THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: IV. GALACTOMANNANS I FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII

1965 ◽  
Vol 43 (1) ◽  
pp. 30-39 ◽  
Author(s):  
C. T. Bishop ◽  
M. B. Perry ◽  
F. Blank ◽  
F. P. Cooper
Keyword(s):  
Aqueous Solutions ◽  
Copper Complexes ◽  
Trichophyton Rubrum ◽  
Periodate Oxidation ◽  
Structural Features ◽  
Water Soluble ◽  
Major Constituent ◽  
Branch Points ◽  
Terminal Units ◽  
Hydrolysis Of

A group of polysaccharides, called galactomannans I, were precipitated as their insoluble copper complexes from aqueous solutions of the crude polysaccharides obtained from each of the organisms designated in the title. The five galactomannans I were homogeneous under conditions of electrophoresis and ultracentrifugation and had high positive specific rotations. The major constituent monosaccharide was D-mannose; amounts of D-galactose ranged from nil for the polysaccharide from T. rubrum to 13% for that from T. schönleinii. Methylation and hydrolysis of the five galactomannans I yielded varying amounts of the following: 2,3,5,6-tetra-O-methyl-D-galactose (not present in the products from T. rubrum), 2,3,4,6-tetra-O-methyl-D-mannose, 2,3,4-tri-O-methyl-D-mannose, 2,4,6-tri-O-methyl-D-mannose, 3,4-di-O-methyl-D-mannose, and 3,5-di-O-methyl-D-mannose. Periodate oxidation results agreed with the methylation studies. The gross structural features of each galactomannan I appear to be the same, namely, a basic chain of 1 → 6 linked α-D-mannopyranose units for approximately every 22 of which there is a 1 → 3 linked α-D-mannopyranose residue. Branch points occur along the 1 → 6 linked chain at the C2 positions of the D-mannopyranose units and once in every 45 units at the C2 position of a 1 → 6 linked D-mannofuranose residue. The D-galactose in the polysaccharides is present exclusively as non-reducing terminal furanose units; non-reducing terminal units of D-mannopyranose are also present. The variations in the identities and relative amounts of the non-reducing terminal units were the only apparent differences in the gross structural features within this group of polysaccharides.

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: V. GALACTOMANNANS II FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII

1966 ◽  
Vol 44 (19) ◽  
pp. 2291-2297 ◽  
Author(s):  
C. T. Bishop ◽  
M. B. Perry ◽  
F. Blank
Keyword(s):  
Trichophyton Rubrum ◽  
Structural Difference ◽  
Structural Features ◽  
Water Soluble ◽  
Branch Points ◽  
Trichophyton Interdigitale ◽  
Hydrolysis Of

Polysaccharides obtained from each of the organisms designated in the title have been resolved into three groups: galactomannans I, galactomannans II, and glucans. The five galactomannans II were homogeneous under conditions of electrophoresis, and had positive specific rotations. Methylation and hydrolysis of the five galactomannans II yielded varying amounts of the following: 2,3,5,6-tetra-O-methyl-D-galactose, 2,3,4,6-tetra-O-methyl-D-mannose, 2,3,4-tri-O-methyl-D-mannose, 3,4,6-tri-O-methyl-D-mannose, 3,5-di-O-methyl-D-mannose, and 3,4-di-O-methyl-D-mannose. The galactomannans II were therefore very similar to each other in their gross structural features. The unbranched portions of the polysaccharides were formed by 1 → 2 and 1 → 6 linked α-D-mannopyranose units, with the former predominating. Branch points were formed through substitutions at the C-2 and C-6 positions of D-mannofuranose and D-mannopyranose, and branches were terminated by D-galactofuranose and D-mannopyranose units. The presence of 1 → 2 linked α-D-mannopyranose units in the linear portions of the galactomannans II constitutes a major structural difference between this group of polysaccharides and the galactomannans I. The two groups of galactomannans differ serologically.

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: II. A GLUCAN FROM MICROSPORUM QUINCKEANUM

1963 ◽  
Vol 41 (10) ◽  
pp. 2621-2627 ◽  
Author(s):  
H. Alfes ◽  
C. T. Bishop ◽  
F. Blank
Keyword(s):  
Saccharomyces Cerevisiae ◽  
Candida Albicans ◽  
Minimum Degree ◽  
Relative Number ◽  
Degree Of Polymerization ◽  
Water Soluble ◽  
Molar Ratio ◽  
Branch Points ◽  
Degree Of Branching ◽  
Hydrolysis Of

