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Chemical Synthesis and Gas Chromatographic Behaviour of γ-Stearidonic (18:4n-6) Acid

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Journal of the American Oil Chemists' Society

Abstract

γ-Stearidonic acid, 18:4n-6, a potential product of β-oxidation of arachidonic acid (20:4n-6), was only recently positively identified in a living organism—a thermophilic cyanobacterium Tolypothrix sp., albeit at low levels, whilst some indirect evidence suggests its wider presence, e.g. in a unicellular marine alga. We have prepared 18:4n-6 using an iodolactonisation chain-shortening approach from 22:5n-6 and obtained its 1H-, 13C-, COSY- and HSQC NMR spectra, with 18:5n-3 spectra also recorded for a comparison. The GC and GC-MS behaviour of its methyl ester was also studied. Like another Δ3 polyunsaturated acid, octadecapentaenoic (18:5n-3), 18:4n-6 rapidly yields 2-trans isomer upon formation of dimethyloxazoline derivative. On a polar ionic liquid phase (SLB-IL100, 200 °C) the methyl ester could be mistaken for 18:3n-3, while on methylsilicone phase (BP1, 210 °C) it eluted ahead of 18:3n-6 and 18:4n-3, suggesting that when present it may be easily misidentified during GC analysis of fatty acids.

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Notes

  1. Previous affiliation of MV: Laboratory of Comparative Biochemistry, Institute of Marine Biology, Vladivostok, Russia.

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Acknowledgments

Authors are grateful to Dr Kevin Mitchell for help with HPLC, Dr Yinrong Lu for QToF MS support, Dr. Herbert Wong for NMR-spectra recording, Alison Speakman for invaluable help with information retrieval and Dr Michael Steward for editing the manuscript (all—Callaghan Innovation, New Zealand) and to anonymous reviewers for their help in improving the manuscript. Dr. Roderick Weston (Industrial Research Limited, New Zealand) participated in the project during the initial stage of the work. Pig testes were a gift from Taranaki Abattoir Co., North Island, New Zealand. DME extract of pig testes was prepared by Dr Peter Dyer (Callaghan Innovation, New Zealand). This work was supported by the New Zealand Foundation for Research, Science and Technology grant C08X0709 "High value lipids" and by the Callaghan Innovation SIF project “Novel bioactives”.

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Authors and Affiliations

  1. Callaghan Innovation, 69 Gracefield Road, P.O. Box 31310, Lower Hutt, 5040, New Zealand

    Mikhail Vyssotski, Kirill Lagutin & Andrew MacKenzie

  2. Laboratory of Bioanalytical Chemistry, Faculty of Fisheries Sciences, Hokkaido University, Hakodate, 041-8611, Japan

    Yutaka Itabashi

Authors
  1. Mikhail Vyssotski
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  2. Kirill Lagutin
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  3. Andrew MacKenzie
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  4. Yutaka Itabashi
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Correspondence to Mikhail Vyssotski.

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Vyssotski, M., Lagutin, K., MacKenzie, A. et al. Chemical Synthesis and Gas Chromatographic Behaviour of γ-Stearidonic (18:4n-6) Acid. J Am Oil Chem Soc 92, 383–391 (2015). https://doi.org/10.1007/s11746-014-2588-x

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  • DOI: https://doi.org/10.1007/s11746-014-2588-x

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