The occurrence of internal (1,5)-linked arabinofuranose and arabinopyranose residues in arabinogalactan side chains from soybean pectic substances

CDTA-extractable soybean pectic substances were subjected to enzymatic digestion with arabinogalactan degrading enzymes yielding a resistant polymeric pectic backbone and arabino-, galacto-, and arabinogalacto-oligomers. The complex digest was fractionated using size-exclusion chromatography. Monosaccharide composition analysis, HPAEC fractionation and MALDI-TOF MS analysis of the resulting fractions showed that each contained a mixture of oligosaccharides of essentially the same degree of polymerisation, composed of only arabinose and galactose. MALDI-TOF MS analysis was used for molecular mass screening of oligosaccharides in underivatised HPAEC fractions. The monosaccharide sequence and the branching pattern of oligosaccharides (degree of polymerisation from 4 to 8) were determined using linkage analysis and ES-CID tandem MS analysis of the per-O-methylated oligosaccharides in each of the HPAEC fractions. These analyses indicated the presence of common linear (1¿4)-linked galacto-oligosaccharides, and both linear and branched arabino-oligosaccharides. In addition, the results unambiguously showed the presence of oligosaccharides containing (1¿4)-linked galactose residues bearing an arabinopyranose residue as the non-reducing terminal residue, and a mixture of linear oligosaccharides constructed of (1¿4)-linked galactose residues interspersed with an internal (1¿5)-linked arabinofuranose residue. The consequences of these two new structural features of pectic arabinogalactan side chains are discusse

Loss of internal 1 → 6 substituted monosaccharide residues from underivatized and per-O-methylated trisaccharides

The fragmentation behavior of [M + H]+ ions of a series of underivatized and per-O-methylated trisaccharides having 1 → 6 linked residues, of which one or two is a deoxy-fluoro or deoxy residue and thus has a unique mass, has been studied by using collision-induced dissociation fast-atom bombardment mass spectrometry. In addition to the usual fragment ions resulting from glycosidic bond cleavage, fragment ions were observed which must have been generated following an unusual rearrangement process which can be rationalized in terms of the loss of an internal monosaccharide residue

Studies of polysaccharides from three edible species of Nostoc (cyanobacteria) with different colony morphologies : structural characterization and effect on the complement system of polysaccharides from Nostoc commune

The cyanobacterium Nostoc commune Vaucher produces quite complex extracellular polysaccharides. The cyanobacterium is nitrogen fixing, and on growing the cyanobacterium in media with and without nitrogen, different types of extracellular polysaccharides were obtained. These were also different from the polysaccharides present in N. commune collected in the field. High pH anion exchange chromatography (HPAEC) of weak acid hydrolysates of the culture-grown material demonstrated that, in this case, HPAEC was useful for comparison of the different polymers. The main differences between the polymers from the field group and the culture-grown samples were the presence of substantial amounts of arabinose, 2-O-methylglucose, and glucuronic acid in the latter. Methylation studies also revealed a difference in the branching points on the glucose units between the field and cultured samples, being 1,4,6 for the first and 1,3,6 for the latter. The field acidic fraction gave, on weak acid hydrolysis and separation on BioGel P2 and HPAEC, 12 oligosaccharide fractions that were isolated and studied by different mass spectroscopy techniques. The structures of the oligosaccharides were determined, and two different series that can originate from two repeating pentamers were identified: GlcA1-4/6GlcM1-4Gal1-4Glc1-4Xyl and GlcA1-4/6Glc1-4Gal1-4Glc1-4Xyl. The difference between these oligosaccharides lies in the methyl substituent on carbon 2 of the glucose unit next to the nonreducing glucuronic acid unit. The polysaccharides from field material were shown to have a strong effect on the complement system

α-D-Glcp-(1↔1)-β-D-Galp-containing oligosaccharides, novel products from lactose by the action of β-galactosidase

A mixture of oligosaccharides produced by beta-galactosidase using lactose as a substrate was fractionated according to degree of polymerization using gel filtration, followed by high-pH anion-exchange chromatography. The fractions obtained were analyzed using monosaccharide analysis, methylation analysis, mass spectrometry, and NMR spectroscopy. Twelve novel non-reducing oligosaccharides were characterized, namely, [beta-D-Galp-(1->4)]n-alpha-D-Glcp-(11)-beta-D-Galp[-(42)-alpha-D-Glcp-(11)-beta-D-Galp