A naturally occurring deaminated neuraminic acid, 3-deoxy-D-glycero-D-galacto-nonulosonic acid (KDN). Its unique occurrence at the nonreducing ends of oligosialyl chains in polysialoglycoprotein of rainbow trout eggs

Abstract

An unknown deaminated sialic acid has been isolated from Salmo gairdneri (rainbow trout) egg polysialoglycoprotein. A combination of structural methods including gas-liquid chromatography, chemical and enzymatic analyses, mass spectrometry, and 400-MHz 1H NMR spectroscopy was used to determine the structure as 2-keto-3-deoxy-D-glycero-D-galacto-nononic acid (= 3-deoxy-D-glycero-D-galacto-nonulosonic acid; KDN). This structure has been confirmed by comparison with a chemically synthesized authentic sample of KDN. The natural occurrence of deaminated sialic acid in biological material has not been previously reported. A series of KDN-containing oligosialic acids were isolated from the polysialoglycoprotein after pH 4.7-catalyzed hydrolysis. Structural studies including methylation analysis, mass spectrometry, 1H NMR spectroscopy, and chemical reactivity were also used to confirm the structures of the sialyloligosaccharides as KDN alpha 2[8NeuGc alpha 2-]n (n = 1-7). The exclusive location of KDN at the nonreducing termini in polysialoglycoproteins protects oligo(poly)sialyl chains from exosialidases. Terminal capping of these chains may be important in egg activation in salmonid fishes.