THE CONSTITUTION OF A SYNTHETIC XYLAN: I. GENERAL STRUCTURAL FEATURES

1962 ◽  
Vol 40 (8) ◽  
pp. 1479-1482 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau
Keyword(s):  
Infrared Spectrum ◽  
Ethylene Glycol ◽  
Periodate Oxidation ◽  
Phosphorous Acid ◽  
Structural Features ◽  
Synthetic Polymer ◽  
Partial Hydrolysis ◽  
Complete Hydrolysis ◽  
Carbonyl Band ◽  
Hydrolysis Of

The polysaccharide was obtained by polymerization of D-xylose at 140 °C in the presence of phosphorous acid. Complete hydrolysis of the xylan followed by bromine oxidation showed that the synthetic polymer contained only xylose. Periodate oxidation resulted in formation of a considerable quantity of formaldehyde, the origin of which is not known. Periodate oxidation of borohydride-reduced xylan gave additional formaldehyde and, from this, the average D. P. of the polymer was estimated to be about 55. Complete hydrolysis of the polyalcohol gave ethylene glycol, glycerol, and xylose in a ratio of 2:9:1. Partial hydrolysis gave ethylene glycol, glycerol, and at least seven non-reducing components. Hydrolysis of the fully methylated xylan gave tri-, di-, mono-methyl xyloses and xylose in a 32:32:18:5 ratio, and a carbonyl band was evident in the infrared spectrum of the hydrolyzate. No such band was evident in the hydrolyzate of the unsubstituted xylan. The xylan is highly branched and contains some D-xylofuranose units.

THE STRUCTURE OF A SYNTHETIC GLUCAN: I. GENERAL STRUCTURAL FEATURES

1962 ◽  
Vol 40 (6) ◽  
pp. 1196-1200 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau
Keyword(s):  
Petroleum Ether ◽  
Acid Hydrolysis ◽  
Direct Evidence ◽  
Periodate Oxidation ◽  
Structural Features ◽  
Degree Of Polymerization ◽  
Molar Ratio ◽  
Partial Hydrolysis ◽  
Large Numbers ◽  
Hydrolysis Of

Only D-glucose was obtained on acid hydrolysis of the glucan. Periodate oxidation released formaldehyde, which was believed to arise from C6 of D-glucofuranose units. From the additional formaldehyde liberated from the borohydride-reduced glucan the degree of polymerization was estimated to be about 165. Complete hydrolysis of the derived polyalcohol gave glycerol, erythritol, D-glucose, and D-xylose. Partial hydrolysis gave glycerol, erythritol, and at least seven non-reducing oligosaccharides. Direct evidence for the existence of relatively large numbers of 1 → 6 and 1 → 4 linkages was found, together with smaller numbers of 1 → 2 linkages. The methylated glucan was freely soluble in chloroform – petroleum ether (5:95), and hydrolysis gave tetra, tri, di, and mono-O-methyl-D-glucoses in a 6:6:3:1 molar ratio.

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.

scholarly journals Studies of the polysaccharide fraction from the lipopolysaccharide of Pseudomonas alcaligenes

1974 ◽  
Vol 139 (3) ◽  
pp. 633-643 ◽  
Author(s):  
James A. Lomax ◽  
George W. Gray ◽  
Stephen G. Wilkinson
Keyword(s):  
Gel Filtration ◽  
Periodate Oxidation ◽  
Side Chain ◽  
Partial Hydrolysis ◽  
Methylation Analysis ◽  
Mild Acid Hydrolysis ◽  
Pseudomonas Alcaligenes ◽  
Crude Polysaccharide ◽  
Hydrolysis Of ◽  
Mild Acid

