Structural studies on the specific type VII pneumococcal polysaccharide

The specific type VII pneumococcal polysaccharide was isolated from the crude capsular material by precipitative and chromatographic methods. It contained D-galactose, D-glucose, L-rhamnose, 2-acetamido-2-deoxy-D-glucose, and 2-acetamido-2-deoxy-D-galactose in the molar ratio of 3.5:2.3:3.0:2.1:1.0. Some of its structural features were revealed by methylation studies, time-lapse hydrolysis, periodate oxidation, and enzymic hydrolysis. The polysaccharide is branched at residues of D-galactose and 2-acetamido-2-deoxy-D-galactose. Non-reducing end groups consisted of D-galactopyranose and 2-acetamido-2-deoxy-D-glucopyranose residues, with the former predominating. Major components of the linear chains were (1→3)-linked L-rhamnose and (1→4)-linked D-glucose; the minor ones were (1→2)-linked L-rhamnose, (1→6)-linked D-galactose, and (1→6)-linked 2-acetamido-2-deoxy-D-glucopyranose. The (1→4)-linked D-glucose components may be present as cellobiose residues. The results are in accord with structural features deduced from the serological cross-reactivity of this polysaccharide.     

Structural studies of the capsular polysaccharide of Klebsiella type 33.

The structure of the capsular polysaccharide from Klebsiella type 33 has been investigated. Methylation analysis, various specific degradations, graded hydrolysis with acid, and n.m.r. spectroscopy were the principal methods used. It is concluded that the polysaccharide is composed of pentasaccharide repeating-units having the following structure. (formula, see manual). The D-galactopyranosyl group, with pyruvic acid linked as a ketal to O-3 AND O-4, was degraded on treatment of the fully methylated polysaccharide with strong base. It is proposed that methyl pyruvate is eliminated, in an E2 type of reaction.     

Structural studies of the capsular polysaccharide of Klebsiella type 81.

The structure of the capsular polysaccharide from Klebsiella Type 81 has beeninvestigated. Methlylation analysis, uronic acid degradation, Smith degradation, andgraded acid hydrolysis were the principle methods used. Theanomeric nature of theglycosidic linkages was determined by characterization of fragments obtained from thevarious methods of degradation used. One of the L-rhamnosidic linkages was notpresent in any of these fragments, but is assumed to be an alpha-linkage from consideerationsof optical-rotation data. These studies show that they polysaccharide consits of thefollowing hexasaccharide repeating-unit: yield2)-alpha-L-Rhap-(1yields3)-alpha-L-Rhap-(1-yields4)-beta-D-GlcAP-(1-yields2)-alpha-L-Rhap-(1-yields3)-alpha-L-Rhap-(1-yields3)-beta-D-Galp-(1-yields.     

Structural studies of the capsular polysaccharide of Klebsiella type 59.

The structure of the capsular polysaccharide from Klebsiella type 59 has been investigated by methylation analysis, a modified Smith-degradation procedure, and uronic acid degradation followed by oxidation and elimination of the substituents of the oxidized residue. The oligomeric fragments produced by these degradative procedures were isolated and characterized. O-Acetyl groups were identified and their position determined. The polysaccharide consists of the following pentasaccharide repeating-unit (dotted lines indicate that only some of the residues carry the O-acetyl substituent). See article.     

Structural studies on the hexose region of the lipopolysaccharide from Escherichia coli C

Escherichia coli C is an R-strain, and hence its lipopolysaccharide consists only of lipid A joined to a basal core. Intact core-polysaccharides have been prepared from this strain, and from mutants of the same strain defective in various stages of core biosynthesis. Using sugar and methylation analyses, and chemical and enzymic degradations, the hexose region of the core of the parent strain has been shown to be a pentasaccharide for which the following structure is proposed:

     

Structural studies of the capsular polysaccharide of Klebsiella type 52

The structure of the capsular polysaccharide from Klebsiella Type 52 has been investigated. Methylation analysis, characterization by gas-liquid chromatography-mass spectrometry of oligosaccharide derivatives obtained on partial hydrolysis of the methylated polysaccharide with acid, and specific degradation of the methylated polysaccharide by successive treatments with base and acid followed by characterization of the product, were the principal methods used. The polysaccharide is composed of hexasaccharide repeating-units containing D-glucuronic acid, D-galactose, and L-rhamnose, in the ratios 1:3:2. A structure for these units, disregarding the anomeric natures of the sugar residues, is proposed.     

Structural investigation on the lipopolysaccharide of Escherichia coli rough mutant F653 representing the R3 core type.

The chemical structure of the core oligosaccharide of the lipopolysaccharide isolated from Escherichia coli rough mutant strain F653, representing the enterobacterial R3 core type, was investigated by quantitative and methylation analyses, nuclear magnetic resonance spectroscopy, gas-liquid chromatography/mass spectrometry, and determined as [formula: see text] All sugars are present as alpha-pyranosides but the anomeric configurations of the 3-deoxy-D-manno-octulopyranosonic acid (Kdo) residues could not be determined. The third Kdo and the heptose-linked GlcN residue are present in nonstoichiometric amounts; the GlcN residues may be, at least partially, N-acetylated.     

Structural studies of the core region of Aeromonas salmonicida subsp. salmonicida lipopolysaccharide

The core oligosaccharide structure of the in vivo derived rough phenotype of Aeromonas salmonicida subsp. salmonicida was investigated by a combination of compositional, methylation, CE-MS and one- and two-dimensional NMR analyses and established as the following: [carbohydrate: see text] where R=alpha-D-Galp-(1-->4)-beta-D-GalpNAc-(1--> or alpha-D-Galp-(1--> (approx. ratio 4:3). Comparative CE-MS analysis of A. salmonicida subsp. salmonicida core oligosaccharides from strains A449, 80204-1 and an in vivo rough isolate confirmed that the structure of the core oligosaccharide was conserved among different isolates of A. salmonicida.     

