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TOXIC SUBSTANCES, HETEROCAPSATOXIN A AND B TOWARDS OYSTER FROM RED TIDES, HETEROCAPSA CIRCULARISQUAMA, APPREARED IN SETO INLAND SEA

Research Project

Project/Area Number 14380275
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 環境保全
Research InstitutionHIROSHIMA UNIVERSITY

Principal Investigator

HIRAGA Yoshikazu  HIROSHIMA UNIV., GRADUATE SCHOOL OF SCIENCE, ASSISTANT, 大学院・理学研究科, 助手 (10238347)

Co-Investigator(Kenkyū-buntansha) OHKATA Katsuo  HIROSHIMA UNIV., GRADUATE SCHOOL OF SCIENCE, PROFESSOR, 大学院・理学研究科, 教授 (50033882)
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 2004: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2003: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2002: ¥3,500,000 (Direct Cost: ¥3,500,000)
KeywordsRed Tide Plankton / Dinoflagellate / Heterocapsa circularisquama / Toxic substance / Heterocapsatoxin / NMR / Ozonolysis / MALDI-MS / アセチル化 / オゾン分解 / 酸素官能基 / 二枚貝 / 単純脂質 / ガラクトース / 脂肪酸 / 細胞溶解活性 / チラコイド膜
Research Abstract

Harmful phytoplankton blooms have caused serious social and environmental problems and heavy damage to fisheries throughout the world. In recent years, a novel dinoflagellate Heterocapsa circularisquama has caused mass mortality of bivalves, e.g. oysters and pearl oysters, in several inner bay of Japan. In our research the toxic substance in this plankton, two novel compounds exhibit the toxicity towards oyster were isolated.
The algae of cultured H.circularisquama was extracted with 1-BuOH, and the 1-BuOH extract was partitioned between hexane and 80% MeOH. The residue from the 80% MeOH-soluble fraction was subjected to column chromatography on reversed phase silica gel to afford the biologically active fractions. Further separation by silica gel column chromatography, gel permeation chromatography, and HPLC (reverse phase) yielded two toxic substances named heterocapsatoxin A (HTX-A, molecular weight 5024) and heterocapsatoxin B (HTX-B, molecular weight 1980). Analysis of ^1H and ^<13>C NMR spectra of HTX-A and HTX-B, they have a very similar structures which contained the several C=C double bonds and many oxygen functionalities.
In order to elucidate the structure of HTX-A,HTX-A was subjected to ozonolysis to give two major products, which were named HTX-A1 and HTX-A2. HTX-A1 was determined to have the molecular formula C_<46>H_<84>O_<22> by high-resolution FABMS. The structural elucidation of HTX-A1 was performed mainly by NMR experiments consisting ^1H and ^<13>C NMR,COSY,HMQC, and HMBC.

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (24 results)

All 2004 2003 2002 Other

All Journal Article (16 results) Publications (8 results)

  • [Journal Article] 1H and 13C NMR spectroscopic studies of half-esters from monohydrolysis of dialkyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylates2004

    • Author(s)
      Hiraga, Yoshikazu
    • Journal Title

      Spectroscopy 18

      Pages: 469-483

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Relationship between the hydrophobicity of dipeptides and the Michaelis-Menten constant Km of their hydrolysis by carboxypeptidase-Y and carboxypeptidase-A2004

    • Author(s)
      Kanosue, Yoshifumi
    • Journal Title

      Bull.Chem.Soc.Jpn 77

      Pages: 1187-1193

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 1H and 13C NMR spectroscopic studies of half-esters from monohydrolysis of dialkyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylates2004

    • Author(s)
      Hiraga, Yoshikazu, Niwayama, Satomi
    • Journal Title

      Spectroscopy 18

      Pages: 469-483

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Relationship between the hydrophobicity of dipeptides and the Michaelis-Menten constant Km of their hydrolysis by carboxypeptidase-Y and carboxypeptidase-A.2004

    • Author(s)
      Kanosue, Yoshifumi, Kojima, Satoshi, Hiraga, Yoshikazu, Ohkata, Katsuo
    • Journal Title

      Bull.Chem.Soc.Jpn. 77

      Pages: 1187-1193

    • NAID

      130004151711

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] ^1H and ^<13>C NMR spectroscopic studies of half-esters from monohydrolysis of dialkyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylates2004

    • Author(s)
      Yoshikazu Hiraga
    • Journal Title

      Spectroscopy 18・3

      Pages: 469-483

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Relationship between hydrophobicity of dipeptides and Michaelis-Menten constant K_m of their enzymatic hydrolysis2004

    • Author(s)
      Yoshifumi Kanosue
    • Journal Title

      Bulletin of the Chemical Society of Japan 77・6

      Pages: 1187-1193

    • Related Report
      2004 Annual Research Report
  • [Journal Article] New exo/endo selectivity observed in monohydrolysis of dialkyl bicyclo[2.2.1]hept-5-ene- 2,3-dicarboxylates2003

