物質認識機能を有する高分子の精密合成と応用に関する研究

1992 Fiscal Year Annual Research Report

• Project/Area Number: 03303010
• Research Institution: Nagoya University
• Principal Investigator: 岡本 佳男 名古屋大学, 工学部, 教授 (60029501)
• Co-Investigator(Kenkyū-buntansha): 中浜 精一 東京工大, 工学部, 教授 (90016410) ; 竹本 喜一 大阪大学, 工学部, 教授 (50029170) ; 松田 実 東北大学, 非水溶液化学研究所, 教授 (90006297) ; 清水 剛夫 京都大学, 工学部, 教授 (10025893) ; 国武 豊喜 九州大学, 工学部, 教授 (40037734)
• Keywords: 認識機能 / ポルフィリン / リビング重合 / 不斉識別 / 立体規制 / 酵素触媒重合 / 光機能 / 糖

Research Abstract

1)光認識機能:二分子膜層間へのポルフィリンの導入ならびに層間を鋳型とするクラスターの合成など光学的に興味深い結果を得た(国武)。ポルフィリン誘導体を光機能分子として用いるオリゴヌクレオチドの設計と合成を行った(清水)。光電変換素子の作製を目指して、ポリシランの骨格の制御およびその物性について検討した(松田)。
2)低分子化合物認識機能:種々のヌクレオシドをシリカゲルに固定化した樹脂を合成し、HPLC用固定相としての分離能の評価を行った(竹本)。空孔の大きさと形態が制御された多孔質膜を作成し、その周辺に反応性基を導入することに成功した(中浜)。リビングカチオン重合により、一定鎖長の抜からなる両親媒性の星型ポリマーを合成し、低分子化合物の捕捉能について検討した(東村)。
3)光学異性体認識機能:合成ペプチドの金属錯体を用いることにより高い不斉認識機能を発現させることに成功した(井上)。セルロースのトリス(3,5-ジメチルフェニルアルバメート)を膜として用いることによりβ-ブロッカーなどの医薬品が効率よく分離できることを見出した(岡本)。セルロースやアミロースなどの多糖の化学合成に成功し、これらを不斉素子として用いる道を開いた(小林)。D-マンニトールからなるポリマーが高分子イオノフォアとして興味深い性質を有することを見出した(横田和)。
4)山分子物質認識機能:L-ラムノースから(1-4)-β-ピラノース構造を有するポリマークを合成することができた。(瓜生)。マンノース側鎖をもつ櫛型立体規則性多糖を合成した(岡田)。立体規則性ポリメタルクリル酸エステルのステレオコンプレックス形成について検討した(畑田)。周期ポリマーを合成し、その水素結合形成能を評価した(横田健)。

Research Products

• [Publications] Y.Kaida and Y.Okamoto: "Efficient Optical Resolution of 4-Hydroxy-2-cyclopentenone Derivatives by HPLC on 1-Phenylethylcarbamates of Cellulose and Amylose" Chemistry Letters.85-88 (1992)
• [Publications] Y.Kaida and Y.Okamoto: "Optical Resolution of β-Lactams on 1-Phenylethylcarbamates of Cellulose and Amylose" Chirality.4. 122-124 (1992)
• [Publications] Y.Kaida and Y.Okamoto: "Optical Resolution by Supercritical Fluid Chromatography Using Polysaccharide Derivatives as Chiral Stationary Phases" Bull.Chem.Soc.Jpn.,. 65. 2285-2288 (1992)
• [Publications] E.Yashima,J.Noguchi,and Y.Okamoto: "Enantiomer Separation with Cellulose Tris(3,5-dimethylphenylcarbamate)Membrance.Enantioselective Adsorption and Desorption" Chmistry Letters,. 1959-1962 (1992)
• [Publications] Y.Kaida and Y.Okamoto: "The Separaion of Optically Acteve Copper (1)Catenates" Tetrahedron Letters,. 34. 1019-1022 (1993)
• [Publications] T.Hargitai,Y.Kaida,and Y.Okamoto: "Preparation and chromatographic evaluation of3,5-dimethylphenyl carbamoylated β-cyclodextrin stationary phases for normal-phase highperformance liquid chromatographic separation of enantiomers" Journal of Chromatography.628. 11-12 (1993)
