Stereochemical factors determining the effects of glycosylation on the <sup>13</sup>C chemical shifts in carbohydrates

Shashkov, Alexander S.; Lipkind, Grigory M.; Knirel, Yuriy A.; Kochetkov, Nikolay K.

doi:10.1002/mrc.1260260904

Cited by 357 publications

(133 citation statements)

References 17 publications

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“…if it is substituted by a-Rha the C2 chemical shift is 70 p.p.m and if substituted by b-Rha it is 68 p.p.m. The difference is as expected from previous studies of glycosylation effect [12].…”

Section: Molecular Modellingsupporting

confidence: 88%

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

Molinaro

Castro

Lanzetta

et al. 2002

European Journal of Biochemistry

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Xanthomonas campestris pv. vitians is a Gram-negative plant-associated bacterium that acts as causative agent of bacterial leaf spot and headrot in lettuce. The lipopolysaccharide of this bacterium is suspected to be an important molecule for adhesion to and infection of the plants. The lipopolysaccharide has been isolated from the phenol phase and the O-specific chain characterized by compositional analysis, high field NMR and MALDI-TOF MS. It consists of a nonrepetitive branched polysaccharide with a rhamnan backbone to which Fuc3NAc is linked. The NMR and MS approach led to the characterization of the fine structure of the polymer, which is randomly assembled. The rhamnan backbone is built up of b-Rhap and a-Rhap, this last is present in one, two or three adjacent units and branched by an a-Fucp3NAc unit. This is a real case of a random constituted O-specific chain, therefore biosynthetic studies towards the comprehension of this irregular biosynthesis are needed.

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Section: Molecular Modellingsupporting

confidence: 88%

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

Molinaro

Castro

Lanzetta

et al. 2002

European Journal of Biochemistry

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“…tabaci (36) and were found to be in agreement with the results of NOE linkage analysis. Glycosylation effects for anomeric carbons were calculated and used for the determination of absolute configurations (26,34). The relatively small glycosylation effect for C-1 of residue E (5.0 ppm) indicates different absolute configurations of residues E and D, because for the same absolute configuration of these residues the effect would be 9 ppm.…”

Section: Resultsmentioning

confidence: 99%

Structural studies of the side chain of outer membrane lipopolysaccharide from Pseudomonas syringae pv. coriandricola W-43

et al. 1994

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The lipopolysaccharide (LPS) was isolated from Pseudomonas syringae pv. coriandricola W-43 by hot phenol-water extraction. Rhamnose and 3-N-acetyl-3-deoxyfucose were found to be the major sugar constituents of the LPS together with N-acetylglucosamine, N-acetylgalactosamine, heptose, and 3-deoxy-D-mannooctulosonic acid (Kdo). The main fatty acids of lipid A of the LPS were 3-OH-C:10, C12:0, 2-OH-C12:0, and 3-OH-C12:0. The 0-specific polysaccharide liberated from the LPS by mild-acid hydrolysis was purified by gel permeation chromatography. The compositional analysis of the 0-specific polysaccharide revealed the presence of L-rhamnose and 3-N-acetyl-3-deoxy-D-fucose in a molar ratio of 4:1. The primary structure of the 0-specific polysaccharide was established by methylation analysis together with 1H and 13C nuclear magnetic resonance spectroscopy, including two-dimensional shift-correlated and one-dimensional nuclear Overhauser effect spectroscopy. The polysaccharide moiety was found to consist of a tetrasaccharide rhamnan backbone, and 3-N-acetyl-3-deoxy-D-fucose constitutes the side chain of the branched pentasaccharide repeating unit of the polysaccharide.The phytopathogenic fluorescent pseudomonads are collectively classified as Pseudomonas syringae, which contain more than 40 distinct pathovars (44). These pathovars damage many agriculturally important plants (15) and generally possess a narrow host range (11). The mechanisms for this host specificity are still unclear although various bacterial products such as low-molecular-weight toxins, extracellular polysaccharides, and enzymes have been analyzed.The pseudomonads are gram-negative organisms and contain lipopolysaccharide (LPS), which is a major amphiphilic glycolipid molecule anchored in the outer leaflets of the outer membranes of the bacteria. It has a three-in-one type of architecture, composed of a heteropolysaccharide, the 0-specific chain, which is in turn linked to a central heteropolysaccharide, the core, which is linked to an acylated oligosaccharide of lipidic character, termed lipid A. The O-specific sugar chain seems to be involved in distinct cell recognition processes. Plant-associated bacteria are assumed to recognize their specific hosts, thereby determining the host range spectrum of the phytopathogenic bacteria (different pathovars). It is reported that the LPS of the bacterium may bind with the specific receptor on the host cell and thus may be involved in the recognition phenomenon (12). The extensive studies of bacterial LPS have also provided numerous examples of chemotaxonomic applications of compositional and structural data (28). Strains of P. syringae pathovars are reported to be heterogeneous, and on the basis of the LPS composition they were divided into nine serogroups (31). During the past few years, several structural studies on the O-specific polysaccharide parts of the LPS molecules isolated from P. syringae pathovars have been reported (4,13,(20)(21)(22)(23)(24)(35)(36)(37)(38)(39)(40). The results of these studies wil...

