Monosaccharides sulfated

In addition to the esters of uridine 5 -pyrophosphate with monosaccharide sulfates, hen oviduct contains corresponding esters with two saccharides. The first known member of this series was a unique derivative 41, in which the monosaccharide residues are linked... 

M. Namekata, T. Tanaka, N. Sakamoto, and K. Moro, Oligosaccharide sulfates and monosaccharide sulfates for medical purposes. Antiulcerogenic properties of sucrose sulphate-aluminium complex, Yakugaku Zasshi, 87 (1967) 889-893 Chem. Abstr., 68 (1968) 2083 Id. 

Elliott, H., and Hopwood, J. J., Detection of the Sanifilippo D syndrome by the use of a radiolabeled monosaccharide sulfate as the substrate for the estimation of N-acetylglucora-niine 6-sulfate sulfatase. Anal. Biochem. 138, 205-209 (1984). 

Guiseley, K.B. and Ruoff, P.M. (1961) Monosaccharide sulfates. I. Glucose-6-sulfate. Preparations, characterization of the crystalline potassium salt, and kinetic studies. 7. Org. Chem. 26 1248-1254. 

Monosaccharides such as glucose and fmctose are the most suitable as starting materials. When starch is used, it is first hydrolyzed with oxahc acid or sulfuric acid into a monosaccharide, mainly glucose. It is then oxidized with nitric acid in an approximately 50% sulfuric acid solution at 63—85°C in the presence of a mixed catalyst of vanadium pentoxide and iron(III) sulfate. 

Considers only the basic monosaccharide units. A derivatized monosaccharide unit, such as a D-galactopyranosyl 6-sulfate unit, is not considered as a unit separate from a D-galactopyranosyl unit, for example. 

PhB(OH)2, PhH or Pyr. A polymeric version of the phenyl boronate has been developed.Phenyl boronates are stable to the conditions of stannyla-tion and have been used for selective sulfation to produce monosulfated monosaccharides. Phenyl boronates were found to be stable to oxidation with pcc ... 

A classical, and still most useful, physicochemical parameter for characterizing glycosaminoglycans is their specific optical rotation. For pure heparins from common sources, [a]80 = + 45 to + 53 ° (see Table II). The actual value depends on the relative proportions of monosaccharide constituents (that is, the L-idosyluronic acid residues make a less positive contribution than the n-glucosyluronic residues), and on the degree of sulfation of the preparation (that is, although sulfate groups may have little direct influence on the molecular rotation, they lower the value by acting as diluents ). 

Extracts of Flavobacterium heparinum that had been induced to grow on heparin-like polysaccharides contain a number of enzymes that may ultimately degrade heparin and heparan sulfate to monosaccharides.137,145 240 The enzymes that cause the primary cleavage of heparinlike chains are heparinase (EC 4.2.2.7) and heparanase (EC 4.2.2.8, formerly called heparitinase241,242). 

Dermatan sulfate, also termed chondroitin sulfate B, a related glycosaminoglycan constituent of connective tissue, was known to be composed of galactosamine and a uronic acid, originally believed to be glucuronic acid but then claimed to be iduronic acid based largely on color reactions and paper chromatography. However, the d or L-enantiomer status of the latter monosaccharide was not clear. Jeanloz and Stoffyn unequivocally characterized the monosaccharide as L-iduronic acid by consecutive desulfation, reduction, and hydrolysis of the polysaccharide, followed by isolation of the crystalline 2,3,4-tri-0-acetyl-l,6-anhydro-/ -L-idopyranose, which was shown to be identical to an authentic specimen synthesized from 1,2-0-isopropylidene-/ -L-idofuranose.34... 

Once assignments of polysaccharide signals are known, they may be used as a basis in determination of the position of substitution by such groups as acetate, malonate, phosphate, and sulfate, whose a- and /3-shifts may be estimated by referral to suitable monosaccharide models. For phosphate, the phosphated carbon atoms and adjacent resonances may be identified, as they give coupled signals and are subject to lanthanide-induced shifts. These data are described in Section VI, 8. 

In such cases, it is practical to apply the following considerations. The analysis usually provides data that can be expressed as numbers of moles of each monosaccharide derivative per mole of sample. The expression [NS] - [DS] - 2 [TS] - 3 [TeS] (where NS = nonsubsti-tuted (terminal), DS = disubstituted (branched), TS = trisubstituted, and TeS = tetrasubstituted sugars) should theoretically give a value of unity. If values far below unity are encountered, several sources of analytical error must be considered. Undermethylation must be considered, as well as erroneously low values for terminal sugars caused by the volatility of their methylated derivatives. Nonglycosidic substituents, such as sulfate,56 phosphate, and acetal groups must also be considered.48... 

An exo-linker according to Fig. 10.1 must contain an enzyme labile group R, which is recognized and attacked by the biocatalyst Possible combinations could be phenylacetamide/penicillin amidase, ester/esterase, monosaccharide/glycosid-ase, phosphate/phosphatase, sulfate/sulfatase and peptides/peptidases [41]. The following systems have been worked out (Tab. 10.2). 

Methanolysis of standard uronic acids has been studied by Inoue and Miyawaki in regard to the depolymerization of chondroitin sulfate and dermatan sulfate. These workers found the glucosiduronic linkage to ga-lactosamine to be rather resistant to methanolysis, but that it is more efficiently cleaved after deamination of the amino galactoside, with its conversion into 2,5-anhydrotalose. For iduronic, glucuronic, and man-nuronic acids released from a polymer, it was found that the peaks monitored for these acids, relative to an internal standard, increase during the first 8 h of methanolysis (M hydrogen chloride, 100°) and remain constant for up to 20 h of methanolysis. This indicated that 8 h is required for complete methanolysis, and that the monosaccharides liberated are stable to the conditions of methanolysis. 

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