• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Circular Dichroism of Crystals

Research Project

Project/Area Number 14340220
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionEhime University

Principal Investigator

KOSHIMA Hideko  Ehime University, Faculty of Engineering, Associate Professor (20304644)

Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 2003: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2002: ¥12,300,000 (Direct Cost: ¥12,300,000)
KeywordsCrystal Optical Activity / Circular Dichroism Spectra / Optical Rotatory Power / Chiral Crystals / Organic Crystals / Birefringence / Chirality / Helical Structure / 光学活性特性
Research Abstract

Every chiral organic crystal has inherent optical activity. The sign and the magnitude of the optical activity of an organic crystal should reflect the molecular structure as well as the packing arrangement because the freedom of molecules is severely restricted in the crystal lattice, which is very different from the high mobility of molecules in solution. However, the optical activity of organic crystals has been scarcely measured and therefore never correlated with the crystal structure until the present time. The reason for this is that the measurement of optical activity of a crystal is accompanied with much difficulty due to birefringence being 10^3 times larger birefringence than the gyration tensor, so in this case the latter effect is masked. A few years ago, we first introduced a high accuracy universal polarimeter (HAUP) in chemistry. Recently, we prepared a new version of HAUP in order to measure circular dichroism spectra of crystals. Now the check of performance is in progress.
Herein the rotatory powers of helical-type cocrystal formed between tryptamine and 4-chlorobenzoic acid were determined by the HAUP method. After much trial and error, we could overcome the sample polish problem by using soft Fe_2O_3 polish agent and obtain satisfactorily the rotatory powers of the cocrystal from tryptamine and 4-chlorobenzoic acid. The results revealed that the helically arranged aromatic π electrons as well as the helical ionic and hydrogen bond networks in the crystal contributed to the enhancement of the magnitude of these rotations. This is the the first measurement of the optical activity of organic-organic cocrystal formed from two different achiral molecules.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (23 results)

All 2004 2003 Other

All Journal Article (9 results) Book (1 results) Publications (13 results)

  • [Journal Article] Preparation of Cocrystals of 2-Amino-3-nitropyridine with Benzenesulfonic Acids for Second Order Nonlinear Optical Materials2004

    • Author(s)
      H.Koshima, H.Miyamoto, I.Yagi, K.Uosaki
    • Journal Title

      Crystal Growth and Design 4

      Pages: 807-811

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Photoreaction of 9-Methylbenz[c]acridine with Diphenylacetic Acid in the Chiral Cocrystal2003

    • Author(s)
      H.Koshima, A.Nakata, M.Nagano, H.Yu
    • Journal Title

      Heterocycles 60

      Pages: 2251-2252

    • NAID

      40005940529

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Preparation and Photoreaction of Organogels Based on Benzophenone2003

    • Author(s)
      H.Koshima, W.Matsusaka, H.Yu
    • Journal Title

      Journal of Photochemistry and PhotoBiologyA : Chemistry 156

      Pages: 83-90

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Absolute Asymmetric Photoreactions of Acridines with Diphenylacetic Acid in the Cocrystals

    • Author(s)
      H.Koshima
    • Journal Title

      Molecular Crystals and Liquid Crystals (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Optical Activity Induced by Helical Arrangements of Tryptamine and 4-Chlorobenzoic Acid in their Cocrystal

    • Author(s)
      H.Koshima, M.Nagano, T.Asahi
    • Journal Title

      Journal of American Chemical Society (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Design of Absolute Asymmetric Photocyclization of Isopropylbenzophenone Derivatives by Cocrystal Approach and the SingleCcrystal-to-single-Crystal Transformation

    • Author(s)
      H.Koshima, H.Kawanishi, M.Nagano, H.Yu, M.Shiro, T.Hosoya, H.Uekusa, Y.Ohashi
    • Journal Title

      Journal of organic Chemistry (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Absolute Asymmetric Photoreactions of Acridines with Diphenylacetic Acid in the Cocrystals

    • Author(s)
      H.Koshima
    • Journal Title

      Molecular Crystals and Liquid Crystals (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Optical Activity Induced by Helical Arrangements of Tryptamine and 4-Chlorobenzoic Acid in their Cocrystal

    • Author(s)
      H.Koshima, M.Nagano, T.Asahi
    • Journal Title

      Journal of American Chemical Society (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Design of Absolute Asymmetric Photocyclization of Isopropylbenzophenone Derivatives by Cocrystal Approach and the SingleCcrystal-to-single-Crystal Transformation

    • Author(s)
      H.Koshima, H.Kawanishi, M.Nagano, H.Yu, M.Shiro, T.Hosoya, H.Uekusa, Y.Ohashi
    • Journal Title

      Journal of organic Chemistry (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Book] Chiral Photochemistry2004

    • Author(s)
      H.Koshima
    • Total Pages
      665
    • Publisher
      Marcel Dekker, Inc.
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Koshima, A.Nakata, M.Nagano, H.Yu: "Photoreaction of 9-Methylbenz[c]acridine with Diphenylacetic Acid in the Chiral Cocrystal"Heterocycles. 60. 2251-2258 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima, W.Matsusaka, H.Yu: "Preparation and Photoreaction of Organogels Based on Benzophenone"J.Photochem.Photobiol., A : Chem.. 156. 83-90 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima, Masashi Kubota: "High-Throughput Synthesis of Alkylbenzophenones with Indium Triflate in the Absence of Solvents Using Microwave"Synth.Commun. 33. 3983-3988 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Yu, H.Koshima: "A Convenient Asymmetric Alkylation of Glycine Imine Esters Using Solid Supports"Tetrahedron Lett.. 44. 9209-9211 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima, H.Miyamoto, I.Yagi, K.Uosaki: "Cocrystals of 2-Amino-5-nitropyridine with Benzenesulfonic Acids for Second Order Nonlinear Optical Materials"Mol.Cryst.Liq.Cryst.. (In press).

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima: "Absolute Asymmetric Photoreactions of Acridines with Diphenylacetic Acid in the Cocrystals"Mol.Cryst.Liq.Cryst.. (In press).

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima: "Chiral Photochemistry"Marcel Dekker, Inc.(In press).

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Koshima, K.Kutsunai: "Rapid Synthesis of Acridines Using Microwave"Heterocycles. 57. 1299-1302 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Koshima, W.Matsusaka: "N-Bromosuccinimide Catalyzed Condensations of Indoles with Carbonyl Compounds under Solvent-free Conditions"Journal of Heterocyclic Chemistry. 39. 1089-1091 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Koshima, M.Hamada: "Solvent-free Condensation of Aromatic Aldehydes and 2,3-Dimethyl-1-phenyl-3-pyrazolin-5-one Catalyzed by p-Toluenesulfonic Acid"Journal of Heterocyclic Chemistry. 39. 1087-1088 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Koshima, M.Hamada, M.Tani, S.Iwasaki, F.Sato: "High-throughput Synthesis of Symmetrically 3,5-Disubstituted 4-Amino-1,2,4-tnazoles from Aldehydes Using Microwave"Heterocycles. 57. 2145-2148 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Koshima, W.Matsusaka, H.Yu: "Preparation and Photoreaction of Organogels Based on Benzophenone"J. Photochem. Photobiol., A : Chem.. 156. 83-90 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Koshima: "Organic Solid State Reactions"Kluwer Academic Publishers. 275 (2002)

    • Related Report
      2002 Annual Research Report

URL: 

Published: 2002-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi