lett.Ed.27. 209-213 (1989)
[Publications] Y.Ishikawa: "Formation of Calixarene Monolayers Which Selectively Respond to Metal Ions" J.Chem.Soc.,Chem.Commun.736-738 (1989)
[Publications] T.Arimura: "“Template Effects"on Calixarene Conformations through HostーGuest Interaction" Tetrahedron Lett.30. 2563-2566 (1989)
[Publications] S.Shinkai: "Molecular Recognition of CalixareneーBased Host Molecules" J.Inclusion Phenom.,Mol.Recog.Chem.7. 193-201 (1989)
[Publications] S.Shinkai: "CalixareneーCatalyzed Basic Hydrolysis of pーNitropheny1 Dodecanoate:A Posible Change in the Mechanism fron“Deshielding"To“HostーGuest"" J.Am.Chem.soc.111. 5477-5478 (1989)
[Publications] S.Shinkai: "Selective Ion Permeation across Membranes Contraining Crown Ethers with Steroid Moieties" Macromol.Chem.,Rapid Commun.10. 361-366 (1989)
[Publications] T.Arimura: "HostーGuest Properties of New Waterーsoluble Calixarenes Derived from pーChloromethylcalixarenes" J.Org.Chem.54. 3766-3768 (1989)
[Publications] S.Shinkai: "Selective Extraction and Transport of UO_2^<2+> with Calixareneーbased Uranophiles" J.Chem.Soc.,Perkin Trans.2. 1167-1171 (1989)
[Publications] S.Shinkai: "Cationic WaterーSoluble Calixarenes:New Host Molecules With Catalyse Basic Hydrolysis of a Phosphate Ester" J.Chem.Soc.,Perkin Trans.1. 1859-1860 (1989)
[Publications] I.Yoshida: "Solvent Extraction of Copper(II)Ion with pーtーButylcalix〔6〕arene from the Ammonia Alkaline Solution" Chem.Lett.1535-1538 (1989)
[Publications] K.Araki: "On the Conformational Isomers in TetraーOーalkylcalix〔4〕arenes" Chem.Lett.1747-1750 (1989)
[Publications] S.Shinkai: "Specific inhibition of Flavin Catalyses by a“Molecular Hinge"" Tetrahedron Lett.30. 5895-5898 (1989)
[Publications] S.Shinkai: "Syntheses and Aggregation Properties of New WaterーSoluble Calixarenes" J.Chem.Soc.,Perkin Trans.1. 2039-2045 (1989)
[Publications] S.Shinkai: "(2ーPyridymethoxy)calixarenes:New Versatile Ionophores for Metal Extraction" Bull.Chem.Soc.Jpn.62. 4055-4057 (1989)
[Publications] S.Shinkai: "NMR Determination of Association Constants for Aqueous Calixarene Complexes and Guest Template Effects on the Conformational Freedom" Bull.Chem.Soc.Jpn.62. 3856-3862 (1989)
[Publications] S.Shinkai: "Synthesis and Reactivity Studies of Novel Flavinophanes and 5ーDazaflavinophanes" J.Am.Chem.Soc.111. 4928-4935 (1989)
[Publications] S.Shinkai: "Novel DiastereoーDifferentiating Hydrogen Transfer and“RopeーSkipping Racemization in Chiral Flavinophanes and 5ーDeazaflavinophanes" J.Am.Chem.Soc.111. 4935-4940 (1989)
[Publications] K.Koga: "Cylophanes as Hosts for Aromatic and Aliphatic Guests" J.Inclusion Phenomena. 7. 53-60 (1989)
[Publications] K.Koga: "Biomimetic Studies Using Artificial Systems.V.Design and Synthesis of Novel WaterーSoluble Bisーcyclophanes" Chem.Pharm.Bull.37. 2351-2354 (1989)
[Publications] Teruo Shinmyozu: "Synthesis of Tripleーand Quadrupleーlayerd〔3.3〕Metacyclophanes." J.Org.Chem.(1990)
[Publications] Teruo Shinmyozu: "Synthesis and Xーray Structure Determination of antiー〔3.3〕Metacyclopahne Quinhydrone Dimethy1 Ether;antiー15,18ーDimethoxy〔3〕ーPーbenzoquinono〔3〕metacyclophaneー2,11ーdione." J.Org.Chem.(1990)
[Publications] Kenichi Sugimoto: "A Simple Synthetic Method of Tetraaza〔3.3.3.3〕metaー'and Paracyclophanes by Alkylation of NーSubstituted Trifluoroacetamide." Synthesis. (1990)
[Publications] Katsuya Sako: "Conformational Analysis of〔3.3〕Paracyclophane." Chem.Ber.(1990)
[Publications] Tatsuya Meno: "Conformational Analysis of〔3.3.3〕(1,3,5)Cyclophane." Can.J.Chem.(1990)
[Publications] Y.Nakatsuji: "New Type of Ionophores for Lithium Ion:NーPivot Lariat Ethers Based on Monoazaー14ーCrownー4" J.Org.Chem.54. 2988-2990 (1989)
[Publications] Fumio Toda: "Optical Resolution of Amine NーOxides by Diastereoisomeric Complex Formation with Optically Active Host Compound" Tetrahedron Lett.30. 1841-1844 (1989)
[Publications] Fumio Toda: "NaBH_4 Reduction of Ketones in the Solid State" Angew.Chem.Int.Ed.Engl.28. 320-321 (1989)
[Publications] Fumio Toda: "Oxidative Coupling Reactions of Phenols with FeCl_3 in the Solid State" J.Org.Chem.54. 3007-3009 (1989)
[Publications] Fumio Toda: "Enantioselective Reduction of Ketones in Optically Active Host Compound with a BH_3ーEthylenediamine Complex in the Solid State" J.Chem.Soc.,Chem.Commun.1245-1246 (1989)
[Publications] Fumio Toda: "New Reduction Method of αーDiketones,Oxo amides,and Quinones with ZnーEtoH in the Presence of a Salt" J.Chem.Soc.Perkin 1,. 1555-1556 (1989)
[Publications] Fumio Toda: "Enantioselective Reduction of Ketones in Inclusion Complexes with Cyclomaltoheptaose in the Solid State:Acceleration of the Reaction by Ultrasound" Carbohydrate Research. 192. 363-365 (1989)
[Publications] 新海征治: "包接化合物の基礎と応用" NTS, 32( ) (1989)
[Publications] 戸田扶三夫(監修): "包接化合物の基礎と応用" 株式会社NTS, 349 (1989)
[Publications] 戸田扶三夫: "季刊化学総説「光学異性体の分離」" 学会出版センター, 238 (1989)

