Abstract
Novel sulfated and nonsulfated oligosialyglycosphingolipids were isolated from sperm of the sea urchin,Hemicentrotus pulcherrimus, and their structures were established as follows: ±HSO3→Neu5Acα2→(8Neu5Acα2→)n→6G1cβ1→1´Cer, wheren=0, 1, 2, 3. This provides the first evidence for the natural occurrence of a tetrasialic acid structure in glycosphingolipids. The finding of sulfated oligosialyl chains is especially noteworthy in that the sulfate group exclusively resides on the C-8 of the nonreducing terminal residues of oligo/polysialyl chains and that sulfation appears to be a termination signal for elongation of oligosialyl chains. Sulfation at the nonreducing terminal Neu5Ac residues of oligosialyl chains was also found to facilitate the formation of an inter-residue lactone between the carboxyl group at the nonreducing terminal sulfated Neu5Ac and the hydroxyl group at C-9 of the penultimate Neu5Ac residue. The long chain base was 4-hydroxysphinganine (t18:0) and the major fatty acid species were identified as C20:1, C21:1, and C22:1.
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Abbreviations
- C:M:
-
chloroform:methanol
- FAB-MS:
-
fast atom bombardment mass spectrometry
- GLC:
-
gas-liquid chromatography
- GSL:
-
glycosphingolipid
- HPTLC:
-
high performance thin-layer chromatography
- Neu5Ac8HSO3 or HSO3 → Neu5Ac:
-
5-N-acetyl-8-O-sulforylneuraminic acid
- Neu5Gc9HSO3 :
-
5-N-glycolyl-9-O-sulforylneuraminic acid
- NMR:
-
nuclear magnetic resonance
- PB:
-
sodium phosphate buffer, pH 7.2
- Sia:
-
sialic acid
- HSO3 → Sia:
-
sulfated sialic acid
- polySia:
-
polysialic acid
- TFA:
-
trifluoroacetic acid
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Since the dividing line between oligo- and polysialic acids is not rigidly defined, we propose here that those containing more than penta-sialic acid chains can be referred to as the polysialic acid group. The rationale for this is that α2 → 8-linked pentasialic acid is the minimum chain length to exhibit the conformational property of polysialic acid [of Michon, F, Brisson, J-R, Jennings, H (1987)Biochemistry 26: 8399–405] and to act as a substrate for the endosialidase, Endo-N [Hallenbeck, PC, Vimr, ER, Yu, F, Bassler, B, Troy, FA (1987)J Biol Chem 262: 3553–61].
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Ijuin, T., Kitajima, K., Song, Y. et al. Isolation and identification of novel sulfated and nonsulfated oligosialyl glycosphingolipids from sea urchin sperm. Glycoconjugate J 13, 401–413 (1996). https://doi.org/10.1007/BF00731473
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DOI: https://doi.org/10.1007/BF00731473