Studies of the lipopolysaccharide of Pseudomonas alcaligenes strain BR 1/2 were extended to the polysaccharide moiety. The crude polysaccharide, obtained by mild acid hydrolysis of the lipopolysaccharide, was fractionated by gel filtration. The major fraction was the phosphorylated polysaccharide, for which the approximate proportions of residues were; glucose (2), rhamnose (0.7), heptose (2–3), galactosamine (1), alanine (1), 3-deoxy-2-octulonic acid (1), phosphorus (5–6). The heptose was l-glycero-d-manno-heptose. The minor fractions from gel filtration contained free 3-deoxy-2-octulonic acid, Pi and PPi. The purified polysaccharide was studied by periodate oxidation, methylation analysis, partial hydrolysis, and dephosphorylation. All the rhamnose and part of the glucose and heptose occur as non-reducing terminal residues. Other glucose residues are 3-substituted, and most heptose residues are esterified with condensed phosphate residues, possibly in the C-4 position. Free heptose and a heptosylglucose were isolated from a partial hydrolysate of the polysaccharide. The location of galactosamine in the polysaccharide was not established, but either the C-3 or C-4 position appears to be substituted and a linkage to alanine was indicated. In its composition, the polysaccharide from Ps. alcaligenes resembles core polysaccharides from other pseudomonads: no possible side-chain polysaccharide was detected.

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.

Some structural features of the heteropolysaccharides of Candida bogoriensis

1968 ◽  
Vol 46 (21) ◽  
pp. 3407-3411 ◽  
Author(s):  
P. A. J. Gorin ◽  
J. F. T. Spencer
Keyword(s):  
Main Chain ◽  
Glucuronic Acid ◽  
Structural Features ◽  
Side Chain ◽  
Partial Hydrolysis ◽  
Exocellular Polysaccharides ◽  
Hydrolysis Of

The two exocellular polysaccharides of Candida bogoriensis contain D-mannose, D-fucose, L-rhamnose, D-glucuronic acid, and D-galactose residues. The main heteropolymer (> 80%) has an α-D-(1 → 3)-linked mannan main-chain as shown by successive Smith degradations. Partial hydrolysis of the heteropolymers provided several methylpentose-containing oligosaccharide fragments corresponding to possible side-chain components.

Structure of the Capsular Polysaccharide of Klebsiella K-type 56

1973 ◽  
Vol 51 (18) ◽  
pp. 3021-3026 ◽  
Author(s):  
Yuen-Min Choy ◽  
Guy G. S. Dutton
Keyword(s):  
Uronic Acid ◽  
Capsular Polysaccharide ◽  
Periodate Oxidation ◽  
Side Chain ◽  
Partial Hydrolysis ◽  
Hydrolysis Of

Methylation, periodate oxidation, and partial hydrolysis studies on the capsular polysaccharide of Klebsiella K-type 56 show the structure to be a repeating unit consisting of[Formula: see text]The nature of the anomeric linkages was determined by p.m.r. spectroscopy of isolated oligosaccharides. The position of the L-rhamnose side chain was defined by characterization of the di- and tetrasaccharides obtained by partial hydrolysis of the fully methylated polysaccharide.This structure represents the first capsular polysaccharide lacking uronic acid to be studied in the genus Klebsiella.

Local Structure of Ferrihydrite and Feroxyhite by Exafs Spectroscopy

Clay Minerals ◽  
1993 ◽  
Vol 28 (2) ◽  
pp. 165-184 ◽  
Author(s):  
A. Manceau ◽  
V. A. Drits
Keyword(s):  
Local Structure ◽  
Temperature Stability ◽  
Coherent Scattering ◽  
Structural Features ◽  
Exafs Spectroscopy ◽  
Partial Hydrolysis ◽  
Ferric Nitrate ◽  
Static Disorder ◽  
Local Structures ◽  
Hydrolysis Of

AbstractSynthetic 2-line and 6-line ferrihydrite and feroxyhite samples prepared from ferric salt solutions have been investigated by EXAFS spectroscopy. All these materials have been found to be short-range ordered, consisting of Fe octahedra linked by comers, edges, and faces. Their local structures are related to those of well-crystallized (oxyhydr)oxides, and the absence of hkl reflections in some samples is attributed to the small size of coherent scattering domains. The presence of face sharings indicates that these materials have structural similarities with hematite. Based on Fe-Fe distances and the analysis of the static disorder, it has been concluded that the local structure of feroxyhite is close to that of hematite, whereas ferrihydrite has common structural features with both hematite (αFe203) and cdβFeOOFI. The local structure of ferrihydrite thus differs from that of aqueous Fe polymers obtained by the partial hydrolysis of ferric nitrate and chloride solutions. Differences of local structures among hydrous Fe oxides and aqueous polymers have been interpreted on the basis of a room temperature stability phase diagram established for well-crystallized (oxyhydr)oxides.

