The Preferred Conformation of Oligosaccharides Derived from the Complex‐Type Carbohydrate Portions of Glycoproteins

Bock, Klaus; Arnarp, Jan; Lōnngren, Jörgen

doi:10.1111/j.1432-1033.1982.tb07036.x

Cited by 95 publications

(33 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Through the acquisition of a 1 H-13 C HMBC spectrum, we were able to elucidate the interglycosidic linkage pattern, and we also confirmed that the glycan is O linked to the pilin peptide fragments via C1 of ␣Araf. In support of our structural characterization of the glycan, the 13 C chemical shift assignments for the ␣Araf units closely match values that have been previously reported for this monosaccharide (5).…”

Section: Pa5196 Pilins Are Modified With a Novel Glycan That Is Not Tsupporting

confidence: 71%

Glycosylation of Pseudomonas aeruginosa Strain Pa5196 Type IV Pilins with Mycobacterium-Like α-1,5-Linked d -Ara f Oligosaccharides

et al. 2007

View full text Add to dashboard Cite

Pseudomonas aeruginosa is a gram-negative bacterium that uses polar type IV pili for adherence to various materials and for rapid colonization of surfaces via twitching motility. Within the P. aeruginosa species, five distinct alleles encoding variants of the structural subunit PilA varying in amino acid sequence, length, and presence of posttranslational modifications have been identified. In this work, a combination of mass spectrometry and nuclear magnetic resonance spectroscopy was used to identify a novel glycan modification on the pilins of the group IV strain Pa5196. Group IV pilins continued to be modified in a lipopolysaccharide (wbpM) mutant of Pa5196, showing that, unlike group I strains, the pilins of group IV are not modified with the O-antigen unit of the background strain. Instead, the pilin glycan was determined to be an unusual homo-oligomer of ␣-1,5-linked D-arabinofuranose (D-Araf). This sugar is uncommon in prokaryotes, occurring mainly in the cell wall arabinogalactan and lipoarabinomannan (LAM) polymers of mycobacteria, including Mycobacterium tuberculosis and Mycobacterium leprae. Antibodies raised against M. tuberculosis LAM specifically identified the glycosylated pilins from Pa5196, confirming that the glycan is antigenically, as well as chemically, identical to those of Mycobacterium. P. aeruginosa Pa5196, a rapidly growing strain of low virulence that expresses large amounts of glycosylated type IV pilins on its surface, represents a genetically tractable model system for elucidation of alternate pathways for biosynthesis of D-Araf and its polymerization into mycobacterium-like ␣-1,5-linked oligosaccharides.Pseudomonas aeruginosa is a gram-negative opportunistic pathogen that can infect immunocompromised, burned, and cystic fibrosis patients (12, 14, 40, 45) but does not typically cause disease in healthy individuals. Among the factors used by P. aeruginosa to colonize both living and nonliving surfaces are its polar type IV pili (T4P). T4P are long, thin, flexible, proteinaceous surface appendages required for adherence to a variety of materials and for twitching motility, a unique form of surface translocation (7,23,28,41,45,48,52,59). The T4P of P. aeruginosa are composed of monomeric subunits (pilins) encoded by pilA (66) and belong to the NMePhe class of pilins (44,48,65). T4P are expressed by many bacteria including Neisseria spp

show abstract

Section: Pa5196 Pilins Are Modified With a Novel Glycan That Is Not Tsupporting

confidence: 71%

Glycosylation of Pseudomonas aeruginosa Strain Pa5196 Type IV Pilins with Mycobacterium-Like α-1,5-Linked d -Ara f Oligosaccharides

et al. 2007

View full text Add to dashboard Cite

show abstract

“…These minima are also consistent with previous calculations for this linkage that did not implicitly consider flexibility (26)(27)(28)(29). In two crystal structures of small molecules with this linkage this conformation is indeed found (20,30).…”

Section: Coi$ornzational Analysissupporting

confidence: 80%

Syntheses of model oligosaccharides of biological significance. XII. Synthesis, NMR, and conformational analysis of trideuteriomethyl 4-O-(β-D-mannopyranosyl)- 2-acetamido-2-deoxy-β-D-glucopyranoside: the use of DEPT ¹H to ¹³C transfer for T₁ measurements and NOE assignments of tightly coupled ¹H nuclei

Lee¹,

Congson²,

Whitfield³

et al. 1992

Can. J. Chem.