• [Publications] T.Kumitake: "Synthetic Bilayer Membranes:Molecular Design and Self Organization" Angewandte Chemie. 104. 692-710 (1992)
• [Publications] M.Sano,D.Y.Sasaki T.Kunitake: "Scanning Tunneling Microscopy of Hydrogen Bonded Sheet of Epitaxiaeey Polymerized on Graphite" Science. 258. 441-443 (1992)
• [Publications] M.Marek,Jr.,K.Fukuta,T.Kunitake: "Preparation of Multilayered Film of Ultratkin Poly(tetraallylammonium bromide)Network" Chemistry Letters. 291-294 (1993)
• [Publications] T.Shimidzu,H.Segawa,M.Kitamura and A.Nimura: "Syntheses of oligonucleotide derivatives with P(V) Porphyrin and their properties" Nucleic Acids Symposium Series. 27. 97-98 (1992)
• [Publications] M.Kitamura,H.Ozaki K.Yamana and T.Shimidzu: "Chiral Phosphoromorpholidate Derivatives of Oligothymidylate and Their Hybridization Abilities" Nucleosides & Nucleotides. 11. 473-482 (1992)
• [Publications] T.Shimidzu,T.Iyoda,H.Segawa and K.Honda: "Functionalizations of conducting polymers toward molecular devices" mol.Cryst.Liq.Cryst.,. 216. 91-94 (1992)
• [Publications] H.Segawa,K.Kunimoto A.Nakamoto and T.shimidzu: "Synthesis of Axial Dialkoxy Phosphorus(V)porphyrin Derivatives-Novel Hypervalent Phosphorus Compounds" J.Chem.Soc.Perkin.Trans.1. 8. 939-940 (1992)
• [Publications] H.Segawa,N.Nakayama and T.Shimidzu: "Electrochemical Synthesis of One-dimensional Donor-Acceptor Polymers containing Oligothiophenes and Phosphorus Porphyrins" J.Chem.Soc.,Chem.Commun.,. 10. 784-785 (1992)
• [Publications] H.Segawa,A.Nakamoto and T.Shimidzu: "Photoinduced Axial Bond Exchange Reaction of DichioroPhosphorus(V)tetraphenylporphyrin Chloride:Photochemical Activation of Central 3c-4e Bond through the σ-π Interaction" J.Chem.Soc.,Chem.Commun.,. 15. 1066-1067 (1992)
• [Publications] A.Watanabe,and M.matsuda: "Photodegradation of Alkyl-and Ary1-substituted Polysilanes Obtained by Electrochemical Symthesis" Macromolecules. 25. 484-489 (1992)
• [Publications] A.Watanabe,H.Miike,Y.Tsutsumi,and M.Matsuda: "Photochemical Properties of Network and Branched Polysilanes" Macromolecules,in Press.
• [Publications] A.Watanabe,Y.Tsutsumi,and M.Matsuda: "Effect of Si-Skeleton Dimensionality on Optical and Electrical Properties of Poly(methylphenylsilylene)and Poly(phenylsilyne)" Synthetic metals,submitting.
• [Publications] A.Watanabe,Y.Natau,M.Matsuda,M.Suezawa,K.Sumino: "Amorphous Silicon Structure of Heat-Treated Poly(n-propylsilane)Studied by Far-Infrared Spectroscopy" Chem.Phys.Sett.,submitting.
