Polysaccharide reaction with

Acetalation. As polyhydroxy compounds, carbohydrates react with aldehydes and ketones to form cycHc acetals (1,13). Examples are the reaction of D-glucose with acetone and a protic or Lewis acid catalyst to form l,2 5,6-di-0-isoprop5lidene-a-D-glucofuranose [582-52-5] and its reaction with benzaldehyde to form 4,6-0-benzyhdene-D-glucopyranose [25152-90-3]. The 4,6-0-(l-carboxyethyhdine) group (related to pymvic acid) occurs naturally in some polysaccharides. 

By 1945, Stacey speculated about the possibility of a structural relationship between Pneumococcus capsular polysaccharides and those produced by other organisms. With Miss Schliichterer, he had examined the capsular polysaccharide of Rhizobium radicicolum. This polysaccharide gave a precipitin reaction in high dilution, not only with Type III Pneumococcus antiserum, but also mixed with antisera from other Pneumococcus types. The chemical evidence indicated that the polysaccharide resembled the specific polysaccharides of Types I and II Pneumococcus. A decade later, the acidic capsular polysaccharide from Azoto-bacter chroococcum, a soil organism, was studied. It, too, produced serological cross-reactions with certain pneumococcal specific antisera. Although the molecular structure of the polysaccharide was not established, adequate evidence was accumulated to show a structural relationship to Type III Pneumococcus-specific polysaccharide. This was sufficiently close to account for the Type III serological cross-relationship. 

Already in 1988 and 1991, Gao et al. [65,66] detected four different polysaccharides present in the leaves of Panax ginseng that had an effect on the complement system, but only two of them, the neutral, GL-NIa, and one of the acidic ones, GL-AIa, had potent activities at low concentrations. GL-NIa was found to be mainly an arabinigalactan type II polymer. GL-AIa was a polysaccharide with a rhamnogalacturonan core with neutral side chains of the AG-II type, confirmed by a strong reaction with the Yariv reagent and the methylation results. It was shown that the crude polysaccharide fraction contained KDO and DHA, suggesting the presence of Rhamnogalacturonan II in... 

Some sugar residues in bacterial polysaccharides are etherified with lactic acid. The biosynthesis of these involves C)-alkylation, by reaction with enol-pyruvate phosphate, to an enol ether (34) of pyruvic acid, followed by reduction to the (R) or (5) form of the lactic acid ether (35). The enol ether may also react in a different manner, giving a cyclic acetal (36) of pyruvic acid. 

A second method of immunotoxin preparation by reductive amination involves the use a polysaccharide spacer. Soluble dextran may be oxidized with periodate to form a multifunctional crosslinking polymer. Reaction with antibodies and cytotoxic molecules in the presence of a reducing agent forms multivalent immunotoxin conjugates. The following sections discuss these options. 

Hydrazide derivatives also may be prepared from a periodate-oxidized dextran polymer or from a carboxyl-containing dextran derivative by reaction with te-hydrazidc compounds (Chapter 4, Section 8). A hydrazide terminal spacer provides reactivity toward aldehyde- or ketone-containing molecules. Thus, the hydrazide-dextran polymer can be used to conjugate specifically glycoproteins or other polysaccharide-containing molecules after they have been oxidized with periodate to form aldehydes (Chapter 1, Section 4.4). 

If branching is (1 —> 3), no glycol grouping will be present in any central unit and it may be seen that reaction will only occur on the terminal units. Such is the case with the polysaccharide laminarin, with the glucan of yeast membrane, and with a galactose-containing polysaccharide isolated from agar.146-148... 

The Mn + complexed ions appear to be the most selective and efficient initiator system for grafting to polysaccharides so far described. The mechanism of the initiation reaction has been studied in our laboratories by model experiments and ESR spectroscopy. There are two possible reactions indicated. Bond cleavage of a vicinal diol according to reaction (22) is one possibility. Another and faster reaction with Mn3+ giving radicals appears to be oxidation of aldehyde groups (24) to alkoxy radicals ... 

The reaction with aldoses and ketoses is different and the procedure may be used to distinguish between them. Free monosaccharides and glycosides do not react in an identical manner with periodic acid and this reveals information about the structure, sequence and linkage of monosaccharides or their derivatives in a polysaccharide. 

The function of the sulfate residue in these polysaccharides is unknown but the suggestion has been made that just as starch is synthesised from D-glucose 1-phosphate by the action of phosphorylase, so the seaweed polysaccharides are formed from the appropriate sugar sulfate by reaction with a sulfatase. ... 

Hydrolysis is the process by which a compound is broken down by reaction with water, thus it can be thought of as the opposite reaction of dehydration, where water is of course removed. Hydrolysis is a key reaction type in biomass chemistry, for it is central in the depolymerisation of polysaccharides to simpler monosaccharide building blocks, such as fructose, glucose, and xylose. 

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