Polysaccharides amides

Tables 1 and 2 Hst the important physical properties of formamide. Form amide is more highly hydrogen bonded than water at temperatures below 80°C but the degree of molecular association decreases rapidly with increa sing temperature. Because of its high dielectric constant, formamide is an excellent ionizing solvent for many inorganic salts and also for peptides, proteias (eg, keratin), polysaccharides (eg, cellulose [9004-34-6] starch [9005-25-8]) and resias.

Acyl groups are common in bacterial polysaccharides. The parent acids are fatty acids, hydroxy acids, and amino acids. The simplest acid, formic acid, has only been found as the amide. The occurrence of O-formyl groups had been reported, but proved to be incorrect. A-Formyl groups have been found in different polysaccharides for example, in the 0-specific side-chains of the LPS from Yersinia enlerocolitica 0 9, which are composed of 4,6-dideoxy-4-formamido-D-mannopyranosyl residues. The formyl group can assume two main conformations, s-cis (41) and s-trans (42), which are... 

In several polysaccharides containing glycuronic acid residues, the carboxyl groups of these are linked to the amino group of amino compounds, forming amides. In the simplest examples, these are primary amides, such as the 2-formamido- and 2-acetamido-2-deoxy-D-galacturonamide (49) residues in 0-specific polysaccharides from different strains of Pseudomonas... 

In the cell-wall antigen from Staphylococcus aureus M, taurine is linked as an amide (51) to a 2-acetamido-2-deoxy-D-galactosyluronic residue. l-Threonine and L-glutamic acid are linked as amides to D-glucuronic acid residues in the LPS from Rhodopseudomonas sphaeroides ATCC 17023 and in the capsular polysaccharide from Klebsiella K82, respectively. In the capsular polysaccharide from E. coli K54, L-serine and L-threonine, in the ratio 1 9, are linked to the carboxyl group of a D-glucuronic acid residue. In the capsular polysaccharide from Haemophilus influenzae type d,... 

Carboxymethylcellulose, polyethylene glycol Combination of a cellulose ether with clay Amide-modified carboxyl-containing polysaccharide Sodium aluminate and magnesium oxide Thermally stable hydroxyethylcellulose 30% ammonium or sodium thiosulfate and 20% hydroxyethylcellulose (HEC) Acrylic acid copolymer and oxyalkylene with hydrophobic group Copolymers acrylamide-acrylate and vinyl sulfonate-vinylamide Cationic polygalactomannans and anionic xanthan gum Copolymer from vinyl urethanes and acrylic acid or alkyl acrylates 2-Nitroalkyl ether-modified starch Polymer of glucuronic acid... 

J. G. Batelaan and P. M. van der Horts. Method of making amide modified carboxyl-containing polysaccharide and fatty amide-modified polysaccharide so obtainable. Patent WO 9424169,1994. 

A bacterial phosphatidylinositol specific phospholipase C (PI-PLC) had been available for many years before it was demonstrated to strip a number of membrane-bound proteins from eukaryotic cell surfaces [1], Such proteins are anchored by a PI moiety in which the 6 position of inositol is glycosidically linked to glucosamine, which in turn is bonded to a polymannan backbone (Fig. 3-10). The polysaccharide chain is joined to the carboxyl terminal of the anchored protein via amide linkage to ethanolamine phosphate. The presence of a free NH2 group in the glucosamine residue makes the structure labile to nitrous acid. Bacterial PI-PLC hydrolyzes the bond between DAG and phosphati-dylinositols, releasing the water-soluble protein polysac charide-inositol phosphate moiety. These proteins are tethered by glycosylphosphatidylinositol (GPI) anchors. 

Derivatives (Table I) formed by the reaction of the chosen polysaccharide with an isocyanate or acid chloride are carbamates and esters respectively. However, chitin or poly[(1+4)(N-acetyl-2-amino-2-deoxy-f3-glucopyranose)] actually used in this experiment contains approximately 16% free amine groups which can form urea and amide derivatives with the above reagents. 

More recent developments in the field of the Pirkle-type CSPs are the mixed r-donor/ r-acceptor phases such as the Whelk-Of and the Whelk-02 phases.The Whelk-Of is useful for the separation of underiva-tized enantiomers from a number of families, including amides, epoxides, esters, ureas, carbamates, ethers, aziridines, phosphonates, aldehydes, ketones, carboxylic acids, alcohols and non-steroidal anti-inflammatory drugs.It has been used for the separation of warfarin, aryl-amides,aryl-epoxides and aryl-sulphoxides. The phase has broader applicability than the original Pirkle phases. The broad versatility observed on this phase compares with the polysaccharide-derived CSPs... 

Fig. 7 Maltotetraose hybrids with various carriers resulting in different chain architectures A poly(ethylene oxide) Ba and Bb poly(acrylic acid), amylose, cellulose, and other polysaccharides Ca cyclodextrin and multifunctional acids Cb amylopectin D crosslinked poly(acryl amide) [156] - Reproduced by permission of Wiley...

Mixed protein/polysaccharide micro-beads have also been found to be promising delivery vehicles for immobilized bifidobacteria (Guerin et al, 2003). Such micro-beads were made by a transacylation reaction involving the formation of amide bonds between protein and alginate (Levy and Edwards-Levy, 1996). This produces a membrane on the bead surface, protecting the immobilized bifidobacteria against both the very acidic conditions (pH 1-2) and the pepsin activity in the stomach. 

Figure 7.23 Influence of low-methoxyl amidated pectin on microstructure of caseinate gels acidified with giucono-8-lactone. The images show the gels (2 wt%) after 6 hours of acidification to pH = 4.0 for different added polysaccharide concentrations (wt%) (a) 0 (b) 0.1 (c) 0.4 (d) 0.8. Scale bar = 10 pm. Reproduced from (Matia-Merino et al., 2004) with permission.

The study of Saa has so far concentrated on their use as biopolymer building blocks to mimic oligo- and polysaccharide structures via amide bond linkages.1In 1994 the first example of a Saa as a new type of peptidomimetic [replacement of amino acid(s) by Saa] was reported/44 which was later extended to the Saa construction kit 7-16, and others, a versatile tool for the manipulation of peptide properties 45"51 (Scheme 2). 

Infrared spectra of glycosaminoglycans in D20 and DC1 were used165 for quantitative evaluation of the uronic acid and acetamido groups in this class of polysaccharide. The results showed that i.r. spectroscopy of compounds in D20 solution provides a simple, quantitative basis for examination of ras(COJ) and amide I bands in heparin and chondroitin 4-sulfate. In DC1, analysis was based on p(C02H) and amide I bands which were well resolved. The apparent acid-dissociation constants of the studied polysaccharides were estimated from the absorbance of p(C02) or p(C02H) bands, or both, at different pH (pD) values. 

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