A levorotatory glucan with a minimum degree of polymerization of 36 has been isolated from the water-soluble polysaccharides of the dermatophyte Microsporum quinckeanum. Hydrolysis of the methylated glucan yielded the following O-methyl-D-glucoses: 2,3,4,6-tetra-(10.2 mole%); 2,3,4-tri- (57.7 mole%); 2,4,6-tri- (22.2 mole%); 2,4-di- (8.2 mole%); and 2-mono- (1.6 mole%). The glucan consumed 1.53 moles of periodate with production of 0.70 mole of formic acid per mole anhydroglucose. Reduction and hydrolysis of the periodate-oxidized glucan yielded glycerol, erythritol, and D-glucose in a molar ratio of 72.3:0.6:27.1. The results showed that the glucan consisted of β-D-glucopyranose units joined in straight chains by 1 → 6 (57%) and 1 → 3 (24%) linkages. Approximately 3 in every 37 glucose residues constitute branch points in the glucan with branches occurring at the C6 and C3 positions of the same glucose unit. The glucan bears some resemblance to the yeast glucans of Saccharomyces cerevisiae and Candida albicans but differs from them in the relative number of 1 → 6 and 1 → 3 linkages and in the degree of branching.

CONSTITUTION OF A WATER SOLUBLE HEMICELLULOSE FROM AMERICAN BEECHWOOD (FAGUS GRANDIFOLIA)

1957 ◽  
Vol 35 (6) ◽  
pp. 556-564 ◽  
Author(s):  
G. A. Adams
Keyword(s):  
Average Molecular Weight ◽  
Periodate Oxidation ◽  
Reducing Power ◽  
Fagus Grandifolia ◽  
Water Soluble ◽  
Hot Water ◽  
Molar Ratio ◽  
Weight Average Molecular Weight ◽  
Homogeneous Fraction ◽  
Hydrolysis Of

Extraction of beechwood chlorite holocellulose with hot water yielded a hemicellulose in 13.4% yield (based on original extractive-free wood) containing D-xylose 72%, D-galactose 11.0%, and uronic acid 13.2%. Purification of the crude hemicellulose by complexing with Fehling's solution yielded a chemically homogeneous fraction containing D-xylose 83% and 4-O-methyl-D-glucuronic acid 15.5%. Hydrolysis of the fully methylated hemicellulose yielded 2,3,4-tri-O-methyl-D-xylose, 2,3-di-O-methyl-D-xylose, 3-O-methyl-D-xylose, and 3-O-methyl-2-O-(2,3,4-tri-O-methyl-D-glucopyranosyluronic acid)-D-xylose in a molar ratio of 2:35:3:5. On the basis of the methylation data, periodate oxidation, reducing power determinations, and weight average molecular weight values a possible structure for the hemicellulose is proposed.

CHARACTERIZATION OF THREE HEMICELLULOSES FROM THE WOOD OF AMABILIS FIR (ABIES AMABILIS)

1963 ◽  
Vol 41 (6) ◽  
pp. 1381-1388 ◽  
Author(s):  
E. C. A. Schwarz ◽  
T. E. Timell
Keyword(s):  
Periodate Oxidation ◽  
Specific Rotation ◽  
Water Soluble ◽  
Partial Hydrolysis ◽  
Abies Amabilis ◽  
A Value ◽  
Linear Framework ◽  
Molecular Rotations ◽  
Hydrolysis Of

An arabino-4-O-methylglucuronoxylan (10:14:76), a water-soluble galactoglucomannan (1:1:3), and an alkali-soluble galactoglucomannan (0.1:1:3) have been isolated in yields of 7, 4, and 8% from the wood of amabilis fir (Abies amabilis). The structure of the polysaccharides was established by methylation and periodate oxidation techniques. The xylan ([Formula: see text]) contained side chains of (1 → 2)-linked 4-O-methyl-α-D-glucuronic acid and (1 → 3)-linked α-L-arabinofuranose residues, both attached directly to a linear framework of (1 → 4)-linked β-D-xylose residues. The galactoglucomannans ([Formula: see text] 76 and 95) contained (1 → 6)-linked α-D-galactopyranosyl residues attached directly to a backbone of (1 → 4)-linked β-D-mannose and β-D-glucose residues. Partial hydrolysis of the two hexosans yielded 10 and 13 oligosaccharides, respectively, containing (1 → 4)-β-D-mannose, (1 → 4)-β-D-glucose, and (1 → 6)-α-D-galactopyranose residues. The molecular rotations of a series of mannooligosaccharides corresponded to a value of −54° for the specific rotation of an infinitely long mannan. It is concluded that the main hemicelluloses in amabilis fir wood are the same as those occurring in the wood of gymnosperms from other genera. The same three hemicelluloses are also present in the bark of this species.

