Galactomannan from Cassiaabsus seed. I. Nature of sugars present, methylation, and periodate oxidation studies

1969 ◽  
Vol 47 (15) ◽  
pp. 2883-2887 ◽  
Author(s):  
V. P. Kapoor ◽  
S. Mukherjee
Keyword(s):  
Formic Acid ◽  
Main Chain ◽  
Periodate Oxidation ◽  
Branch Points ◽  
Ca 50 ◽  
Hydrolysis Of

A galactomannan composed of D-galactose (1 mole) and D-mannose (3 moles) was isolated from the seed of Cassiaabsus. Methylation and hydrolysis of the galactomannan produced 2,3,4,6-tetra-O-methyl-D-galactose (2 moles), 2,3,6-tri-O-methyl-D-mannose (4.2 moles), 2,3-di-O-methyl-D-mannose (1 mole), and 4,6-di-O-methyl-D-mannose (1 mole). Periodate consumption was 1.09 moles for each hexose unit with concomitant liberation of 0.26 mole of formic acid. The periodate oxidized and the reduced galactomannan afforded, on hydrolysis, glycerol (1.94 moles), erythritol (5 moles), and D-mannose (1.08 moles).On the basis of the above findings, a structure for the galactomannan can be proposed in which mannose units form the main chain and the galactose units are present as branches, the former being attached mostly through 1 → 4 (ca. 85%) and the rest which is nearly half the branch points through 1 → 3 or 1 → 2, and branches of single galactose units are attached through 1 → 6 (ca. 50%) and the rest through 1 → 2 or 1 → 3.

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: 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 STRUCTURE OF LINSEED MUCILAGE: PART II

1962 ◽  
Vol 40 (7) ◽  
pp. 1266-1279 ◽  
Author(s):  
K. Hunt ◽  
J. K. N. Jones
Keyword(s):  
Galacturonic Acid ◽  
Main Chain ◽  
Periodate Oxidation ◽  
Neutral Fraction ◽  
Acetate Solution ◽  
Partial Acid Hydrolysis ◽  
Cupric Acetate ◽  
Acidic Fraction ◽  
Degraded Material ◽  
Hydrolysis Of

Linseed mucilage has been separated into an acidic and a neutral fraction. The acidic fraction was further separated, by the use of cupric acetate solution, into two fractions, CuI and CuII. Fraction CuI contained L-rhamnose, L-galactose, and D-galacturonic acid. The methylated reduced polysaccharide gave on hydrolysis 2,3,4-tri-O-methyl-L-rhamnose, 3,4-di-O-methyl-L-rhamnose, 4-O-methyl-L-rhamnose, 2,3,4,6-tetra-O-methyl-D-galactose, 2,3,6-tri-O-methyl-D-galactose, and 2,3-di-O-methyl-D-galactose (?); L-galactose was lost during the methylation process. Periodate oxidation studies on the material indicated that the polymer was composed of a main chain of L-rhamnose units with most of the L-galactose units attached as non-reducing end groups. Fraction CuII contained L-rhamnose, L-fucose, L-galactose, and D-galacturonic acid. The methylated reduced polysaccharide gave on hydrolysis 2,3,4-tri-O-methyl-L-fucose, 2,3,4,6-tetra-O-methyl-L-galactose, 2,3,6-tri-O-methyl-D-galactose, 4-O-methyl-L-rhamnose, L-rhamnose, and possibly 2,3-di-O-methyl-D-galactose and 3-O-methyl-D-galactose. Periodate oxidation studies and a degradation by the Smith procedure indicated the presence of a L-rhamnose backbone with L-fucose and L-galactose units attached as non-reducing end groups.The neutral fraction yielded a periodate-oxidizable material after one Smith-type degradation. Periodate oxidation studies indicated that the degraded material was branched. Methylation of the degraded polysaccharide followed by hydrolysis yielded 2,3,4-tri-O-methyl-D-xylose, 2,3-di-O-methyl-D-xylose, 2,4-di-O-methyl-D-xylose, 4-O-methyl-D-xylose, D-xylose, and traces of 2,3,4-trt-O-methyl- or 2,5-di-O-methyl-L-arabinose, 2,4-di-O-methyl-D-xylose, and 3-O-methyl-D-xylose. The main backbone of the degraded polysaccharide appeared to consist of (1 → 4)-linked D-xylose units. Linkages of the (1 → 3) type were also present. The smaller fragments from the Smith-type degradation, L-arabinose, 2-O-α-L-arabinosyl glycerol, and glycerol were characterized. A partial acid hydrolysis of the neutral fraction yielded a number of oligosaccharides.