1989 Fiscal Year Annual Research Report

分子認識場の設計

Principal Investigator

新海 征治 九州大学, 工学部, 教授 (20038045)

Research Products

[Publications] S.Shinkai: "Autoaccelarative Diazo Coupling with Clix〔4〕arene:Unusual Coーoperativity of the Calixarene Hydroxy Groups" J.Chem.Soc.,Perkin Trans.1. 195-196 (1989)

[Publications] K.Airaki: "Actvation Parameters for Calixcarene Ring Inversion As Determined by Computer-Assisted Spectrum Simulation" Chem.Lett.581-584 (1989)

[Publications] T.Arimura: "Formation of SolventーSeparated Ion Pairs in Calixarene EsterーAlkali Picrate Complexes" Bull.Chem.Soc.Jpn.62. 1674-1676 (1989)

[Publications] S.Shinkai: "New WaterーSoluble Calixarenes Bearing the Sulphonate Groups on the“Lower Rim":Relations between the Calixarene Shape and the Binding Ability" J.Chem.Soc.,Perkin Trans.1. 1073-1074 (1989)

[Publications] S.Shinkai: "DiazoーCoupling Reactions with Calix〔4〕arenes.pK_a Determination with Chromophoric Azocalix〔4〕arenes" Chem.Lett.931-934 (1989)

[Publications] S.Shinkai: "Ion Permeation through Polymerーsupported Steroidal Crown Membranes" J.Polym.Sci.,Polym.Lett.Ed.27. 209-213 (1989)

[Publications] Y.Ishikawa: "Formation of Calixarene Monolayers Which Selectively Respond to Metal Ions" J.Chem.Soc.,Chem.Commun.736-738 (1989)

[Publications] T.Arimura: "“Template Effects"on Calixarene Conformations through HostーGuest Interaction" Tetrahedron Lett.30. 2563-2566 (1989)

[Publications] S.Shinkai: "Molecular Recognition of CalixareneーBased Host Molecules" J.Inclusion Phenom.,Mol.Recog.Chem.7. 193-201 (1989)

[Publications] S.Shinkai: "CalixareneーCatalyzed Basic Hydrolysis of pーNitropheny1 Dodecanoate:A Posible Change in the Mechanism fron“Deshielding"To“HostーGuest"" J.Am.Chem.soc.111. 5477-5478 (1989)

[Publications] S.Shinkai: "Selective Ion Permeation across Membranes Contraining Crown Ethers with Steroid Moieties" Macromol.Chem.,Rapid Commun.10. 361-366 (1989)

[Publications] T.Arimura: "HostーGuest Properties of New Waterーsoluble Calixarenes Derived from pーChloromethylcalixarenes" J.Org.Chem.54. 3766-3768 (1989)

[Publications] S.Shinkai: "Selective Extraction and Transport of UO_2^<2+> with Calixareneーbased Uranophiles" J.Chem.Soc.,Perkin Trans.2. 1167-1171 (1989)

[Publications] S.Shinkai: "Cationic WaterーSoluble Calixarenes:New Host Molecules With Catalyse Basic Hydrolysis of a Phosphate Ester" J.Chem.Soc.,Perkin Trans.1. 1859-1860 (1989)

