Polysaccharides selective

Of the attempted replacements of various ester groups of polysaccharide esters by halide, the displacement of the p-tolylsulfonyloxy group has been the most successful, although nitric esters undergo the reaction to some extent. The reactions reported have been performed on polysaccharides selectively sulfonylated at 0-6, namely, 2,3-di-O-acetyl-6-O-p-tolylsulfonylcellulose, 6-O-p-tolylsulfonylamylose, 6-O-p-tolylsulfonylstarch, 6-O-p-tolylsulfonylcellulose, and 2,3-di-O-benzyl-6-0-p-tolylsulfonylamylose, to give the 6-deoxy-6-iodo derivatives. 

FroUini E., Reed W.F., Milas M., Rinaudo M., Polyelectrolytes from polysaccharides Selective oxidation of guar gum - A revisited reaction, Carbohydr. Polym., 27, 1995, 129-135. 

There are many different routes to organic chemicals from biomass because of its high polysaccharide content and reactivity. The practical value of the conversion processes selected for commercial use with biomass will depend strongly on the availabiUty and price of the same chemicals produced from petroleum and natural gas. 

Oxidation of polysaccharides is a far more attractive route to polycarboxylates, potentially cleaner and less cosdy than esterification. Selectivity at the 2,3-secondary hydroxyls and the 6-primary is possible. Total biodegradation with acceptable property balance has not yet been achieved. For the most part, oxidations have been with hypochlorite—periodate under alkaline conditions. In the 1990s, catalytic oxidation has appeared as a possibiUty, and chemical oxidations have also been developed that are specific for the 6-hydroxyl oxidation. 

Table 1. Classification of Selected, Native Polysaccharides by Structure...

Based on this background, a selected number of preparative, semipreparative, and analytical aqueous SEC systems for the analysis of polysaccharides, summarized in Table 16.1, are presented and discussed briefly in this chapter. 

Polysaccharide-based CSPs incorporate derivatives of cellulose and amylose adsorbed on silica gel. The selectivity of these CSPs depends upon the nature of the substituents introduced during the derivatization process. The secondary structure of the modified polysaccharide is believed to play a role in selectivity, but the chiral recognition mechanisms have not been fully elucidated [55]. 

Separations of polysaccharides by fractionation on a preparative scale were also examined. Stemming from earlier work in his laboratory on the isolation of acidic polysaccharides by precipitation as their insoluble Cetavlon salts, Stacey and coworkers showed that it was possible to fractionate neutral polysaccharides by selective precipitation with Cetavlon after the formation of borate complexes. 

The present chapter, therefore, will present certain topics based on a selection of references, mainly in view of providing a perception of the current developments and great potential of chitin today. The reader is referred to books and reviews [1-17] where basic information and specific subjects are treated in a more systematic way. These polysaccharides are described not only in encyclopaedias, handbooks, monographs and articles, but also in the American Standard Testing Materials standard guides and in the Pharmacopoeias of various coimtries [10,16,17]. 

Figure 48-9. Structure of heparin. The polymer section illustrates structural features typical of heparin however, the sequence of variously substituted repeating disaccharide units has been arbitrarily selected. In addition, non-O-sulfated or 3-0-sulfated glucosamine residues may also occur. (Modified, redrawn, and reproduced, with permission, from Lindahl U et al Structure and biosynthesis of heparin-like polysaccharides. Fed Proc 1977 36 19.)...

The availability of these novel enzymes, next to the known pectic enzymes, offer new opportunities to use them as analytical tools in revealing the structure of oligo- and polysaccharides [31,32]. In contrast with frequently used chemical degradation methods, which usually have a poor selectivity, these enzymes act in a deflned way. To be able to recognize different structural units within the polymer, endo-acting types of enzyme are preferred, although accessory enzymes might be essential as well [30]. 

Other polysaccharides of primary cell walls.-A complex mixture of enzymes including endopolygalacturonase, pectin methylesterase, and/or pectin lyase solubilizes a mixture of polysaccharides from the primary cell walls of fruits [57-64]. Food scientists have referred for some 15 years to this mixture of polysaccharides as the hairy region to describe the highly branched character of the polysaccharides in the fraction and to emphasize the contrast to unbranched homogalacturonan. The recent discovery of rhamnogalacturonan hydrolase [65,66], which selectively cleaves the backbone of RG-I, led to the realization that the hairy... 

It would be easier to describe those classes of compounds not normally separated by RPLC than to catalogue the applications to which RPLC has been turned. Applications for reversed phase can be found in virtually every area of analysis and are reviewed regularly in the journal Analytical Chemistry. RPLC has not been in general use for the analysis of inorganic ions, which are readily separated by ion exchange chromatography polysaccharides, which tend to be too hydrophilic to separate by RPLC polynucleotides, which tend to adsorb irreversibly to the reversed phase packing and compounds which are so hydrophobic that reversed phase offers little selectivity. 

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