Chitobiose

F.a.b.-m.s. has contributed to a detailed analysis of the high-mannose carbohydrate chains of prostaglandin endoperoxide synthase from sheep. Oligosaccharides released by hydrazinolysis were analyzed after N-re-acetylation and reduction. The f.a.b. data defined the compositions of the oligosaccharides, and showed that hydrazinolysis had effected a partial fission of the chitobiose core. 

Fig. 20.—Circular Dichroism of Chitobiose (- - ), Chito etraose (—), and Chitohexaose (----) in Aqueous Solution. (Redrawn from Ref. 34.)...

CieHss Ou 3 HaO 2-Acetamido-4-0-(2-acetamido-2-deoxy-J -D-glu-copyranosyl)-2-deoxy-/ -D-glucopyranose, trihydrate [N,N -diacetyl-/ -chitobiose, trihydrate] (BCHllT lO)94... 

Fig. 15.1. The A/-glycan biosynthetic pathway, illustrating how the three classes of A/-glycans (high mannose, hybrid and complex glycans) are derived from a common biosynthetic precursor. The trimannosyl-chitobiose core, which is common to all A/-glycans, is outlined on the precursor A/-glycan. Glc, o Man, GIcNAc.

This conclusion10 has been reached mainly from crystallographic studies on chitin and on acetylchitobiose obtained from chitin by acetoly-sis.107 The chitobiose was isolated in the form of its crystalline octa-acetate which could also be obtained108 by acetylation of the hydrolyzate produced by the action of fuming hydrochloric acid on chitin. A hen-decaaeetylchitotriose also was obtained by this procedure. 

The chitobiose unit has been treated as a rigid body, and by using the full-matrix, least-squares, rigid-body, refinement procedure, the structure was refined to an R factor of 40.7%. Visually estimated intensities were used. The structure was found to be free from short contacts, and to be stabilized by an intrachain OH-3—0-5 hydrogen-bond and one interchain N-H—O hydrogen-bond. 

Endo-2-acetamido-2-deoxy-)3-D-glucosidase has been used in structural studies of glycopeptides.30 The enzyme cleaves the linkage between the two 2-amino-2-deoxyglucose residues that constitute the chitobiose residue linked to L-asparagine in glycoproteins containing... 

N-glycosylically-linked saccharide chains. The endo-2-amino-2-deoxyglucosidases from different sources have different structural specificities towards the substitution of the mannotriose structure linked to the chitobiose unit.30,81... 

In order to construct the L-asparagine derivative of per-O-acetylated 0-(2-acetamido-2-deoxy-/ -D-glucopyranosyl( 1 — 4)-2-acetamido-2-deoxy-D-glucose (7), Spinola and Jeanloz (13) used (the sensitive) silver azide for conversion of the a-chloro anomer of the chitobiose derivative 8 into the / -azido derivative 9. Kunz and associates (14,15) have accomplished the conversion of the a-chloro anomer of 8 into 9 using sodium azide in the presence of tri-n-octyl-methylammonium chloride as a phase-transfer catalyst in chloroform water. 

The combination of the N-terminal allyloxycarbonyl (Aloe) group (34) with the tert-butyl ester proved to be a particularly efficient tool in the synthesis of complex glycopeptides, as has been demonstrated in the synthesis of sensitive fucosyl chitobiose glycopeptides (19). The Aloe group was... 

Similarly Thiem and Wiemann (92) conducted the galactosylation of the 2-acetamido-2-deoxy-D-glucose-L-asparagine derivative 183 and the chitobiose-L-asparagine derivative 187 to furnish the di- and trisaccharide derivatives 185 and 188, respectively, by using galactosyltransferase. 

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