MAHESH JASEJA, RABINDRA N. REJ, FRANCOIS SAURIOL, and ARTHUR S. PERLIN. Can. J. Chem. 67, 1449 (1989).Nuclear magnetic resonance spectroscopic evidence is presented in characterizing three new structurally modified forms of heparin. One of these, polymer M-I, represents a conversion of about two-thuds of the a-L-iduronic acid 2-sulfate residues (1) into residues of a 2,3-anhydro derivative (3), through the action of sodium hydroxide. The formation of 3 is attributed to a base-catalysed displacement of the sulfate group of 1 by an intramolecular attack of 0 -3 on C-2. In more concentrated sodium hydroxide solution, heparin is transformed almost quantitatively into polymer M-11, which differs from it in having residues of (non-sulfated) a-L-iduronic acid (4) in place of 1. It is likely that 3 is an intermediate, and that a selective nucleophilic attack of hydroxide ion at C-2 accounts for the ido configuration in 4. The third modification, giving polymer M-111, is induced when a neutral or weakly alkaline solution of M-I is heated at 70°C or above, which promotes a different stereochemistry in the hydrolysis of the 2,3-oxirane ring of 3. Hence, in contrast to residues of 4 in M-11, most of the uronic acid residues of M-I11 appear to have the alternate, a-L-galacto, configuration. As shown by a comparison of beef lung and hog mucosal heparin, the rate at which M-I is converted into M-111 is facilitated by the higher level of structural heterogeneity in the mucosal heparin. Whereas the formation of M-I, -II, and -1II is accompanied by only moderate depolymerization, these novel polymers retain little of the anti-coagulant and anti-XA activities of the unmodified heparin.Key words: NMR spectroscopy, heparin, desulfation, anhydroaldoside, base-catalysed displacement. On prCsente les spectres de rdsonance magnCtique nuclCaire de trois nouvelles formes d'hCparine modifiCes structuralement. Dans l'une d'elles, le polymkre M-I, environ les deux tiers des rCsidus sulfates de I'acide a-L-iduronique (1) ont Ct C transformCs en rCsidu du dCrivC dthydro-2,3 (3) sous I'action de l'hydroxyde de sodium. On attribue la formation du dCrivC 3 au dCplacement, catalysk par une base, du groupe sulfate du composC 1 par suite d'une attaque intramolCculaire de I'oxygkne en position 3 (0-3) sur le carbone en position 2 (C-2). Dans une solution plus concentrke d'hydroxyde de sodium, I'hCparine se transforme presque quantitativement en polymkre M-11 qui difEre de I'hCparine par la prksence de rksidus (non sulfatks) de l'acide a-L-iduronique (4) au lieu du composC 1. I1 est comrnunCment admis que le compost! 3 est un intermkdiaire, et qu'une attaque nucltophile sklective de I'ion hydroxyde en C-2 est responsable de la configuration ido dans le composC 4. La troisikme modification, conduisant au polymkre M-111, est obtenue par chauffage B 70°C ou au-dessus d'une solution neutre ou faiblement alcaline du polymkre M-I, ce qui favorise une sterkochimie diffkrente dans I'hydrolyse du cycle oxyrane-2,3 du compost 3. Cependant, contrairement au rCsi...
Carbon-13 chemical shifts for sugars and methyl glycosides are reported. The following general effects have been observed: (a) a comparison of chemical shifts with expected electron densities suggests that 13C-2 and -4 experience relatively stronger shielding than do 13C-1, -3, and -5, possibly because they oppose the ring 0 ; (b) inversion of an equatorial 0 to axial 0 is associated with increased shielding of the 13C nucleus to which it is bonded, of adjacent I3C nuclei, and of those in the p-position (i.e., having a n opposing axial H or 0 ) ; (c) removal of a gauche 0 , O interaction is associated with 13C deshielding. It appears that since these same steric relationships affect stability, the overall shielding states of I3C nuclei of the different isomers reflect variations in the magnitude of repulsive interactions in the molecules; on this basis, the anomeric effect does not arise through instability of the equatorial anomeric C-0 bond. A destabilizing interaction appears to cause polarization of most C-H bonds in a molecule, 13C becoming more shielded, and ' H less shielded, suggestive of a concerted means for delocalizing the instability. In comparing anomers or epimers, this polarization is evident as a reordering of the shielding state of different nuclei, e.g., for several sugars and their glycosides increased shielding o f 13C-l is accompanied by deshielding of the bonded H and increased shielding of the appended 0-H or methoxyl 13C nucleus.
ABSTRACT, .I lie soluble poly-0-D-glucan from oats has been subjected to degradation by two different types of cnzylues. "Cellulase" converts the polysaccharide to a trisaccharide, 4-0-0-~-Iaminaribiosyl-D-glucose, and two tetrasaccharides, 3'-0-~-~-ce~~obiosyl-~-ce~lobiose and 4'-0-P-Dlaminaribiosyl-D-cellobiose." Uegradatio~l by the second enzyme, "laminarinase", produces a trisaccharide, 3-O-P-~-cellobiosyl-~-&cose, and a tetrasaccharide, 3-O-p-D-~ell0tri0syl-Dgl~~cose.t These products, which account for 75-85% of the polymer in each experiment, have bee11 characterized by cl~emical methods. The data show that the glucan is composed almost entirely of two types of s t r u c t~~r a l sequences: one is a tetrameric unit in which a single P-(1 + 3) lii?l;age alternates with two P-(1 + 4) linl;ages, and the other, a pentameric unit in which a s~ngle 0-(1 + 3) linkage alternates with three consec~itive P-(1 + 4) 1inl;ages.The soluble pol!-P-D-glucan from barley has been shown by enzymolysis with the "celli~-lase" to be closely related in detailed structure to the oat polymer.Steric aspects of the enzymic degradations are discussed.
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