Galactomannan from the seed of Lotus pedunculatus

1968 ◽  
Vol 21 (8) ◽  
pp. 2107 ◽  
Author(s):  
EL Richards ◽  
RJ Beveridge ◽  
MR Grimmett
Keyword(s):  
Formic Acid ◽  
Acid Hydrolysis ◽  
Periodate Oxidation ◽  
Water Extraction ◽  
Side Chains ◽  
Linear Chains ◽  
Formic Acid Hydrolysis ◽  
Lotus Pedunculatus ◽  
Hydrolysis Of

A galactomannan composed of D-galactose (49%) and D-mannose (51%) was isolated in 2.2 % yield from the seeds of Lotus pedunculatus by water extraction. On periodate oxidation it consumed 1.5 moles of oxidant per hexose unit, releasing 0.53 mole of formic acid. Hydrolysis of the methylated polysaccharide gave, as the major products, 2,3,4,6-tetra-O-methyl-D-galactose (6 parts), 2,3-di-O-methyl-D-mannose (6.25 parts), and 2,3,6-tri-O-methyl-D-mannose (1 part). It is concluded that the polysaccharide contains essentially linear chains of l → 4-linked P-D-mannopyranose units with side-chains of a-D-galactopyranose units attached to C6 of approximately six out of every seven D-mannopyranose units. The galactomannan is more highly branched than similar galactomannans isolated from the seeds of other legumes.

scholarly journals CONSTITUTION OF A GLUCOMANNAN FROM TAMARACK (LARIX LARICINA)

1961 ◽  
Vol 39 (4) ◽  
pp. 889-896 ◽  
Author(s):  
P. Kooiman ◽  
G. A. Adams
Keyword(s):  
Free Boundary ◽  
Main Chain ◽  
Periodate Oxidation ◽  
Larix Laricina ◽  
Hydrolysis Of

A hemicellulose fraction containing D-mannose, D-glucose, and D-galactose in a ratio of 70:25:3 has been isolated from tamarack wood. The product was homogeneous under conditions of free boundary electrophoresis and of sedimentation in the ultracentrifuge. Hydrolysis of the fully methylated hemicellulose yielded 2,3,4,6-tetra-O-methyl-D-glucose (1.2%); 2,3,4,6-tetra-O-methyl-D-galactose (2.2%); 2,3,6-tri-O-methyl-D-glucose (24.0%); 2,3,6-tri-O-methyl-D-mannose (68.8%); 2,3-di-O-methyl-D-mannose (1.6%); and 2,3-di-O-methyl-D-glucose (1.7%). This data and that from periodate oxidation indicated that the glucomannan had a linear backbone of approximately 35 (1 → 4) linked β-D-glucopyranose and β-D-mannopyranose units; approximately two thirds of the chains were terminated at the non-reducing ends by D-galactose and the remainder by D-glucose. Branching, if present, must occur through C6 of the hexoses in the main chain.