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“…Thus for "y-gauche" interactions between anomeric proton H-1 ' and the equatorial proton at the P position of the aglycon (which could be realized in (I-3)-linked glycosylgalactosides and glycosylmannosides (glycosylrhamnosides)), the glycosylation effects for C-p (C-4 in the first case and C-2 in the second one) could be -3 to -5 ppm (23), i.e., chemical shifts for the above-mentioned atoms are observed at a higher field. At the same time the glycosylation-effect values for linear oligo-and polysaccharides are preserved (24), so their I3C NMR spectra could be calculated according to an additive scheme.…”

Section: Glycosylation Effectsmentioning

confidence: 99%

NMR and conformational study of branched oligosaccharides containing 2,3-disubstituted residues of α-L-rhamnose

Lipkind¹,

Nifant'ev²,

Shashkov³

et al. 1990

Can. J. Chem.

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1238 (1990).'H and 13C NMR spectra have been recorded and the nuclear Overhauser enhancements (in DzO), after pre-irradiation of the anomeric protons, have been measured for tri-and tetrasaccharides containing 2,3-disubstituted residues of a-L-rhamnose and the corresponding disaccharides. The proximity of the conformational states of the disaccharide units in these branched oligosaccharides and in the corresponding disaccharides has been shown, on the basis of both the nOe experimental data and theoretical conformational analysis. This conclusion is also confirmed by data for glycosylation effects in the I3c NMR spectra of the oligosaccharides. - 1238 (1990).On a dCterminC les spectres RMN du 'H et du I3C et on a LvaluC les e o n (dans le DzO, aprks irradiation des protons anomtriques) de tri-et de tCtrasaccharides contenant des rksidues 2,3-disubstituCs du a-L-rhamnose ainsi que des disaccharides correspondants. En se basant sur les donnCes expCrimentales relatives aux e o n ainsi que sur les rCsultats d'une analyse conformationnelle thCorique, on a montrC que les Ctats conformationnels des unites disaccharides de ces oligosaccharides ramifies ressemblent i ceux des disac~harides~corres~ondants. Cette conclusion est confirmCe par les donnCes relatives aux effets de glycosylation sur les spectres RMN de 13c des oligosaccharides.Mots clis : oligosaccharides ramifiCs, spectres RMN du 'H et du I3C, conformations.[Traduit par la revue]

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Stereochemical factors determining the effects of glycosylation on the ¹³C chemical shifts in carbohydrates

Cited by 357 publications

References 17 publications

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

Structural studies of the side chain of outer membrane lipopolysaccharide from Pseudomonas syringae pv. coriandricola W-43

NMR and conformational study of branched oligosaccharides containing 2,3-disubstituted residues of α-L-rhamnose

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Stereochemical factors determining the effects of glycosylation on the 13C chemical shifts in carbohydrates

Cited by 357 publications

References 17 publications

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

NMR and MS evidences for a random assembled O‐specific chain structure in the LPS of the bacterium Xanthomonas campestris pv. Vitians

Structural studies of the side chain of outer membrane lipopolysaccharide from Pseudomonas syringae pv. coriandricola W-43

NMR and conformational study of branched oligosaccharides containing 2,3-disubstituted residues of α-L-rhamnose

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Stereochemical factors determining the effects of glycosylation on the ¹³C chemical shifts in carbohydrates