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ゼロバックグラウンド吸収を用いたキラル分子の光制御

Research Project

Project/Area Number 08875190
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field 高分子構造・物性(含繊維)
Research InstitutionThe University of Tokyo

Principal Investigator

山下 俊  東京大学, 大学院・工学研究科, 講師 (70210416)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1997: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1996: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywordsスルホキシド / 不斉反転 / 自由体積
Research Abstract

1.光学活性色素・光学活性前駆体色素の合成
フェニルトリルスルホキシドおよびそのピレン誘導体を合成し、光学物性の評価を行った。これらの色素は、紫外に吸収をもち、モル楕円率はあまり高くないが、光励起により不斉反転することが分かった。光不斉反転反応の量子収率は0.02程度で、溶媒の極性などには影響をうけないことが分かった。
2.光異性化反応に伴う不斉誘起反応の解析
合成した不斉反転型色素の溶液中および高分子固相中での光不正反転反応挙動を調べた。反応の量子収率は高分子固相中でも溶液中とあまり変わらず、この色素の不斉反転に要する自由体積はきわめて小さいことが分かった。しかし、光反応後期では、一次反からのずれが見られ、自由体積分布を反映していることが分かった。さらに、そのダイナミクスの温度化を室温から液体窒素温度までの範囲で測定したところ、80Kでは、反応速度は低下することが分かった。これは、動的自由体積の影響をうけるためと考えられる。これらの知見から、この色素はこれまでにないミクロ環境を反映するプローブ素であることが分かったが、さらに、不斉ポリマーなどを用いれば、不斉反応場の環境プローブとしての応用が期待される。

Report

(2 results)
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] H.Yu, T.Yamashita, and K.Horie: "Synthesis and Chemically Amplified Photo-Cross-Linking Reaction of a Polyimide Containing an Epoxy Group" Macromolecules. 29(4). 1144-1150 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] 伊藤、氏平、浅野、山下: "アクリルアミド系ゲルの温度、メタノール/水による体積相転移の自由体積パラメータ変化-陽電子消滅寿命測定、蛍光プローブの蛍光異方性比測定、および回転拡散運動測定で得られた結果の比較" 高分子論文集. 53(6). 366-374 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.W.Huang, K.Horie, T.Yamashita, W.Machida, M.Sone, M.Tokita, J.Watanabe Y.Maeda: "Fluorescence Study on Intermolecular Interaction Between Mesogenic Biphenyl Moieties of a Thermotropic Liquid-Crystalline Polyester(PB-10)" Macromolecules. 29(10). 3485-3490 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.S.Yu, T.Yamashita, K.Horie: "Influence of a Photo-acid Generator on Photoreactivity of a Photosensitive Polyimide Containing Epoxy Groups" Polym.J.28(8). 703-707 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Takahashi, K.Horie, T.Yamashita, M.Sone, J.Watanabe: "Fluorescence Study on a Thermotropic Liquid Crystal:Bis(p-hexyloxyphenyl)terephthalate" Liquid Crystals. 21(4). 505-510 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Takahashi, K.Horie, T.Yamashita, S.Machida, D.T.B.Hannah, D.C.Sherrigiton: "Fluorescence Study of the Microstructure of a Lyotropic Liquid Crystalline Polyester Substituted with Sulfonate and Nitro Groups" Macromol.Chem.Phys.197(9). 2703-2712 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.A.Lee, T.Yamashita, K.Horie: "Photoconductivity of Aliphatic Polyimide" J.Photopolymer Sci.Tech.9(2). 355-362 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Tomoyose, D.-L.Jiang, T.Aida, H.Horie, T.Yamashita, Y.Okamoto, E.Yashima: "Aryl Ether Dendrimers with an Interior Metalloporphyrin Functionality as a Spectroscopic Probe:Interpenetrating Interaction with Dendritic Imidazoles." Macromolecules. 29. 5236-5238 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Nishiyama, S.Machida, T.Yamashita, K.Horie: "Persistent Spectral Hole Burning of Resazurin Sodium Salt in Glassy Polymer Matrices" Chem.Lett.1996. 1015-1016 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Tanaka, S.Machida, T.Yamashita, K.Horie: "Low-Temperature Structural Relaxation in Poly(alkyl methacrylate)s and Related Polymers Probed by Photochemical Hole Burning" Macromol.Chem.Phys.197. 4095-4103 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] 森野慎也, 木下耕一, 山下俊, 堀江一之: "有機光導波材料の光学物性の評価" 東京大学工学部総合試験所年報. 55. 121-125 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Itoh, Y.Ujihira, T.Yamashita, K.Horie: "Positron Annihilation Lifetime Studies of the Volume Phase Transition of Polyacrylamides" J.Radioanal.Nuclear.Chem.210(2). 505-511 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.L.Li, Y.Ujihira, S.Tanaka, T.Yamashita, K.Horie: "Variation of Free Volume Parameters of Polyalkylmethacrylate Derivatives in the Range from 15 to 300K Probed by Positron Annihilation" J.Radioanal.Nuclear.Chem.210(2). 543-553 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Yasunari Maekawa, Takao Miwa, Takashi Yamashita: "Solution Properties of Polyamic Acids and their Amine Salts" Reactive Polymers. 30. 71-73 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.A.Lee, T.Yamashita, K.Horie, T.Kozawa: "Transient Absorption Spectra of Photoconductive Polyimides and Their Model Compound by Picosecond Pulse Radiolysis" J.Phys.Chem.B101. 4520-4524 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 李 洪玲, 氏平祐輔, 田中聡美, 山下 俊, 堀江一之: "ポリメタクリル酸アルキルの低温分子運動緩和の陽電子消滅寿命から求めた自由体積による観察" 高分子論文集. 54. 391-400 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.A.Lee, T.Yamashita, K.Horie: "Photoconductivity of a Polyimide with an Alicyclic Diamine Doped with N,N,N',N' Tetramethyl-p-phenylenediamine(TMPD)" Polym.J.29. 752-758 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Tsuneda, T.Endo, K.Saito, K.Sugita, K.Horie, T.Yamashita, T.Sugo: "Local Mobility of Polymer Chain Grafted onto Polyethylene Monitored by Fluorescence Depolarization" Chem.Phys.Lett. 275. 200-210 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Tsurutani, T.Yamashita, K.Horie: "Photoinversion Reaction of a Pyrenyl Substituted Sulfoxide in Solution and in Polymer Matrix" Polymer J.30. 11-16 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.L.Li, Y.Ujihira, T.Yoshino, T.Tanaka, K.Yoshii, T.Yamashita, K.Horie: "Free Volumes and Their Distribution in Crosslinked Polysiloxahes Probed by Positron Annihilation Lifetime Technique" Polymer.