scholarly journals Studies of lipid A fractions from the lipopolysaccharides of Pseudomonas aeruginosa and Pseudomonas alcaligenes

1973 ◽  
Vol 133 (3) ◽  
pp. 563-572 ◽  
Author(s):  
David T. Drewry ◽  
James A. Lomax ◽  
George W. Gray ◽  
Stephen G. Wilkinson
Keyword(s):  
Pseudomonas Aeruginosa ◽  
Lipid A ◽  
Gel Filtration ◽  
Structural Features ◽  
Partial Hydrolysis ◽  
Hexadecanoic Acid ◽  
Alkaline Methanolysis ◽  
Pseudomonas Alcaligenes ◽  
Hydrolysis Of ◽  
Derivatives Of

Lipid A fractions from Pseudomonas aeruginosa and Pseudomonas alcaligenes have similar compositions and structural features. By means of hydrazinolysis of the parent lipopolysaccharides and partial hydrolysis of the deacylation products, it was established that both lipids are derived from the β-(1→6)-linked disaccharide of glucosamine. Phosphorylated derivatives of the disaccharide from Ps. aeruginosa were also characterized. The lipids differ mainly in the absence of hexadecanoic acid and 2-hydroxydodecanoic acid from the lipid from Ps. alcaligenes. Evidence that in Ps. aeruginosa these acids are ester-linked to residues of 3-hydroxyalkanoic acids (including 3-hydroxydecanoic acid) was obtained. Heterogeneity of lipid A fractions was indicated by t.l.c., and by gel filtration of de-O-acylation products from mild alkaline methanolysis of the lipids.

The Synthesis of High Molecular Weight Partially Hydrolysed Poly(vinyl alcohol) Grades Suitable for Nanoparticle Fabrication

2008 ◽  
Vol 8 (11) ◽  
pp. 5739-5747 ◽  
Author(s):  
Jasminder Chana ◽  
Ben Forbes ◽  
Stuart Allen Jones
Keyword(s):  
Vinyl Alcohol ◽  
High Probability ◽  
Chemical Properties ◽  
Synthetic Polymer ◽  
Partial Hydrolysis ◽  
Poly Vinyl Alcohol ◽  
Scanning Calorimetry ◽  
Manufacture Process ◽  
Wide Range ◽  
Hydrolysis Of

Poly(vinyl alcohol) (PVA) is a highly versatile synthetic polymer that is formed by full or partial hydrolysis of poly(vinyl acetate) (PVAc). A wide range of PVA partially hydrolysed grades are commercially available, but the amphiphilic grades of the polymer (30–60% hydrolysis), which probably the most interesting in terms of drug delivery, are not readily available. As a consequence few studies have assessed the application of low hydrolysis PVA polymers to form nanocarriers. The aims of this study were to synthesise amphiphilic grades of PVA on a laboratory scale, analyse their chemical properties and determine whether these grades could be used to form nanoparticles. PVA 30%, PVA 40%, PVA 50% and PVA 60% were synthesised via direct saponification of PVAc. All grades of PVA synthesised had degrees of hydrolysis close to those predicted from the stoichiometry of the saponification reaction. The PVA grades displayed <1.5% batch to batch variability (n = 3) in terms of percentage hydrolysis, demonstrating the manufacture process was both reproducible and predictable. Analysis of the polymer characteristics using 13C nuclear magnetic resonance and differential scanning calorimetry revealed that all PVA grades contained block distributions (i.e., η < 1) of vinyl alcohol monomers (η ranged from 0.33–0.45) with a high probability of adjacency calculated for the hydroxylated units (POH ranged 0.926–0.931). All the grades of PVA formed nanoparticles using a precipitation technique with a trend towards smaller particle size with increasing degree of PVA hydrolysis; PVA 30% resulted in significantly larger nanoparticles (225 nm) compared to PVA 40–60% (137–174 nm).

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