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2000 Fiscal Year Final Research Report Summary

Development of chiral fluorescent derivatization reagents for discrimination of enantiomers having chiral centers far remote from the derizatizable functional groups and their application to determination of absolute configuration of natural products

Research Project

Project/Area Number 10460046
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field Bioproduction chemistry/Bioorganic chemistry
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

OHRUI Hiroshi  Graduate school of Agriculturalscience, TOHOKU UNIVERSITY, professor, 大学院・農学研究科, 教授 (20100050)

Co-Investigator(Kenkyū-buntansha) AKASAKA Kazuaki  Graduate school of Agriculturalscience, TOHOKU UNIVERSITY, Assistant professor, 大学院・農学研究科, 助教授 (10201881)
Project Period (FY) 1998 – 2000
Keywordsdiscrimination of remote chirality / branched fatty acid / branched alcohol / chiral discrimination / fluorescent chiral derivatization reagent / ^1H-NMR / HPLC
Research Abstract

We have open a way to the chiral discrimination of enantiomers having chiral center far remote from the diastereomeric-derivatizable functional groups that has been thought impossible for long time. Thus, a new chiral derivatization reagents, (R)-and (S)-2A-1P-O-Tf (1) and (R)-and (S)-1A-2P-O-Tf (2) are developed and the chiral discriminations of the carboxylic acids with methyl branching at from 2 to 11 by ^1H-NMR and those from 2 to 8 by HPLC were attainedby labelling with 1 and 2. A new reagent to improve the shortcomings of 1 and 2, (R,R)-and (S,S)-2A-CH-OH (3), was developed and the chiral discrimination of methyl branched fatty acids with branching from 2 to 24 was attained with 3. By these system, the absolute configuration of ceramides, gangliosides, and glycerol were determined using μ〜ng of samples.
Chiral derivatization reagents for chiral alcohols (R,R)-and (S,S)-2A-CH-COOH (4) and 3,4,6-O-Ac-2A-2d-β-Glu-Br (5) were prepared, and a system for the determination of absolute configuration of chiral alcohols by use of 4 was developed.

