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A new cytotoxic fatty acid (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid and the sterols from the far Eastern sponge Geodinella robusta

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Lipids

Abstract

A new fatty acid, (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid (1a), and a rare fatty acid, (5Z,9Z)-23-methyl-5,9-tetracosadienoic acid (2a), the predominant constituents of the free fatty acid fraction from the lipids of the sponge Geodinella robusta, were isolated and partly separated by reversed phase high-performance liquid chromatography, followed by multifold crystallization from MeOH to give 1a and 2a in 70% and 60% purity, respectively. These fatty acids were identified as (5Z,9Z)-22-and (5Z,9Z)-23-methyl-5,9-tetracosadienoic acids by nuclear magnetic resonance techniques, including distortionless enhancement by polarization transfer, heteronuclear multiple quantum connectivity, and correlation spectroscopy experiments, as well as from mass-spectrometric data for their methyl esters, the methyl esters of their perhydro derivatives, and their pyrrolidides. Mixtures of 1a and 2a showed cytotoxic activity against mouse Ehrlich carcinoma cells and a hemolytic effect on mouse erythrocytes. The sterol fraction from the same sponge was analyzed by gas liquid chromatography mass spectrometry, and 24-methylenecholesterol was identified as a main constituent of this fraction. The implications of the co-occurrence of membranolytic long-chain fatty acids and 24-methylenecholesterol as a main membrane sterol are discussed in terms of the phenomenon of biochemical coordination.

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Abbreviations

GOSY:

correlation spectroscopy

ECL:

equivalent chain length

EI-MS:

electron impact mass spectrometry

GLC:

gas-liquid chromatography

GLC-MS:

gas-liquid chromatography coupled with mass spectrometry

HPLC:

high-performance liquid chromatography

NMR:

nuclear magnetic resonance

TLC:

thin-layer chromatography

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Authors and Affiliations

  1. Laboratory of the Marine Natural Products, Pacific Institute of Bioorganic Chemistry of the Russian Academy of Sciences, Pr. 100-letya Vladivostoka 159, 690022, Vladivostok, Russian Federation

    Tatyana N. Makarieva, Irina A. Gorshkova, Andrei S. Dmitrenok, Vladimir I. Gorbach & Valentin A. Stonik

  2. Bioorganic Chemistry and Biotechnology Department, Institute of Chemistry and Applied Ecology, Far-Eastern State University, 690600, Vladivostok, Russian Federation

    Elena A. Santalova & Alla G. Guzii

  3. Institute of Marine Biology of the Russian Academy of Sciences, 690022, Vladivostok, Russian Federation

    Vassilii I. Svetashev

Authors
  1. Tatyana N. Makarieva
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  2. Elena A. Santalova
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  3. Irina A. Gorshkova
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  4. Andrei S. Dmitrenok
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  5. Alla G. Guzii
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  6. Vladimir I. Gorbach
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  7. Vassilii I. Svetashev
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  8. Valentin A. Stonik
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Correspondence to Valentin A. Stonik.

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Makarieva, T.N., Santalova, E.A., Gorshkova, I.A. et al. A new cytotoxic fatty acid (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid and the sterols from the far Eastern sponge Geodinella robusta . Lipids 37, 75–80 (2002). https://doi.org/10.1007/s11745-002-0866-6

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  • DOI: https://doi.org/10.1007/s11745-002-0866-6

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