Acid-catalyzed Solvolysis of Isonitriles. I

1971 ◽  
Vol 49 (14) ◽  
pp. 2455-2459 ◽  
Author(s):  
Y. Y. Lim ◽  
A. R. Stein
Keyword(s):  
Formic Acid ◽  
Acid Catalysis ◽  
Hydrolysis Product ◽  
Rate Dependence ◽  
Linear Rate ◽  
First Order ◽  
Methyl Amine ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

The acid-catalyzed hydrolysis of methyl isonitrile has been examined. The initial hydrolysis product is N-methylformamide which is further hydrolyzed to methyl amine and formic acid at a much slower rate. The hydrolysis to N-methylformamide is pseudo-first order in methyl isonitrile and shows a linear rate dependence on concentration of general (buffer) acid at fixed pH. The significance of general acid-catalysis in terms of the mechanism of the hydrolysis is considered and taken as evidence for carbon protonation rather than nitrogen protonation as the initiating step.

STRUCTURE OF THE EXTRACELLULAR POLYSACCHARIDE PRODUCED BY XANTHOMONAS ORYZAE

1962 ◽  
Vol 40 (12) ◽  
pp. 2204-2213 ◽  
Author(s):  
A. Misaki ◽  
S. Kirkwood ◽  
J. V. Scaletti ◽  
F. Smith
Keyword(s):  
Acid Hydrolysis ◽  
Glucuronic Acid ◽  
Periodate Oxidation ◽  
Extracellular Polysaccharide ◽  
Xanthomonas Oryzae ◽  
Sodium Borohydride Reduction ◽  
Glycoside Hydrolysis ◽  
Hydrolysis Of ◽  
Structural Significance ◽  
Molecular Proportion

The extracellular polysaccharide isolated from cultures of Xanthomonas oryzae is composed of D-glucose (5 molecular proportions), D-glucuronic acid (2 molecular proportions), and D-mannose (5 molecular proportions). Acid hydrolysis of this polysaccharide, which contains 0.3% combined pyruvic acid, yields 2-O-β-D-glucopyranosyluronic acid D-mannose, which has been characterized as its crystalline fully methylated β-glycoside. Hydrolysis of the methylated polysaccharide gives 2,3,4,6-tetra-O-methyl-D-mannose (3 molecular proportions), 2,3,4-tri-O-methyl-D-glucuronic acid (1 molecular proportion), 2,3,6-tri-O-methyl-D-glucose (4 molecular proportions), 3,4,6-tri-O-methyl-D-mannose (2 molecular proportions), 2,6-di-O-methyl-D-glucose (3 molecular proportions), 2,3-di-O-methyl-D-glucose (1 molecular proportion). The polyalcohol derived from the polysaccharide by periodate oxidation followed by sodium borohydride reduction gives upon acid hydrolysis glycerol (2 molecular proportions), erythritol (1 molecular proportion), and D-glucose (1 molecular proportion). The general structural significance of these findings is discussed.

STRUCTURE OF A GALACTURONAN FROM SUNFLOWER PECTIC ACID

1966 ◽  
Vol 44 (11) ◽  
pp. 1275-1282 ◽  
Author(s):  
V. Zitko ◽  
C. T. Bishop
Keyword(s):  
Galacturonic Acid ◽  
Periodate Oxidation ◽  
Degree Of Polymerization ◽  
Critical Assessment ◽  
Molar Ratio ◽  
Aqueous Methanol ◽  
Pectic Acid ◽  
Potassium Borohydride ◽  
Rate Of Hydrolysis ◽  
Hydrolysis Of

Fractions of sunflower pectic acid containing 89.8%, 94.2%, and 91.4% of D-galacturonic acid were carboxyl reduced as their methyl or ethylene glycol esters by potassium borohydride. Critical assessment of the effects of three different solvents (water, 80% aqueous dimethyl sulfoxide, and 80% aqueous methanol) on the efficiency of reduction showed that the latter solvent was best. The reductions caused a decrease in the degree of polymerization from 270 to 21. Measurement of the rates of hydrolysis of partially reduced pectic acids containing 90%, 41.6%, 19.9%, 11.0%, and 0.65% of D-galacturonic acid showed that the rate of hydrolysis was directly related to the proportion of galacturonosidic linkages present. Methylation and hydrolysis of the carboxyl-reduced pectic acid fractions yielded 2,3,4,6-tetra-O-methyl-D-galactose and 2,3,6-tri-O-methyl-D-galactose in an approximate molar ratio of 1:20. Results of the periodate oxidation of the carboxyl-reduced pectic acid supported the conclusion inferred from the methylation results that the pectic acid was a linear polymer of 1 → 4 linked α-D-galacturonic acid units.

