Structural elucidation of the lipopolysaccharide (LPS) of Haemophilus influenzae, strain Rd, a capsule-deficient type d strain, has been achieved by using high-field NMR techniques and electrospray ionization-mass spectrometry (ESI-MS) on delipidated LPS and core oligosaccharide samples. It was found that this organism expresses heterogeneous populations of LPS of which the oligosaccharide (OS) epitopes are subject to phase variation. ESI-MS of O-deacylated LPS revealed a series of related structures differing in the number of hexose residues linked to a conserved inner-core element,, and the degree of phosphorylation. The structures of the major LPS glycoforms containing three (two Glc and one Gal), four (two Glc and two Gal) and five (two Glc, two Gal and one GalNAc) hexoses were substituted by both phosphocholine (PCho) and phosphoethanolamine (PEtn) and were determined in detail. In the major glycoform, Hex3, a lactose unit, b-d-Galp- (134) The fully extended LPS glycoform (Hex5) has the following structure.PPEtnThe structural data provide the first definitive evidence demonstrating the expression of a globotetraose OS epitope, the P antigen, in LPS of H. influenzae. It is noteworthy that the molecular environment in which PCho units are found differs from that observed in an Rd 2 derived mutant strain (RM

The structure of the oligosaccharide part of the Haemophilus influenzue RM.118-28 lipopolysaccharide (LPS) has been investigated. The oligosaccharide was obtained from the LPS by mild acid hydrolysis followed by gel-permeation chromatography, and was studied by methylation analysis, NMR spectroscopy and mass spectrometry. The structure of the major compound, which is a hexasaccharide, is proposed as follows.PIn the structure, Kdo is 3-deoxy-~-manno-octu~osonic acid, PEtn is phosphoethanolamine, PCho is phosphocholine and L,D-Hep is L-glycero-D-munno-heptose. Electrospray-ionization mass spectrometry on 0-deacylated LPS obtained after treatment with anhydrous hydrazine gave evidence for the presence of two minor compounds, which show additional substitution of the main structure with phosphate and PEtn, respectively. These substitutions have not been localized.

The structure of the lipopolysaccharide of Haemophilus influenzae mutant strain, RM.118-26, was investigated. Electrospray ionization-mass spectrometry on intact lipopolysaccharide, O-deacylated lipopolysaccharide and core oligosaccharides obtained from lipopolysaccharide after mild acid hydrolysis provided information on the composition and relative abundance of the glycoforms. Oligosaccharide samples were studied in detail using high-field NMR techniques. The structure of the major glycoform containing phosphocholine is identical to the Hex2 glycoform described for H. influenzae RM. Haemophilus influenzae lipopolysaccharide (LPS) is composed of a membrane-bound lipid A moiety to which the oligosaccharide portion is attached by a single 3-deoxy-d-mannooct-2-ulosonic acid (Kdo) residue. Molecular structural studies of LPS from mutant and wild-type strains of H. influenzae [1±8] have resulted in a structural model consisting of a conserved triheptosyl inner core moiety in which each of the heptose residues can provide a point for elongation by hexosecontaining oligosaccharide chains or for attachment of noncarbohydrate substituents (Structure 1).In type b strains glycose substitution has been found to occur at each of the heptoses. The highest glycoform (

Alkynyldextrans with a DS in the range 0.1–1.67 have been prepared as reactive intermediates for further polymer‐analogous functionalisation. DS and substituent distribution were determined by GLC and GLCMS after hydrolysis and acetylation, or methanolysis and trimethylsilylation. Reactivity was in the order O‐2 > O‐4 ≥ O‐3 with pronounced differences in the distinct patterns for propargyl ethers and its higher homologous. A large deviation from a random substituent distribution was observed. Propargyldextrans were not stable during long‐time storage in the solid state, while terminal pentynyl and hexynyl ethers are. Pentynyldextrans showed structure formation of various geometries. They bound silver efficiently, yielding silver nanoparticles by reduction.magnified image