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: III. A GALACTOMANNAN FROM TRICHOPHYTON INTERDIGITALE

1964 ◽  
Vol 42 (12) ◽  
pp. 2862-2871 ◽  
Author(s):  
F. Blank ◽  
M. B. Perry
Keyword(s):  
Formic Acid ◽  
Acid Hydrolysis ◽  
Copper Complex ◽  
Periodate Oxidation ◽  
Water Soluble ◽  
Mild Acid Hydrolysis ◽  
Trichophyton Interdigitale ◽  
Soluble Polysaccharide ◽  
Hydrolysis Of ◽  
Mild Acid

The water-soluble polysaccharide preparation from Trichophytoninterdigitale was fractionated to give two distinct galactomannans and a glucan. A galactomannan isolated via its insoluble copper complex had [α]D +75° (water) and was composed of D-galactose (12%) and D-mannose (88%). On periodate oxidation, the galactomannan consumed 1.73 mole periodate and released 0.67 mole formic acid and 0.12 mole formaldehyde per anhydrohexose unit. Hydrolysis of the methylated galactomannan gave 2,3,5,6-tetra-O-methyl-D-galactose (1 part), 2,3,4,6-tetra-O-methyl-D-mannose (1 part), 2,3,4-tri-O-methyl-D-mannose (4 parts), and3,4-di-O-methyl-D-mannose (2 parts). Mild acid hydrolysis of the galactomannan removed all the galactose residues, leaving a mannan having [α]D +84° (water) whose structure was analyzed by periodate oxidation and methylation techniques.

THE CELL WALL POLYSACCHARIDES OF CANDIDA ALBICANS: GLUCAN, MANNAN, AND CHITIN

1960 ◽  
Vol 38 (6) ◽  
pp. 869-881 ◽  
Author(s):  
C. T. Bishop ◽  
F. Blank ◽  
P. E. Gardner
Keyword(s):  
Cell Wall ◽  
Candida Albicans ◽  
Copper Complexes ◽  
Moving Boundary ◽  
Periodate Oxidation ◽  
Borate Buffer ◽  
Cell Wall Polysaccharides ◽  
Pathogenic Yeast ◽  
Hydrolysis Of

Cells of Candida albicans, a pathogenic yeast, have been shown to contain, in addition to chitin, a glucan ([α]D − 30°) and a mannan ([α]D + 78°) in the approximate ratio of 1.00:0.64. The two polysaccharides were easily distinguishable by moving boundary electrophoresis in borate buffer and were separated from each other by fractionation of their copper complexes. Methylation and hydrolysis of the glucan yielded the following O-methyl ethers of D-glucose: 2,3,4,6-tetra-O-methyl (7 moles); 2,3,4-tri-O-methyl (13 moles); 2,4,6-tri-O-methyl (trace); 2,4-di-O-methyl (6 moles); and 2-O-methyl (1 mole). It was concluded that the glucan was a highly branched polysaccharide containing β 1 → 6 and β 1 → 3 linked residues. Periodate oxidation of the glucan supported this conclusion.Methylation and hydrolysis of the mannan yielded the following O-methyl ethers of D-mannose: 2,3,4,6-tetra-O-methyl (1.65 moles); 3,4,6-tri-O-methyl (1.00 mole); 2,3,6-tri-O-methyl (0.18 mole); 3,4-di-O-methyl (1.90 moles). The mannan was therefore a highly branched polysaccharide with short chains of α 1 → 2 linked mannose residues joined together by α 1 → 6 linkages. Results of periodate oxidation agreed with this structure.The differences between these two polysaccharides and glucans and mannans found in other yeasts are discussed.

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: VI. GLUCANS FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII

1966 ◽  
Vol 44 (19) ◽  
pp. 2299-2303 ◽  
Author(s):  
C. T. Bishop ◽  
M. B. Perry ◽  
R. K. Hulyalkar ◽  
F. Blank
Keyword(s):  
Infrared Spectra ◽  
Trichophyton Rubrum ◽  
Water Soluble ◽  
Structural Studies ◽  
Trichophyton Interdigitale ◽  
Electrophoretic Mobilities ◽  
Hydrolysis Of

Polysaccharides obtained from each of the organisms designated in the title have been resolved into three groups: galactomannans I, galactomannans II, and glucans. The five glucans were homogeneous under conditions of electrophoresis, and had identical electrophoretic mobilities and infrared spectra. Methylation and hydrolysis of the glucans yielded varying amounts of the following: 2,3,4,6-tetra-O-methyl-D-glucose, 2,3,4-tri-O-methyl-D-glucose, 2,4,6-tri-O-methyl-D-glucose, and 2,4-di-O-methyl-D-glucose. The glucans were therefore branched polysaccharides, with branches formed by substitution at the C-3 and C-6 positions of D-glucopyranose units and terminated by D-glucopyranose units. The linear portions of the glucans contained 1 → 6 and 1 → 3 linkages but in varying amounts. These differences and some variation in the degrees of branching constituted the only dissimilarities detectable in the glucans by these structural studies.