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Sone, T.Wada, B.R.Harkness, J.Watanabe, H.Takahashi, H.W.Huang, T.Yamashita, K.Horie: "Rigid-rod Polyesters with Flexible Side Chains Based on 1,4-Dialkylesters of Pyromellitic Acid and 4,4'Biphenol.7.Charge Transfer Complex Formation in Layered Mesophase Analyzed with Variable-Temperature Fluorescence Spectroscopy" Macromolecules,.

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ito, Y.Ujihira, T.Yamashita, K.Horie: "Study of Hydro Gel by means of Positron Annihilation Lifetime Measurement [I]Volume Phase Transition of Poly(N-isopropylacrylamide)Gel Induced by Temperature" Macromolecules,.

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Kino, S.Machida, T.Yamashita, K.Horie, S.Yusa, Y.Morishima: "Microenvironments around Tetraphenylporphine Group in Unimacromolecular Micelles Probed by Photochemical Hole Burning" Macromolecules.

    • Related Report
      1997 Annual Research Report
  • [Publications] S.A.Lee, T.Yamashita, K.Horie: "Photoconductivity of a Polyimide with an Alicyclic Diamine;Charge Carrier Photogeneration in the Mixed Layer Packing Arrangement" J.Polym.Sci:Part B:Polym.Phys.

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Yamashita, K.A.Nelson: "Femtosecond Transient Absorption of Polyimides and their Precursore" Chem Phys.Lett.

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Yamashita: "Mechanical Properties of a Polyimide Gels with ISTS Measurement" Macromolecules,.

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ito, Y.Ujihira, T.Yamashita, K.Horie: "Study of Hydrogel by means of Positron Annihilation Lifetime Measurement [II]Volume Phase Transition of Poly(N-isopropylacrylamide) Gel Induced in Methanol/Water Mixed Solven" Macromolecules,.

    • Related Report
      1997 Annual Research Report
  • [Publications] Miwa, Y.Okabe, Y.Maekawa, T.Ueno, G.Rames-Langrade: "Alkali-developbable positive-photosensitive polyimide based on diazonaphthoquinone sennsitizer" 6th SPSJ International Polymer Conference,The Society of Polymer Science,Japan,Kusatsu Japan,. 20-24 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Miwa, Y.Okabe, M.Ishida: "Effect of Precursor Structure and imidization process on thermal expansion coefficient of polyimide(BPDA/PDA)" Polymer. 38. 4945 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Miwa, Y.Okabe, M.Ishida, M.Hasegawa, T.Matano, Y.Shindo, T.Sugimura: "Solution Properties and Imidization Reaction of Polyimide Precursors:Polyamide Acid,Polyamide Acid ester and Polyamide Acid Amine Salt" Polyimides:Trends in Materials and Application. 231 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Yamashita K.Horie: "Proceedings of China-Japan Birateral Symposium on Polymer Materials" Caiyuan Pan,T.Uryu Eds.,Press of University of Scieicne and Technology of Chine, 260 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Yu,T.Yamashita,and K.Horie: "Synthesis and Chemically Amplified Photo-Cross-Linking Reaction of a Polymide Containing an Epoxy Group" Macromolecules. 29(4). 1144-1150 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 伊藤、氏平、浅野、山下、堀江: "アクリルアミド系ゲルの温度、メタノール/水による体積相転移の自由体積パラメータ変化-陽電子消滅寿命測定、蛍光プローブの蛍光異方性比測定、および回転拡散運動測定で得られた結果の比較" 高分子論文集. 53(6). 366-374 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.W.Huang,K.Horie,T.Yamashita,S.Machida,et al.: "Fluorescence Study on Intermolecular Interaction Between Mesogenic Biphenyl Moieties of a Thermotropic Liquid-Crystalline Polyester (PB-10)" Macromolecules. 29(10). 3485-3490 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.S.Yu,T.Yamashita,K.Horie: "Influence of a Photo-acid Generator on Photoreactivity of a Photosenstive Polymide Containing Epoxy Groups" Polym.J.28(8). 703-707 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Takahashi,K.Horie,T.Yama-shita,M.Sone,et al.: "Fluorescence Study on a Thermotropic Liquid Crystal : Bis (p-hexyloxyphenyl) terephthalate" Liquid Crystals. (in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Takahashi,K.Horie,T.Yama-shita,S.Machida,et al.: "Fluorescence Study of the Microstructure of a Lyotropic Liquid Crystalline Polyester Substituted with Sulfonate and Nitro Groups" Macromol.Chem.Phys.197(9). 2703-2712 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Yamashita K.Horie: "Proceedings of China-Japan Birateral Symposium on Polymer MaterialsScinecne" Caiyuan Pan,T.Uryu Eds.,Press of University of Scieicne and Technology of China, 260 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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