Negative electrospray, ion trap multistage mass spectrometry of synthetic fragments of the O-PS of Vibrio cholerae O:1.
Saccharides (mono through hexasaccharides) that mimic the terminal epitopes of O-antigens of Vibrio cholerae O:1, serotypes Ogawa and Inaba, were studied by electrospray ion trap (ESI IT) mass spectrometry (MS) in the negative mode. Anionized adducts are the characteristic ions formed by the capture of H(3)O(2)(-) under the condition of ESI MS analysis. The reactive species are produced by reaction of hydroxyl anions with the molecule of water. Thus the [M + H(3)O(2)](-) have the highest m/z value in the ESI IT negative mass spectra. After dissociation of adducts by loss of 2H(2)O the [M-H](-) ions are produced. The fragmentation pathways were confirmed by multistage measurements (MS(n)). The predominant pathway of fragmentation of the mono- and oligomers is the elimination of a molecule of alpha- hydroxy--gammabutyrolactone from the 4-(3-deoxy-L-glycero-tetronamido) group. The other characteristic pathway occurs by shortening the length of oligosaccharides. In this way, conversion of the Ogawa to Inaba fragments takes place under the conditions of measurement. Negative ESI MS/MS provided sufficient information about molecular mass, the number of saccharide residues, basic structure of saccharides, about the tetronamide part of the compounds investigated and allowed Ogawa and Inaba serotypes to be distinguished.
Institute of Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia. chembeke@savba.sk
Slávka
S
Bekesová
Vladimír
V
Kovácik
Josef
J
Chmelík
Pavol
P
Kovác
D000942:Antigens, Bacterial / Q000737:chemistry*; D002240:Carbohydrate Sequence; D008401:Gas Chromatography-Mass Spectrometry; D008969:Molecular Sequence Data; D011134:Polysaccharides / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D014734:Vibrio cholerae / Q000737:chemistry*
D000942:Antigens, Bacterial; D011134:Polysaccharides