View full text Add to dashboard Cite

Ho HUAT LEE, LIGAYA N. CONGSON, DENNIS M. WHITFIELD, LAJOS R. RADICS, and JIRI J. KREPINSKY. Can. J. Chenl. 70, 2607 (1992).The title disaccharide Manp(p1-4)GlcpNAcpl-OCD, has been prepared by a short synthetic sequence through the inversion of configuration from gluco to marzrzo involving benzyl Glcp(p1-4)GlcpNAc. The disaccharide was subjected to detailed high-field 'H and I3c NMR study. First, conventional and 2D spectra were run to afford a co~nplete set of assigned spectral parameters. Next, steady-state 'H-{'H} NOE and 'H, ',c spin lattice relaxation experiments were performed to infer dynamic spectral data related to ~nolecular conformation. Owing to tight couplings and signal overlaps in the 'H spectrum, proton relaxation and selected NOE data were obtained via "C NMR after transfer of the actual, non-equilibrium, proton magnetization to the "C frequency domain. Using this experimental approach it has been found that T,'s for Manp H-4 and GlcpNAc H-2 were substantially longer than those of the other sugar ring protons, and that the principal interresidue dipolar contact in Manp(p 1 -4)GlcpNAcp 1 -OCD3 takes place between Manp H-l and

show abstract

“…They demonstrated that these glycopeptides show certain distinct conformational features and that they are not completely flexible random coils. In a similar study of synthetic oligosaccharides of the type found in complex asparagine-linked glycopeptides, Bock et al 4 proposed that these branched oligosaccharides take on a rather extended conformation that contrasts with the partially folded conformations found for some of the high mannose chains. Bush et al 5 have used vacuum-uv CD to study a series of complex glycopeptidies, reaching conclusions that were consistent with those of Bock et al 4 Although glycopeptides of the O-linked or mucin type have been less intensively studied, Lemieux et al'j and Lemieux and Bock7 have used conformational energy calculations and NOE results to propose models for synthetic trisaccharide nonreducing terminal fragments of the blood group H-active oligosaccharides.…”

Section: Introductionmentioning

confidence: 96%

Conformations of blood group H‐active oligosacharides of ovarian cyst mucins

Bush

1985

Biopolymers

View full text Add to dashboard Cite

SynopsisSpectroscopic data and conformational energy calculations are reported for eight oligosaccharides from ovarian cyst mucins and from human milk, the nonreducing terminals of which have fucose (a1 -2)galactose linked either (Pl-3) (type I) or (pl-4)(type 11) to Nacetylglucosamine or in ( D l -3 ) linkage to galactosaminitol. The fully assigned proton nmr spectra are reported along with nuclear Overhauser enhancement (NOE) data. Amide proton coupling constants and vacuum-uv CD spectra provide information on the amide plane orientation and amide environment. Our results imply that the fucosidic dihedral angles are similar for all three cases and that the substantial differences in the chemical shifts of the fucosyl protons of type I, type 11, and 3-01 chains result from different perturbations by the amide group of the residue to which the P-galactose is linked. Stereopair diagrams of conformational models for both type I and I1 H chains are presented that are consistent with NOE, coupling constants, conformational energy calculations, and the CD data. While the temperature dependence of the observed NOE of penta-and hexasaccharides indicates that their rotational correlation times are strongly temperature dependent, we conclude that the conformations are essentially independent of temperature.

show abstract

The Preferred Conformation of Oligosaccharides Derived from the Complex‐Type Carbohydrate Portions of Glycoproteins

Cited by 95 publications

References 24 publications

Glycosylation of Pseudomonas aeruginosa Strain Pa5196 Type IV Pilins with Mycobacterium-Like α-1,5-Linked d -Ara f Oligosaccharides

Glycosylation of Pseudomonas aeruginosa Strain Pa5196 Type IV Pilins with Mycobacterium-Like α-1,5-Linked d -Ara f Oligosaccharides

Conformations of blood group H‐active oligosacharides of ovarian cyst mucins

Contact Info

Product

Resources

About