Structural Analysis of the Minor Cerebrosides from a Glass Sponge Aulosaccus sp. Issue 12 (16th October 2015)

• Record Type: Journal Article
• Authors: Santalova, Elena A.; Denisenko, Vladimir A.; Dmitrenok, Pavel S.
• Is Part Of: Lipids. Volume 50:Issue 12(2015)
• Page Start: 1209
• Page End: 1218
• Publication Date: 2015-10-16
• Subjects: Glass sponge -- Hexactinellida -- Aulosaccus -- Cerebroside -- Glycosphingolipid -- 2‐Hydroxy fatty acid -- Sphingoid base; Lipids -- Periodicals; Lipids -- Periodicals; Lipiden; Lipides -- Périodiques; 547.77
• DOI: 10.1007/s11745-015-4077-x
• Languages: English
• ISSNs: 0024-4201

Abstract

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 (2 R )‐2‐hydroxy fatty acids, namely, (2 S, 3 S, 4 R, 11 Z )‐2‐aminoeicos‐11‐ene‐1, 3, 4‐triol, acylated with 15 E ‐22:1, 16 Z ‐21:1, 15 Z ‐21:1, 15 Z ‐20:1, 15 E ‐20:1, 19:0, 18:0 acids, (2 S, 3 S, 4 R )‐2‐amino‐13‐methyltetradecane‐1, 3, 4‐triol—with 19 Z ‐26:1, 16 Z ‐23:1, 23:0, 22:0 acids, (2 S, 3 S, 4 R )‐2‐amino‐14‐methylpentadecane‐1, 3, 4‐triol—with 16 Z ‐23:1, 16 E ‐23:1, 15 Z ‐22:1, 22:0 acids, (2 S, 3 S, 4 R )‐2‐amino‐14‐methylhexadecane‐1, 3, 4‐triol, linked to 16 Z ‐23:1, 15 Z ‐22:1 acids, (2 S, 3 S, 4 R )‐2‐amino‐9‐methylhexadecane‐1, 3, 4‐triol—to 16 Z ‐23:1 acid, and (2 S, 3 S, 4 R )‐2‐aminohexadecane‐1, 3, 4‐triol, attached to 15 Z ‐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.