  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] Kazuaki Akasa,Hiroshi Ohrui,and Hiroshi Meguro: "Determimtiion of Carboxyllc Acids by High-performance Liquid Chromatograpy with 2-(2,3-Anthracend icarboxyimido) ethyl Trifluoromethanesllifonate as a Highly Sensitive Fluorescent Labelling Reagent"Analyst.. 118. 765-768 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Akasa,Hiroshi Ohrui,Hiroshi Meguro: "Fluorometric Determination of Diarrhetic Shellfish Toxins in Scallops and Mussels by High-Performance Liquid Chromatography"Journal of Chromatography A. 729. 391-396 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Akasaka,H.Ohrui,H.Meguro,and T.Yasumoto: "Determination of Dinophysis Toxins-3 by the LC-LC Method with Fluorometric Detection"Analytical Science. 12. 557-560 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Akasa,Hiroshi Meguro,and Hiroshi Ohrui: "Enantiomeric Separation of Carboxylic Acids Having Chiral Centers Remote from the Carboxyl Group by Labelling with a Chiral Fluorescent Derivatization Reagent"Tetrahedron Letters. 38. 6853-6856 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Akasaka,H.Ohrui,H.Meguro,and T.Umezu: "Highly Sensitive Isomeric Determination of Beraprost Sodium in Plasma Using a Fluorescent Chiral Derivatization Reagent"Analytical Sciences. 13. 461-466 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Akasaka,Keiichiro Imaizumi,and Hiroshi Ohrui: "Enantiomeric Separation of Branched Fatty Acids Having Chiral Centers Remote from the Carboxyl Group by Labelling with Chiral Fluorescent Derivatization Reagents"Enantiomer,3,. 3. 169-174 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Akasaka and Hiroshi Ohrui: "Enantlomeric Separation of Branched Fatty Acids after Conversion with 1 trans-2-(2,3-Anthracenedicarboximido) cyclohexanol, a Highly Sensitive Chiral Fluorescent Conversion Reagent"Biosci,Biotechnol. Biochem.. 63. 1209-1215 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 赤坂和昭,今泉啓一郎,大類洋: "蛍光性不斉誘導体化試薬による分岐脂肪酸の遠隔位不斉識別"分析化学. 48. 1085-1094 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Pu Qian,H.Nanjo,T.Yokoyama,M.Suzuki,K.Akasa And H.Ohrui: "Chiral molecular patterns of self-assembled ion pairs composed of (R,S),(S)-16-methyloctadecanoic acid and 4,4'-bispyridine"Chem.Commun,. 2021-2022 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Akasa,S.Shitijyukari,S.Matsuoka,M.Murata,H.Meguro,and H.Ohrui: "Absolute Configuration of a Ceramide with a Novel Branched-chain Fatty Acid Isolated from the Epiphytic Dinoflagellate,Coolia monotis"Biosci,Biotechnol. Biochem... 64. 1842-1846 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大類洋: "蛍光分析試薬の開発とその応用-油化学研究を中心として-"油化学. 44. 949-959 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hiroshi Meguro and Hiroshi Ohrui: "Strategy and Design of Novel Reagents for the Fluorometric Analysis of Biomelecule"Biosci,Biotechnol. Biochem... 60. 1919-1924 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大類洋: "新しいキラル分析法の開発"化学工業. 5. 64-77 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大類洋: "高感度キラル蛍光分析試薬開発の戦略"有機合成化学協会誌. 7. 591-603 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大類洋,赤坂和昭: "蛍光試薬"ぶんせき. 11. 678-683 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Akasaka, Keiichiro Imaizumi, and Hiroshi Ohrui: "Enantiomeric Separation of Branched Fatty Acids Having Chiral Centers Remote from the Carboxyl Group by Labelling with Chiral Fluorescent Derivatization Reagents"Enantiomer. 3. 169-174 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuaki Akasaka and Hiroshi Ohrui: "Enantiomeric Separation of Branched Fatty Acids after Conversion with 1 trans-2-(2,3-Anthracenedicarboximido) cyclohexanol, a Highly Sensitive Chiral Fluorescent Conversion Reagent"Biosci, Biotechnol.Biochem.. 63. 1209-1215 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuaki Akasaka, Keiichiro Imaizumi, and Hiroshi Ohrui: "Enantiomeric Separation of Branched Fatty Acids having chiral centers remote from the carboxyl group by derivatization with chiral fluorescent-labellig reagents"BUNSEKI KAGAKU. 48. 1085-1094 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Pu Qian, Hiroshi Nanjo, Toshiro Yokoyama, Toshishige M.SuZuki, Kazuaki Akasaka And Hiroshi Ohrui: "Chiral molecular patterns of self-assembled ion pairs composed of (R,S), (S)-16-methyloctadecanoic acid and 4,4'-bispyridine"Chem.Commun. 2021-2022 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuaki Akasa, Seiya Shitijyukari, Shigeru Matsuoka, Michio Murata, Hirosbi Meguro, and Hiroshi Ohrui: "Absolute Configuration of a Ceramide with a Novel Branchedchain Fatty Acid Isolated from the Epiphytic Dinoflagellate, Coolia monotis"Biosci, Biotechnol.Biochem.. 64. 1842-1846 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi Ohrui: "Development of New chiral Discrimination Methods"KAGAKU OGYOSYA. 5. 64-77 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi Ohrui: "Strategies for Development of Fluorescent Derivatization Reagents for Highly Sensitive Analysis of Biomolecules"Journal of synthesis organic chemistry. 7. 591-603 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuaki Akasa, Hiroshi Ohrui: BUNSEKI. 11. 678-683 (2000)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2002-03-26  

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