scholarly journals Accumulation of inositol polyphosphate isomers in agonist-stimulated cerebral-cortex slices. Comparison with metabolic profiles in cell-free preparations

1989 ◽  
Vol 258 (1) ◽  
pp. 23-32 ◽  
Author(s):  
I H Batty ◽  
A J Letcher ◽  
S R Nahorski
Keyword(s):  
Cerebral Cortex ◽  
Inositol Phosphates ◽  
Periodate Oxidation ◽  
Chemical Degradation ◽  
Inositol Polyphosphate ◽  
Tissue Slices ◽  
Inositol 1 ◽  
Agonist Stimulation ◽  
Cortex Slices ◽  
Hydrolysis Of

1. Basal and carbachol-stimulated accumulations of isomeric [3H]inositol mono-, bis-, tris- and tetrakis-phosphates were examined in rat cerebral-cortex slices labelled with myo-[2-3H]inositol. 2. In control samples the major [3H]inositol phosphates detected were co-eluted on h.p.l.c. with Ins(1)P, Ins(4)P (inositol 1- and 4-monophosphate respectively), Ins(1,4)P2 (inositol 1,4-bisphosphate), Ins(1,4,5)P3 (inositol 1,4,5-tris-phosphate) and Ins(1,3,4,5)P4 (inositol 1,3,4,5-tetrakisphosphate). 3. After stimulation to steady state with carbachol, accumulation of each of these products was markedly increased. 4. Agonist stimulation, however, also evoked much more dramatic increased accumulations of a second [3H]inositol trisphosphate, which was co-eluted on h.p.l.c. with authentic Ins(1,3,4)P3 (inositol 1,3,4-trisphosphate) and of three further [3H]inositol bisphosphates ([3H]InsP2(s]. 5. Examination of the latter by chemical degradation by periodate oxidation and/or h.p.l.c. allowed identification of these as [3H]Ins(1,3)P2, [3H]Ins(3,4)P2 and [3H]Ins(4,5)P2 (inositol 1,3-, 3,4- and 4,5-bisphosphates respectively), which respectively accounted for about 22%, 8% and 3% of total [3H]InsP2 in extracts from stimulated tissue slices. 6. By using a h.p.l.c. method which clearly resolves Ins(1,3,4,5)P4 and Ins(1,3,4,6)P4 (inositol 1,3,4,6-tetrakisphosphate), only the former isomer could be detected in extracts from either control or stimulated tissue slices. Similarly, [3H]inositol pentakis- and hexakis-phosphates were not detectable either in the presence or absence of carbachol under the radiolabelling conditions described. 7. The catabolism of [3H]Ins(1,4,5)P3 and [3H]Ins(1,3,4)P3 by cell-free preparations from cerebral cortex was also studied. 8. In the presence of Mg2+, [3H]Ins(1,4,5)P3 was specifically dephosphorylated via [3H]Ins(1,4)P2 and [3H]Ins(4)P to free [3H]inositol, whereas [3H]Ins(1,3,4)P3 was degraded via [3H]Ins(3,4)P2 and, to a lesser extent, via [3H]Ins(1,3)P2 to D- and/or L-[3H]Ins(1)P and [3H]inositol. 9. In the presence of EDTA, hydrolysis of [3H]Ins(1,4,5)P3 was greater than or equal to 95% inhibited, whereas [3H]Ins(1,3,4)P3 was still degraded, but yielded only a single [3H]InsP2 identified as [3H]Ins(1,3)P2. 10. The significance of these observations with cell-free preparations is discussed in relation to the proportions of the separate isomeric [3H]inositol phosphates measured in stimulated tissue slices.

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