Structural studies on Klebsiella type 61 capsular polysaccharide

The capsular polysaccharide from klebsiella type 61 was found to contain d-galactose, d-glucose, d-mannose, and d-glucuronic acid in the ratios 1:2:1:1. Acid hydrolysis of the polysaccharide gave one aldobiouronic acid, whose structure was established. Methylation analysis of the polysaccharide provided information about the linkages in the polysaccharide. The polysaccharide is composed of a pentasaccharide repeating unit for which structures are proposed.     

Structural studies of the Vibrio cholerae O:3 O-antigen polysaccharide.

The structure of the Vibrio cholerae O:3 O-antigen polysaccharide has been investigated, mainly by n.m.r. spectroscopy, mass spectrometry, sugar and methylation analysis, and specific degradations, and is proposed to involve the following tetrasaccharide repeating-unit. [formula: see text]. In this structure, D-D-Hep is D-glycero-D-manno-heptose, Asc is 3,6-dideoxy-L-arabino-hexose (ascarylose), and Sug is 2,4-diamino-2,4,6-trideoxy-D-glucose (bacillosamine) in which N-2 is acetylated and N-4 is acylated with a 3,5-dihydroxyhexanoic acid. That the 2,4-diamino-2,4,6-trideoxy-D-glucose residue is linked through O-3 and not through one of the hydroxyl groups in the 3,5-dihydroxyhexanoyl group is indicated but not definitely proved. The configuration of the latter group has not been determined. The f.a.b.-mass spectrum of the methylated O-antigen indicates that the structure given above also represents the biological repeating-unit.     

Structural studies of the cell wall polysaccharide of Nocardia asteroides R 399

As with other bacteria belonging to the corynebacteria, mycobacteria, and nocardia group, Nocardia possess in their cell walls a neutral polysaccharide. Structural analysis of the cell wall polysaccharide of Nocardia asteroides R 399 was undertaken. The carbohydrate polymer contained D-arabinose and D-galactose as in mycobacteria. Besides these two carbohydrates we pointed out the occurrence of two additional components: D-glucose and a polyol. This polyol, because of its small amount and its uneasy detection, had been for a long time ignored. It has been proven to be the 6-deoxy-D-altritol or 1-deoxy-D-talitol. The polymer consists of a main strand composed of----5 Araf 1----and----4Galp1----or----5Galf1----; oligoarabinosyl side chains were localized on C3 of an arabinosyl residue. Other shorter ramifications also occur on some galactosyl units. A characterization of the linkage between polysaccharide and peptidoglycan inside the cell wall has also been carried out. The two polymers are joined by a phosphodiester bond which involves 6-deoxyaltritol. As some corynebacteria previously analyzed were also shown to contain mannose (and sometimes glucose), we can conclude that the main skeleton of cell wall polysaccharides of the corynebacteria, mycobacteria, and nocardia group of bacteria is an arabinogalactan; however, individual structural features of the polysaccharide are varying according to the bacterial species. These results might be connected with variations that were observed in immunological analysis.     

Structural studies of the klebsiella type 47 capsular polysaccharide

The structure of the capsular polysaccharide from Klebsiella Type 47 has been investigated. Methylation analysis and characterization of oligosaccharides obtained on acid hydrolysis were the principal methods used. The polysaccharide is composed of tetrasaccharide repeating-units, and a structure for these units is proposed.     

Structural studies of the capsular polysaccharide from Streptococcus pneumoniae type 5

The structure of the capsular polysaccharide (S5) elaborated by Streptococcus pneumoniae type 5 has been investigated by using n.m.r. spectroscopy, methylation analysis, and various specific degradations. It is concluded that the polysaccharide is composed of pentasaccharide repeating-units having the following structure: (Formula: see text) In this structure, L-PneNAc stands for 2-acetamido-2,6-dideoxy-L-talose (pneumosamine) and D-Sug for 2-acetamido-2,6-dideoxy-D-xylo-hexos-4-ulose. The latter sugar accounts for the lability of S5 towards alkali. N.m.r. spectra indicate heterogeneity in S5, most probably associated with the hexosyl-4-ulose residue.     

Structural studies of capsular polysaccharide of type XII Diplococcus pneumoniae

The capsular polysaccharide of Diplococcus pneumoniae Type XII contains residues of d-glucose and d-galactose in a molar ratio of 2:1. The methylated polysaccharide yielded upon hydrolysis 2,3,4,6-tetra- and 3,4,6-tri-O-methyl-d-glucose and 2,3,4,6-tetra-O-methyl-d-galactose as the only neutral methyl sugars. Periodate oxidation of the polysaccharide resulted in destruction of all neutral sugars and immunochemical activity against rabbit antisera. Periodate oxidation of the methyl O-methylglycosides obtained after hydrolysis of the methylated polysaccharide indicated that at least 30% of the l-fucosamine residues are substituted at C-4 in the polysaccharide. It is concluded that the polysaccharide consists of a hexosamine backbone that is substituted by d-galactosyl and kojibiosyl side-chains. The proposed terminal d-galactosyl residues apparently are sterically hindered from interacting with several d-galactose-binding proteins.     

Structural studies on the specific type-14 pneumococcal polysaccharide.

The structure of the Pneumococcus type-14 capsular polysaccharide has been reinvestigated by using methylation analysis, different specific degradations, and n.m.r. spectroscopy. It is concluded that the polysaccharide is composed of tetrasaccharide repeating-units having the structure: (formula: see text).