Polysaccharides acetals, preparation

Acetates can be used instead of the free polysaccharide for preparing polysaccharide adducts. For example,17 at concentrations of 0.1 M alkali metal (lithium, sodium, and potassium) hydroxide in 25% aqueous ethanol, amylose triacetate is deacetylated to form adducts containing approximately one molecule of alkali metal hydroxide per three D-glucose residues. Partially crystalline amylose adducts can be obtained by immersing stretched filaments of amylose triacetate in the deacetylating solution. 

High molecular weight stereoregular polysaccharides were prepared by the cationic polymerization of bicyclic acetals. Schuerch developed and reviewed this field comprehensively several times and described the mechanism of polymerization, synthetic scope of the method, and applications of these synthetic polysaccharides (97-100). 

DMSO/TBAF is highly efficient as a reaction medium for the homogeneous esterification of cellulose by transesterification and after the in situ activation (see below) of complex carboxylic acids. The acylation using acid chlorides and anhydrides is limited because the solution contains a certain amount of water caused by the use of the commercially available TBAF trihydrate and the residual moisture in the air-dried polysaccharides. Nevertheless, this system has shown a remarkable capacity for the esterification of lignocellulosic mataials, for example, sisal fibres, which contain about 14 per cent hemicellulose [28]. The DS values of cellulose acetate prepared from these fibres with acetic anhydride in mixtures of DMSO/TBAF were found to decrease with increasing TBAF concentration from 6 to 11 per cent (Table 16.4), due to the increased rate of hydrolysis both of the anhydride and the ester moieties. 

In connection with studies on the ring-opening polymerization of cyclic acetals, we have undertaken investigations on the polymerization of bicyclic acetals, bicyclic oxalactone, and bicyclic oxalactam, which yield polysaccharide analogs, macrocyclic oligoesters, and a hydrophilic polyamide, respectively, some of which can be expected to be useful as novel speciality polymers. The monomers employed in the studies were prepared via synthetic routes presented in Scheme 1, starting from 3,4-dihydro-2H-pyran-2-carbaldehyde (acrolein dimer) I. 

Charged polysaccharides can also serve as templates for the growth of metallic, semiconductor and magnetic nanoparticles. For instance, chitosan has been reported as a catalyst and stabilizing agent in the production of gold nanoparticles by the reduction oftetrachloroauric (III) acid by acetic acid. The biopolymer controls the size and the distribution of the synthesized Au nanoparticles and allows the preparation... 

Like in gangliosides, lactones might be found in some bacterial capsular polysaccharides containing 1-carboxyethylsubstituents. But their identification remains problematic due to the conditions of isolation and preparation of analytic samples. To facilitate their detection by NMR, and in order to determine if the formation or hydrolysis of lactones occurred during analytical procedures, synthetic model substances, 2,3- and/or 3,4-lactones based on gluco-12, manno-13, and galactopyranosides 14 were prepared and characterized by NMR spectroscopy (Fig. 2).20 The relative lactonisation rates in acetic acid-fi 4 and hydrolysis rates in buffered D20 were evaluated. 

Natural xylan may occur partially esterified with acetic acid. This possibility arises from the observation that most holocellulose preparations contain a small amount of acetic acid. So far, however, it has not been established which polysaccharides are esterified. Treatment of the holocellulose with the alkaline solutions necessary for xylan extraction brings about complete deacetylation. 

However, in the polysaccharides obtained from some mutant strains, there are deviations from this idealized structure.44 Xanthan is relatively resistant to enzymic hydrolysis, but it has been cleaved by an enzyme preparation from a Bacillus sp. at moderate temperatures and in the presence of buffer salts, yielding mono- and oligo-saccharides 45 A partially purified, enzyme preparation46 hydrolyzed deacetylated or depyruvated xanthan, and also xanthan from several wild-type and mutant strains of Xanthomonas. The release of reducing material varied little with xanthan preparations having differences in O-acetyl and pyruvic acetal contents. Under similar conditions of incubation, cellulase acted only on xanthan from mutant strains that had defective side-chain formation. 

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