[Publications] I.Yoshida: "Solvent Extraction of Copper(II)Ion with pーtーButylcalix〔6〕arene from the Ammonia Alkaline Solution" Chem.Lett.1535-1538 (1989)

[Publications] K.Araki: "On the Conformational Isomers in TetraーOーalkylcalix〔4〕arenes" Chem.Lett.1747-1750 (1989)

[Publications] S.Shinkai: "Specific inhibition of Flavin Catalyses by a“Molecular Hinge"" Tetrahedron Lett.30. 5895-5898 (1989)

[Publications] S.Shinkai: "Syntheses and Aggregation Properties of New WaterーSoluble Calixarenes" J.Chem.Soc.,Perkin Trans.1. 2039-2045 (1989)

[Publications] S.Shinkai: "(2ーPyridymethoxy)calixarenes:New Versatile Ionophores for Metal Extraction" Bull.Chem.Soc.Jpn.62. 4055-4057 (1989)

[Publications] S.Shinkai: "NMR Determination of Association Constants for Aqueous Calixarene Complexes and Guest Template Effects on the Conformational Freedom" Bull.Chem.Soc.Jpn.62. 3856-3862 (1989)

[Publications] S.Shinkai: "Synthesis and Reactivity Studies of Novel Flavinophanes and 5ーDazaflavinophanes" J.Am.Chem.Soc.111. 4928-4935 (1989)

[Publications] S.Shinkai: "Novel DiastereoーDifferentiating Hydrogen Transfer and“RopeーSkipping Racemization in Chiral Flavinophanes and 5ーDeazaflavinophanes" J.Am.Chem.Soc.111. 4935-4940 (1989)

[Publications] K.Koga: "Cylophanes as Hosts for Aromatic and Aliphatic Guests" J.Inclusion Phenomena. 7. 53-60 (1989)

[Publications] K.Koga: "Biomimetic Studies Using Artificial Systems.V.Design and Synthesis of Novel WaterーSoluble Bisーcyclophanes" Chem.Pharm.Bull.37. 2351-2354 (1989)

[Publications] Teruo Shinmyozu: "Synthesis of Tripleーand Quadrupleーlayerd〔3.3〕Metacyclophanes." J.Org.Chem.(1990)

[Publications] Teruo Shinmyozu: "Synthesis and Xーray Structure Determination of antiー〔3.3〕Metacyclopahne Quinhydrone Dimethy1 Ether;antiー15,18ーDimethoxy〔3〕ーPーbenzoquinono〔3〕metacyclophaneー2,11ーdione." J.Org.Chem.(1990)

[Publications] Kenichi Sugimoto: "A Simple Synthetic Method of Tetraaza〔3.3.3.3〕metaー'and Paracyclophanes by Alkylation of NーSubstituted Trifluoroacetamide." Synthesis. (1990)

[Publications] Katsuya Sako: "Conformational Analysis of〔3.3〕Paracyclophane." Chem.Ber.(1990)

[Publications] Tatsuya Meno: "Conformational Analysis of〔3.3.3〕(1,3,5)Cyclophane." Can.J.Chem.(1990)

[Publications] Y.Nakatsuji: "New Type of Ionophores for Lithium Ion:NーPivot Lariat Ethers Based on Monoazaー14ーCrownー4" J.Org.Chem.54. 2988-2990 (1989)

[Publications] Fumio Toda: "Optical Resolution of Amine NーOxides by Diastereoisomeric Complex Formation with Optically Active Host Compound" Tetrahedron Lett.30. 1841-1844 (1989)

[Publications] Fumio Toda: "NaBH_4 Reduction of Ketones in the Solid State" Angew.Chem.Int.Ed.Engl.28. 320-321 (1989)

[Publications] Fumio Toda: "Oxidative Coupling Reactions of Phenols with FeCl_3 in the Solid State" J.Org.Chem.54. 3007-3009 (1989)

[Publications] Fumio Toda: "Enantioselective Reduction of Ketones in Optically Active Host Compound with a BH_3ーEthylenediamine Complex in the Solid State" J.Chem.Soc.,Chem.Commun.1245-1246 (1989)

[Publications] Fumio Toda: "New Reduction Method of αーDiketones,Oxo amides,and Quinones with ZnーEtoH in the Presence of a Salt" J.Chem.Soc.Perkin 1,. 1555-1556 (1989)

[Publications] Fumio Toda: "Enantioselective Reduction of Ketones in Inclusion Complexes with Cyclomaltoheptaose in the Solid State:Acceleration of the Reaction by Ultrasound" Carbohydrate Research. 192. 363-365 (1989)

[Publications] 新海征治: "包接化合物の基礎と応用" NTS, 32( ) (1989)

[Publications] 戸田扶三夫(監修): "包接化合物の基礎と応用" 株式会社NTS, 349 (1989)

[Publications] 戸田扶三夫: "季刊化学総説「光学異性体の分離」" 学会出版センター, 238 (1989)

新海征治九州大学, 工学部, 教授 (20038045)