THE STRUCTURE OF A SYNTHETIC ARABINAN

1965 ◽  
Vol 43 (4) ◽  
pp. 924-927 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau
Keyword(s):  
Vapor Phase ◽  
Paper Chromatography ◽  
Methyl Ether ◽  
Periodate Oxidation ◽  
Borohydride Reduction ◽  
Terminal Units ◽  
Branched Structure ◽  
Hydrolysis Of

Hydrolysis of the fully methylated synthetic arabinan showed it to have a highly branched structure in which about 16% of the terminal units were furanose and 2,3-di-O-methyl-L-arabinose was the principal di-O-methyl ether. A method has been developed whereby mixtures of isomeric di- or mono-O-methyl arabinoses may be qualitatively analyzed by successive borohydride reduction, periodate oxidation, and borohydride reduction. The resulting fragments may be separated directly by vapor phase chromatography or by paper chromatography after demethylation.

STRUCTURE OF AN ARABOGALACTAN FROM WHITE SPRUCE (PICEA GLAUCA (MOENCH) VOSS)

1958 ◽  
Vol 36 (5) ◽  
pp. 755-762 ◽  
Author(s):  
G. A. Adams
Keyword(s):  
Picea Glauca ◽  
Periodate Oxidation ◽  
White Spruce ◽  
Water Soluble ◽  
Molar Ratio ◽  
Glycosidic Bonds ◽  
Spruce Wood ◽  
Soluble Polysaccharide ◽  
Branched Structure ◽  
Hydrolysis Of

A water-soluble polysaccharide isolated from white spruce wood contained D-galactose, L-arabinose, and D-xylose in a molar ratio of 21:3:1. Hydrolysis of the fully methylated polysaccharide yielded 2,3,5-tri-O-methyl-L-arabinose (12 moles); 2,3,4,6-tetra-O-methyl-D-galactose (29 moles); 2,3,4-tri-O-methyl-D-galactose (34 moles); 2,6-di-O-methyl-D-galactose (0.5 moles); 2,4-di-O-methyl-D-galactose (45 moles); 2,3-di-O-methyl-D-xylose (5 moles); and monomethyl xylose (1 mole). When oxidized by periodate the polysaccharide consumed 1.18 moles of oxidant, and yielded 0.56 moles of formic acid per mole of anhydro-D-galactose. The D-xylose was attributed to the presence of a xylan mixed with the arabogalactan in the original polysaccharide preparation. The methylation and periodate oxidation data showed that the arabogalactan possessed a highly branched structure with the anhydro-D-galactose units being joined by 1 → 3 and 1 → 6 glycosidic bonds. All of the L-arabinose was present in the furanoside form as non-reducing terminal units.

Structural features of a lipopolysaccharide isolated from Escherichiacoli 086:Kneg.

1970 ◽  
Vol 48 (16) ◽  
pp. 2500-2508 ◽  
Author(s):  
Prem Pal Singh ◽  
G. A. Adams
Keyword(s):  
Acid Hydrolysis ◽  
Lipid A ◽  
Structural Features ◽  
Branch Points ◽  
Mild Acid Hydrolysis ◽  
Partial Acid Hydrolysis ◽  
E Coli ◽  
Glucan Chain ◽  
Hydrolysis Of ◽  
Mild Acid

Lipopolysaccharide (LPS) prepared from Escherichiacoli 086:Kneg., in 5.5% yield contained D-galactose, D-glucose, L-fucose, L-glycero-D-manno-heptose, D-glucosamine, D-galactosamine, 2-keto-3-deoxy-octulosonic acid (KDO) and lipid A. The molecule appeared to be homogeneous as tested by free boundary electrophoresis, ultracentrifugation, and immunodiffusion against ′O′ specific E. coli antiserum. Methylation studies of the LPS and also of the degraded polysaccharides obtained by partial acid hydrolysis showed that the molecule was highly branched. Sixty percent of the D-galactose units were non-reducing terminal groups, the remainder were linked (1 → 3) and (1 → 2) and 3-O-β-D-galactopyranosyl-D-galactose was identified as a product of mild acid hydrolysis of the parent LPS. Fucose occurred in the polysaccharide as (1 → 4) linked units. Methylation results showed that the D-glucose units were linked (1 → 3) and (1 → 4). Partial acid hydrolysis yielded cellobiose, cellotriose, and laminaribiose, showing that the glucose units formed a glucan chain within the polysaccharide and that the glucosidic linkages were in the β-D-configuration. Approximately one half of the L-glycero-D-manno-heptose units occurred as non-reducing end groups, the other half were linked at C-3 and either one of C-6 or C-7. One half of the D-galactosamine units was linked (1 → 3) with the remainder occurring as double branch points. D-Glucosamine residues occurred exclusively in the lipid A moiety in a (1 → 4) linked core structure.

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