• [Publications] T.Wada,N.Masumi,Y.Inaki,K.Takemoto.: "Synthesis and interaction studies of watersolble nucleic acid analogs containing serine as a spacer." Nucleic Acids Reseach Symp.,. 27,. 115-116 (1992)
• [Publications] T.Wada,Y.Inaki,and K.Takemoto: "Synthesis and interaction studies on water soluble nucleic acid analogs:Poly-L-lysine derivatives containing thymine and hypoxisantine." J.of Bioactive and Compatible Polymers,. 7. 25-38 (1992)
• [Publications] T.Wada,S.Chirachianchai,Y.Inaki,and K.Takemoto: "Preparation of PVA membrane containing nucleic acid analogs and studies on separation of nucleosides and dinucleotides using this membrane." Mol.Cryst.Liq.Cryst.219. 169-172 (1992)
• [Publications] Y.Inaki,T.Wada,H.Kawano,T.Watanabe,and K.Takemoto.: "Immobilization of cytidine and guanosine on silica gel and specific separation of oligonucleotides." Supramolecular Chimistry,. (1993)
• [Publications] Y.Inaki,Y.Wang,and K.Takemoto: "Reversible Photorecording system:Ordered thymine derivatives having long alkyl chain," J.Photopolym.Sci.Technol.,. 4. 259-266 (1991)
• [Publications] Y.Inaki: "Thymine Polymers as High Resolution Photoresists and Reversible Photo-recording Materials," Polymer News,. 17. 365-371 (1992)
• [Publications] K.Iwasaki T.Tokewa A.Hirao.S.Nakahama: "Morphology of Blends of Poly(3-(2-Propeny1)aniline-b-styrene-b-3-(2-Propenyl)aniline)with α,ω-Dicarboxy Poly(ethylene Oxide)" New Polymeric Materials. (1993)
• [Publications] K.Iwasaki,A.Hirao,S.Nakahama: "Morphology of blends of α,ω-diamino polystyrene with α,ω-dicarboxy poly(ethylene oxide)" Macromolecules. (1993)
• [Publications] T.Ishizune J.Tsuchiya,A.Herao,S.Nakahama: "Anionic Polymerization of Monomers Containing Fuyctional Groups.4.Anionic Living Polymerization of N,N-Dialkyl-4-vinylbenzenesulfonamides" Macromolecules. 25. 4840-4847 (1992)
• [Publications] D.G.Castner,B.D.Ratner D.W.Grainger,S.W.Kim T.Okano,K.Suzuki,D.Briggs,S.Nakahama: "Surface characterization of 2-hydroxyethyl methacrylate/styrene copolymers by angle-dependent X-ray Photoelectron spectroscopy and static secondary ion mass spectrometry" J.Biomater.Sci.Polymer Edn,. 3. 463-480 (1992)
• [Publications] H.Ozaki,A.Hirao,S.Nakahama: "Polymerization of Monomers Containing Functional Silyl Groups.11.Anionic Living Polymerization of 3(Tri-2-propoxysilyl)propyl Methacrylate" Macromolecules. 25. 1391-1395 (1992)
• [Publications] A.Hirao,K.Kato,S.Nakahama: "Protection and Polymerization of Functional Monomers.17.Synthesis of Well-Defined poly(vinylacetophenone)s by Means of Anionic Living Polymerization of tert-Buthyldimethylsilyl Enol Ethers of Vinylacetophenones" Macromolecules. 25. 535-540 (1992)
• [Publications] Shokyoku Kanaoka,Takahiro Omura,Mitsuo Sawamoto,Toshinobu Higashimura: "Star-Shaped Polymers by Living Cationic Polymerization.3.Syntheses of Heteroarm Amphiphilic Star-Shaped Poly-mers of Vinyl Ethers With Hyroxyl or Carbonyl Pendant Groups" Macromolecules. 25. 6407-6413 (1992)
• [Publications] Shokyoku Kanaoka,Mitsuo Sawamoto,Toshinobu Higashimura: "Star-Shaped Polymers by Living Cationic Polymerization.4.Selective Host-Guest Interaction of Small Molecules by Amphiphilic Star-Shaped Polymers of Vinyl Ethers" Macrmolecules. 25. 6414-6418 (1992)
• [Publications] Shokyoku Kanaoka,Mitsuo Sawamoto,Toshinobu Higashimura: "Star-Shaped Polymers by Living Cationic Polymerization.5.Core-Functionalized Amphiphilic Star-Shaped Polymers with Hydroxyl Groups:Synthesis and Host-Guest Inter-action" Macromolecules. 26. 254-259 (1993)
• [Publications] Shokyoku Kanaoka,Mitsuo Sawamoto,Toshinobu Higashimura: "Star-Shaped Polymers by Living Cationic Polymerization.6.Amphiphilic Star-Shaped Block Polymers of Vinyl Ethirs with Carboxyl Groups:Syntheses and Host-Guest Inter-action" Makromolekulare Chemie.
• [Publications] Shokyoku Kanaoka,Masanori Sueoka,Mitsuo Sawamoto,Toshinobu Higashimura: "Star-Shaped Polymers by Living Cationic Polymerization.7.Amphiphilic Graft Polymers of Vinyl Ethers With Hydroxyl Groups:Synthesis and Host-Guest Interaction" Journal of Polymer Science,Part A,Polymer Chemistry.
• [Publications] Shokyoku Kanaoka,Mitsuo Sawamoto,Toshinobu Higashimura,and other 6 authors: "Star-Shaped Polymers by Living Cationic Polymerization.8.Size and Shape of Star Poly(vinyl Ether)s Determined by Dynamic Light Scattering and Computer Simulation" Makromolekulare Chimie.
