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Structural Analysis of the Minor Cerebrosides from a Glass Sponge Aulosaccus sp.

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Lipids

Abstract

The minor cerebrosides from a Far-Eastern glass sponge Aulosaccus sp. were analyzed as constituents of some multi-component RP-HPLC fractions. The structures of eighteen new and one known cerebrosides were elucidated on the basis of NMR spectroscopy, mass spectrometry, optical rotation data and chemical transformations. These β-D-glucopyranosyl-(1→1)-ceramides contain sphingoid bases N-acylated with straight-chain (2R)-2-hydroxy fatty acids, namely, (2S,3S,4R,11Z)-2-aminoeicos-11-ene-1,3,4-triol, acylated with 15E-22:1, 16Z-21:1, 15Z-21:1, 15Z-20:1, 15E-20:1, 19:0, 18:0 acids, (2S,3S,4R)-2-amino-13-methyltetradecane-1,3,4-triol—with 19Z-26:1, 16Z-23:1, 23:0, 22:0 acids, (2S,3S,4R)-2-amino-14-methylpentadecane-1,3,4-triol—with 16Z-23:1, 16E-23:1, 15Z-22:1, 22:0 acids, (2S,3S,4R)-2-amino-14-methylhexadecane-1,3,4-triol, linked to 16Z-23:1, 15Z-22:1 acids, (2S,3S,4R)-2-amino-9-methylhexadecane-1,3,4-triol—to 16Z-23:1 acid, and (2S,3S,4R)-2-aminohexadecane-1,3,4-triol, attached to 15Z-22:1 acid. The 13-methyl and 9-methyl-branched trihydroxy sphingoid base backbones (C15 and C17, respectively) have not been found previously in sphingolipids. The ceramide parts, containing other backbones, present new variants of N-acylation of the marine sphingoid bases with the 2-hydroxy fatty acids. The combination of the instrumental and chemical methods used in this study improved the efficiency of the structural analysis of such complex cerebroside mixtures that gave more detailed information on glycosphingolipid metabolism of the organism.

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Abbreviations

FA:

Fatty acid(s)

RP-HPLC:

High-performance liquid chromatography in the reversed-phase mode

DMDS:

Dimethyl disulfide

RT:

Retention time

ESM:

Electronic Supplementary Material

11Z-t20:1:

(2S,3S,4R,11Z)-2-Aminoeicos-11-ene-1,3,4-triol

13-methyl-t14:0:

(2S,3S,4R)-2-Amino-13-methyltetradecane-1,3,4-triol

14-methyl-t15:0:

(2S,3S,4R)-2-Amino-14-methylpentadecane-1,3,4-triol

14-methyl-t16:0:

(2S,3S,4R)-2-Amino-14-methylhexadecane-1,3,4-triol

9-methyl-t16:0:

(2S,3S,4R)-2-Amino-9-methylhexadecane-1,3,4-triol

t16:0:

(2S,3S,4R)-2-Aminohexadecane-1,3,4-triol

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Acknowledgments

This study was financially supported by a Grant of the President of the Russian Federation (Program for State Support of Leading Scientific Schools, Grant NSh-148.2014.4). The authors express their gratitude to Drs O.P. Moiseenko, L.P. Ponomarenko for their kind help in GC and GC–MS analyses and Prof. V.A. Stonik for reading the manuscript and discussion.

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Authors and Affiliations

  1. G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Pr. 100 let Vladivostoku, 159, Vladivostok, 690022, Russia

    Elena A. Santalova, Vladimir A. Denisenko & Pavel S. Dmitrenok

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  1. Elena A. Santalova
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  2. Vladimir A. Denisenko
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  3. Pavel S. Dmitrenok
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Correspondence to Elena A. Santalova.

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The sphingoid bases are abbreviated in accordance with an accepted short-hand nomenclature.

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Santalova, E.A., Denisenko, V.A. & Dmitrenok, P.S. Structural Analysis of the Minor Cerebrosides from a Glass Sponge Aulosaccus sp.. Lipids 50, 1209–1218 (2015). https://doi.org/10.1007/s11745-015-4077-x

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