    • Author(s)
      Niwayama, Satomi
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 8567-8570

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Sterol composition of a cultured marine dinoflagellate, Heterocapsa circularisquama2003

    • Author(s)
      Kaku, Ken
    • Journal Title

      Natural Product Res. 17

      Pages: 263-267

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New exo/endo selectivity observed in monohydrolysis of dialkyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylates2003

    • Author(s)
      Niwayama, Satomi, Hiraga, Yoshikazu
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 8567-8570

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Sterol composition of a cultured marine dinoflagellate, Heterocapsa circularisquama2003

    • Author(s)
      Kaku, Ken, Hiraga, Yoshikazu
    • Journal Title

      Natural Product Res. 17

      Pages: 263-267

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Hydrophobicity and structure of 1,2,4-triazole derivatives bearing 1-carbamoyl and 3-sulfonyl groups2002

    • Author(s)
      Ohkata, Katsuo
    • Journal Title

      Bull.Chem.Soc.Jpn. 75

      Pages: 567-574

    • NAID

      10009175652

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereochemical considerations on the stereoselective cyclopropanation reactions of 3-aryl-2-phosphonoacrylates induced by the (-)-8-phenylmenthyl group as a chiral auxiliary2002

    • Author(s)
      Takagi, Ryukichi
    • Journal Title

      J.Chem.Soc., Perkin Trans.1 2002

      Pages: 179-190

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new digalactosyl diacylglycerol from a cultured marine dinoflagellate Heterocapsa circularisquama2002

    • Author(s)
      Hiraga, Yoshikazu
    • Journal Title

      J.Nat.Prod. 65

      Pages: 1494-1496

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Hydrophobicity and structure of 1,2,4-triazole derivatives bearing carbamoyl and 3-sulfonyl groups2002

    • Author(s)
      Ohkata, Katsuo, Yano, Tomoyuki, Kojima, Satoshi, Hiraga, Yoshikazu, Yoshii, Tomoko, Hori, Masahiro
    • Journal Title

      Bull.Chem.Soc.Jpn. 75

      Pages: 567-574

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereochemical considerations on the stereoselective cyclopropanation reactions of 3-aryl-2-phosphonoacrylates induced by the (-)-8-phenylmenthyl group as a chiral auxiliary2002

    • Author(s)
      Takagi, Ryukichi, Hashizume, Miki, Nakamura, Minoru, Begum, Shahnaz, Hiraga, Yoshikazu, Kojima, Satoshi, Ohkata, Katsuo
    • Journal Title

      J.Chem.Soc., Perkin Trans. 1

      Pages: 179-190

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new digalactosyl diacylglycerol from a cultured marine dinoflagellate Heterocapsa circularisquama2002

    • Author(s)
      Hiraga, Yoshikazu, Kaku, Ken, Omoda, Daisuke, Sugihara, Kinuko, Hosoya, Hiroshi, Hino, Mizuki
    • Journal Title

      J.Nat.Prod. 65

      Pages: 1494-1496

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] Kaku Ken: "Sterol Composition of a Cultured Marine Dinoflagellate, Heterocapsa circularisquama"Natural Product Research. 17・4. 263-267 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Satomi Niwayama: "New Exo/Endo Selectivity Observed in Monohydrolysis of Dialkyl Bicyclo[2.2.1]hept-5-ene-2, 3-Dicarboxylates"Tetrahedron Letters. 44・47. 8567-8570 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshifumi Kanosue: "Relationship between Hydrophobicity of Dipeptides and Mechaelis-Menten Constant Km of Their Enzymatic Hydrolysis"Bulletin of the Chemical Society of Japan. 77(in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshikazu Hiraga: "^1H and ^<13>C NMR Spectroscopic Studies of Half-esters from Monohydrolysis of Dialkyl Bicyclo[2.2.1]hept-5-ene-2, 3-dicarboxylates"Spectroscopy : An International Journal. 18(in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Katsuo Ohkata: "Hydrophobicity and structure of 1,2,4-triazole derivatives bearing 1-carbamoyl and 3-sulfonyl groups"Bull. Chem. Soc. Jpn.. 75. 567-574 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ryukichi Takagi: "Stereochemical considerations of the stereoselective cyclopropanation of 3-aryl-2-phosphonoacrylates induced by the (-)-8-phenylmenthyl group as a chiral auxiliary"J. Chem. Soc., Perkin Trans. 1. 2002. 179-190 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshikazu Hiraga: "A new digalactosyl diacylglycerol from cultured marine dinoflagellate Heterocapsa circularisquama"J. Nat. Prod.. 65. 1494-1496 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ken Kaku: "Sterol composition of a cultured marine dinoflagellate, Heterocapsa circularisquama"Nat. Prod. Lett.. (in press). (2003)

    • Related Report
      2002 Annual Research Report

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

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