• [Publications] A.Mori,D.Yu,S.Inoue: "Enantioselective addition of diethylzinc to aldehyde catalyzed by α-amino acid amide." Synlett. 427-428 (1992)
• [Publications] Y.Iseki,A.Mori,S.Inoue: "Asymmetric epoxidation of allylic alcohols catalyzed by titamium alkoxidepeptide and -α-amino acid complexes anchored by phenolic Schiff base." J.Org.Chem.57. 6329-6331 (1992)
• [Publications] H.Ohno,A.Mori,S.Inoue: "Peptide aluminum complex as a novel chiral Lewis acid.Asymmetric addition of cyanotrimethylsilane to aldehydes." J.Org.Chem.57. 6778-6783 (1992)
• [Publications] H.Abe,A.Mori,S.Inoue: "A facile synthesis of optically active γ-cyanoallylic alcohols using asymmetric hydrocyanation of α,β-alkenyl aldehyde followed by stereospecific [3.3]sigmatropic chirality transfer of the cyanohydrin acetates." Chem.Lett.2443-2446 (1992)
• [Publications] H.Nitta,A.Mori,S.Inoue: "Peptide-titanium complex as catalyst for asymmetric addition of hydrogen cyanide to aldehyde." J.Am.Chem.Soc.114. 7969-7975 (1992)
• [Publications] S.Kobayashi: "Enzymatic Polymerization of α-D-Maltosyl Fluoride Utilizing α-Amylase as the Catalysr:A New Approach for the Synthesis of Maltooligosaccharides" Macromolecules. 25. 3237-3241 (1992)
• [Publications] S.Kobayashi: "Enzymatic Polymerization:The First in Vitro Synthesis of Cellulose via Nonbiosynthetic Path Catalyzed by Cellulase" Die Makromolekulare Chemie,Macromolecular Symposium. 54/55. 509-518 (1992)
• [Publications] S.Kobayashi: "A Novel Method for Synthesis of Cellooligosaccharide Derivatives by Using Enzyme Catalyst" Chemistry Letters,in preparation.
• [Publications] S.Shoda: "A Facile Enzymatic Synthesis of Cellooligosaccharide Derivatives Using β-D-Lactosyl Fluoride" Carbohydrate Research,in preparation.
• [Publications] K.Yokota,T.Kakuchi,K.Sakurai,Y.Iwata,H.Kawai: "Chirality induction arising from the twist of template on the cyclocopolymerization of 2,3-0-isopropylidene-1,4-di 0-methacryloyl-L-threitol with styrene" Makromol.Chem.,Rapid Commun.13. 343-349 (1992)
• [Publications] K.Yokota,T.Kakuchi,T.Yamamoto,O.Hada,T.Hasegawa: "Asymmetric induction arising from the chiral twist of 2,2'-binaphthyl template in the cyclopolymerization of divinyl ethers" Makromol.Chem.193. 1805-1813 (1992)
• [Publications] T.Kakuchi,O.Hada,Y.Harada,H.Hashimoto,K.Yokota: "Synthesis of poly(hemisphrand)via cyclopolymerization of diepoxide" polymer Bulletin. 27. 599-605 (1992)
• [Publications] H.Hashimoto,T.Kakuchi,O.Hada,K.Yokota: "Polymeric chiral crown ethers.8.Synthesis of optically active poly(dibenzo-19-crown-6)s via cyclopolymerization of diepoxides" Macromolecules. 25. 1828-1831 (1992)
• [Publications] T.Kakuchi,O.Hada,K.Yokota: "Cyclopolymerization of divinyl ethers.Synthesis and the cation-dinding property of poly(crown ether)s" Macromolecules. 25. 4854-4858 (1992)
• [Publications] T.Kakuchi,H.Kawai,S.Katho,O.Hada,K.Yokota: "Synthesis of optically active poly(methyl methacrylate)by cyclopolymerization of 1,4-di-0-methacryloly-L-threitol" Macromolecules. 25. 5545-5546 (1992)
• [Publications] T.Yoshida,Y.Katayama,S.Inoue,T.Uryu: "Synthesis of Branched Ribofuranans and Their Sulfates with Potent Anti-AIDS Virus Activity by Selective Ring-Opening Copolymerization of 1,4-Anhydro-α-D-ribopyranose Derivatives" Macromolecules. 25. 4051-4057 (1992)
• [Publications] K.Oda,T.Yoshida,T.Uryu.: "Ring-Opening Polymerization of Modified 1,4-Anhydroribose Derivatives I.1,4-Anhydro-2(ro3-)deoxy-3-(or2-)tert-butyldimethylsilyl-α-D-ribopyranose" Macromolecules.
