Anomeric configurations

The anomeric configuration, a or P, of the glycosidic linkages is designated when known. 

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An important characterization parameter for ceUulose ethers, in addition to the chemical nature of the substituent, is the extent of substitution. As the Haworth representation of the ceUulose polymer shows, it is a linear, unbranched polysaccharide composed of glucopyranose (anhydroglucose) monosaccharide units linked through thek 1,4 positions by the P anomeric configuration. 

The stmcturaUy similar starch amylose polymer is linked through the a anomeric configuration. The three hydroxyl functions pet anhydroglucose unit ate noteworthy these hydroxyls ate the active sites for ether formation. 

Anomeric configuration in cyclic forms of higher aldoses 2-Carb-9. Dialdases... 

Carb-6.2. The anomeric reference atom and the anomeric configurational symbol (a or p)... 

Fic. 2.—Conformations of the 1,4-dioxane ring with (a) differing and (b) the same anomeric configurations of the glycose residues... 

The anomeric configuration is set in the reductive lithiation step, which proceeds via a radical intermediate. Hyperconjugative stabilization favors axial disposition of the intermediate radical, which after another single electron reduction leads to a configurationally stable a-alkoxylithium intermediate. Protonation thus provides the j9-anomer. The authors were unable to determine the stereoselectivity of the alkylation step, due to difficulty with isolation. However, deuterium labeling studies pointed to the intervention of an equatorially disposed a-alkoxylithium 7 (thermodynamically favored due to the reverse anomeric effect) which undergoes alkylation with retention of configuration (Eq. 2). 

Other inverting glucosidases which conform to the pattern of direct hydrolysis of glycosyl fluorides having the correct anomeric configuration, and transglycosylation with inversion if the anomeric configuration is opposite to that of the natural substrates are trehalase from rabbit renal cortex and from the yeast Candida tropicalis, and ) -D-xylosidase from Bacillus pu-milis. ... 

The a anomers of 2-acetamido-2-deoxy-D-glucose and 2-acetamido-2-deoxy-D-galactose have the same nir c.d. bands in 1 1 methanol-water at 0° as the anomeric mixtures have in aqueous solution. This indicates that the anomeric configuration has little influence on the nir c.d. band. 

The anomeric configurations of the sugar residues were determined by chromium trioxide oxidation [14], Oxidation of the fully acetylated polysaccharide and subsequent monosaccharide analysis by GLC indicated that the D-Xyl units are P-linked (oxidized more rapidly) and that die D-GlcA are a-linked (Table II). 

The lack of glycosyl transfer reaction is the class of pectinolytic hydrolases is in agreement with the observed inversion of the anomeric configuration of the newly formed reducing ends of the products. All three polygalacturonases studied here utilize the single displacement mechanism of hydrolysis. 

In the literature, the anomeric configuration of the carbohydrates has usually been deduced from the C-l chemical-shift and from the spectral pattern, if observable. Because relevant model compounds were not previously available for providing C-l chemical-shift data for glycopep-... 

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