Synthesis and NMR spectroscopy of nine stereoisomeric 5,7-diacetamido-3,5,7,9-tetradeoxynon-2-ulosonic acids

Tsvetkov, Yury E.; Shashkov, Alexander S.; Knirel, Yuriy A.; Zähringer, Ulrich

doi:10.1016/s0008-6215(01)00235-x

Cited by 81 publications

(108 citation statements)

References 27 publications

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“…12A). The 1 H and 13 C chemical shifts of the 8-epi-legionaminic acid residue A minor form assigned in this study were in good agreement with those reported previously for the chemically synthesized 8-epi-legionaminic acid (41).…”

Section: Assignment Of 8-epi-legionaminic Acid Residues a And E-supporting

confidence: 91%

“…This large chemical shift perturbation (⌬␦ ϭ ϳ4.5 ppm) likely reflects the differences in the attachment at the 8th carbon. The 21.24 ppm of the C9 carbon of residue A minor form was consistent with having no attachment at the 8th carbon because the chemically synthesized 8-epi-legionaminic acid monosaccharide also has a C9 chemical shift at ϳ20.0 ppm (41).…”

Section: Assignment Of 8-epi-legionaminic Acid Residues a And E-mentioning

confidence: 78%

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O-antigen and Core Carbohydrate of Vibrio fischeri Lipopolysaccharide

Post

Krasity

et al. 2012

Journal of Biological Chemistry

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Background:The structure and function of the Vibrio fischeri O-antigen were unknown. Results: The O-antigen structure was determined using an O-antigen ligase mutant. Conclusion: This mutant had a motility defect, and comparison of its LPS with wild-type LPS showed that the O-antigen contains some unusual sugars. Significance: The O-antigen mutation results in a significantly slower rate of bacterial colonization of the squid light organ.

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Section: Assignment Of 8-epi-legionaminic Acid Residues a And E-supporting

confidence: 91%

Section: Assignment Of 8-epi-legionaminic Acid Residues a And E-mentioning

confidence: 78%

O-antigen and Core Carbohydrate of Vibrio fischeri Lipopolysaccharide

Post

Krasity

et al. 2012

Journal of Biological Chemistry

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“…Upon removal of the CMP group by acid hydrolysis to form III, J 7,8 was determined to be 7.6 Hz (supplemental Fig. S2), in good agreement with the value reported for legionaminic acid (33). To establish the location of the acetamidino group, II was suspended in 95% H 2 O (5% D 2 O), and the pH was lowered through the addition of diluted DCl (pH 3.7) (18).…”

Section: Hilic-ms Purification Of C Coli Vc167 Cmp-activated Metabolsupporting

confidence: 71%

Targeted Metabolomics Analysis of Campylobacter coli VC167 Reveals Legionaminic Acid Derivatives as Novel Flagellar Glycans

McNally

Aubry

Hui

et al. 2007

Journal of Biological Chemistry

104

118

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Glycosylation of Campylobacter flagellin is required for the biogenesis of a functional flagella filament. Recently, we used a targeted metabolomics approach using mass spectrometry and NMR to identify changes in the metabolic profile of wild type and mutants in the flagellar glycosylation locus, characterize novel metabolites, and assign function to genes to define the pseudaminic acid biosynthetic pathway in Campylobacter jejuni 81-176 (McNally, D. J., Hui, J. P., Aubry, A. J., Mui, K. K., Guerry, P., Brisson, J. R., Logan, S. M., and Soo, E. C. (2006) J. Biol. Chem. 281, 18489 -18498). In this study, we use a similar approach to further define the glycome and metabolomic complement of nucleotide-activated sugars in Campylobacter coli VC167. Herein we demonstrate that, in addition to CMP-pseudaminic acid, C. coli VC167 also produces two structurally distinct nucleotide-activated nonulosonate sugars that were observed as negative ions at m/z 637 and m/z 651 (CMP-315 and CMP-329). Hydrophilic interaction liquid chromatography-mass spectrometry yielded suitable amounts of the pure sugar nucleotides for NMR spectroscopy using a cold probe. Structural analysis in conjunction with molecular modeling identified the sugar moieties as acetamidino and N-methylacetimidoyl derivatives of legionaminic acid (Leg5Am7Ac and Leg5AmNMe7Ac). Targeted metabolomic analyses of isogenic mutants established a role for the ptmA-F genes and defined two new ptm genes in this locus as legionaminic acid biosynthetic enzymes. This is the first report of legionaminic acid in Campylobacter sp. and the first report of legionaminic acid derivatives as modifications on a protein.Campylobacter sp. are among the most frequent cause of bacterial diarrhea worldwide and the leading cause of foodborne illness in North America (1, 2). Motility is critical to intestinal colonization by Campylobacter and is required for invasion of epithelial cells in vitro. Campylobacter flagella also function as secretory organelles in the absence of specialized type III secretion systems in this pathogen (3, 4). As such, flagella are recognized as a major virulence factor for Campylobacter sp. (5). The flagellar filament structural protein, FlaA, is the immunodominant protein recognized during infection and has been shown to be an immunoprotective antigen (6 -9). Flagellins from numerous strains of Campylobacter jejuni and the related organism Campylobacter coli have been shown to be among the most heavily glycosylated prokaryotic proteins described (10 -12), and the glycosyl modifications appear to be surface-exposed in the assembled filament and highly immunogenic (13,14). In addition, it appears that unique forms of these glycosyl modifications contribute to the serospecificity of the flagellar filament (11) and the glycans are responsible for autoagglutination and microcolony formation (15).All genes known to be involved in glycosylation of Campylobacter flagellins map near the flaA and flaB structural genes in a region that is one of the most hypervariable in th...

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“…Therefore, the axial hydroxy group at C-4 was converted into the methane-6 and the p-toluenesulphonate 7 6 and 7, respectively; the corresponding trifluoromethanesulphonate was also prepared 8 , but proved to be too unstable in the following reactions using lithium dimethylamide or sodium azide in DMF at 0 °C, respectively. Under the latter conditions however, 6 and 7 could easily be transformed into the corresponding azide 8.…”

Section: Resultsmentioning

confidence: 99%