• [Publications] Koichi Ute: "Stereoregular Oligomers of Methyl Methacrylate 6.Isolation of Isotactic and Syndiotactic MMA Oligomers from 19-mer to 29-mer by Preparative Supercritical Fluid Chromatography and Their Thermal Analysis" Polymer Bulletin. 28. 561-568 (1992)
• [Publications] Koichi Hatada: "Stereospecific Living Polymerization and Copolymerization of Methacrylate and Their Use for Construction of Stereoregular Chain Architecture" Makrmolecular Chemie,Macromolecular Sympolium,in press.
• [Publications] Nobutaka Fujimoto: "Stereocomplex Formation between Isotactic PMMA and Syndiotactic Random Copolymer of Methacryltes" Polymer Journal.
• [Publications] 稲井,横田 他: "Interaction between Aromatic Acceptors and Peotides Possessing a Pair of Aromatic Donors" Bull.Chem.Soc.Jpn.
• [Publications] 稲井,横田 他: "Conformational Anolysis of Aib-Containing Peptide by Comparison between Experimental and Theorectlcal CD Spectra" Biopolymers.
• [Publications] 横田,稲井 他: "Complex Formation between Poly(4-vinylpyridine)and Periodic Methacrylic Acid Copolmers in Solid." Macromolecules.
• [Publications] M.Okada: "Chemical synthesis of 4-deoxy-(1→6)-α-D-xylo-hexopyranan and 3,4-dideoxy-(1→6)-α-D-erythro-hexopyranan" Carbohydrate Research. 226. 345-352 (1992)
• [Publications] M.Okada: "Chemical Synthesis of Polysaccharides XI.Ring-Ppening Polymerization of 1,6-Anhydro-2-ο-(ρ-Substituted Benzoyl) Deoxysugar Derivatives" Polymer Journal. 24. 1137-1145 (1992)
• [Publications] K.Kobayashi: "Steric Control in Ring-Ppening Polymerization of 1,6-Anhydro Galactose Derivatives by Neighboring Group Participation" Polymer Journal. 25. 49-57 (1992)
• [Publications] K.Kobayashi: "Chemical Synthesis of aComb-Shaped,Branched Stereoregular Polysaccharide,4-ο-α-D-mannopyranozyl-(1→6)-α-D-mannopyranan" Carbohydrate Research. (1993)
• [Publications] Osamu Nakagawa: "Preparation of Highly Syndiotactic Block Copolymers of Methyl Methacrylate and Lauryl Methacrylate and Their Characterization" Polymer Bulletin. 29. 579-586 (1992)
• [Publications] Takafumi Nishiura: "Preparation of Stereoregular Block Copolymer Comprising Isotactic PMMA and Polyisobutylene Blocks and Its Characterization" Polymer Bulletin. 27. 615-622 (1992)
• [Publications] 横田,稲井 他: "Complex Formation between Poly(4-Binylpyridine)and Periodic Methacrylic Acid Copolymers in Solution" Macromolecules.
• [Publications] 横田,稲井 他: "Synthesis of Sequence-Ordered Copolymers.3.Glass Transition Temperatures of Sequence-Ordered and Unordered Copolymers" Macromolecules. 25. 5821-5827 (1992)
• [Publications] 岡本 佳男,海田 由里子: "有機合成化学協会誌" 多糖誘導体をキラル固定相に用いる高速液体クロマトグラフィーによる光学分割, 12 (1993)
• [Publications] 清水 剛夫(分担執筆): "膜処理技術大系下巻(応用・資料編)" フジ・テクノシステム, 5 (1991)
• [Publications] T.Shimidzu and M.Yoshikawa: "Pervaporation Membrane Separation Processes" Elsevier, 41 (1991)
• [Publications] 稲木 良昭,和田 健彦,望月 衛子: "「人工核酸」-合成・機能・応用-" IPC出版、, 354 (1992)
• [Publications] 中浜 精一 他高分子学会編共著: "高分子機能材料シリーズ1高分子の合成と反応(1)" 共立出版, 554 (1992)
• [Publications] Toshiyki.Uryu: "Artificial Polysaccharides and TheirBiological Activeties" Pergamon Press,Oxford,UK,