Abstract
Illexin A, illexin B, and illexin C, isolated from ink of the squidIllex argentinus,have been reported to have a structure consisting of linear repeating units of (-6GalNAcα1-3GlcAβ1-3Fucα1-)n[Biochem. Biophys. Res. Commun.198,560 (1994)]. This structure was further investigated using NOESY and atmospheric pressure MS/MS measurement of PA-trisaccharide obtained by acid hydrolysis of illexin C. The results indicated that the structure is, in fact, branched. Observation of both [GalNAc-Fuc-PA]+and [GlcA-Fuc-PA]−obtained as product ions from the molecular ion of PA-trisaccharide on the MS/MS spectra suggested a branched repeating unit. NOEs between H-1 of GalNAc and H-3 of Fuc, and between H-1 of GlcA and H-4 of Fuc, revealed the positions of glycosidic linkages, and from the results of sodium periodate oxidation of illexin C and PA-trisaccharide, the structure was determined to be {-3GlcAβ1-4(GalNAcα1-3)Fucα1-}n.
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