Hydroxylated polysaccharides

Ueda, T., Lee, S. L., Nakatani, Y. et al. (1998). Coating of POPC giant liposomes with hydroxylated polysaccharide. Chemical Letters, 417-18. 

Hydroxyl Polysaccharides (cellulose, agarose, dextran, chitin, chitosan), inorganic glass, polyvinyl alcohol, polyhydroxyethyl methacrylate Cyanogen bromide, triazine method, cyclic frans-2,3-carbonate reaction, carbonylation, periodate oxidation, epoxide activation [168-181]... 

While these attempts to optimize the strength and durability of cement were more or less unsystematic and empirical, the exact details of the chemistry of cement were first elucidated by Le ChateHer (1904). Later developments included the invention of reinforced concrete by Wilkinson and Lambot in 1855, and of blast furnace cement by Emil Langen in 1862. Thereafter, the twentieth century witnessed the invention and optimization of sulfate-resistant alumina cements (1908), the addition of plasticizers such as Hgnosulfonic acid or hydroxylated polysaccharides and superplasticizers such as sulfonated naphthalene-formaldehyde condensate, and the advent of macro-defect-free (MDF) and polymer fiber-reinforced cements, to name only a few. 

The significance of phenoxy anions is well recognized in the isolation of kraft and other water-insoluble technical lignins by acid precipitation. The ioniza tion of phenoHc hydroxyl groups coupled with the reduction of molecular size renders native lignin soluble in the aqueous pulping solution, thus enabling its separation from the polysaccharide components of wood. 

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. 

Catalytic oxidation ia the presence of metals is claimed as both nonspecific and specific for the 6-hydoxyl depending on the metals used and the conditions employed for the oxidation. Nonspecific oxidation is achieved with silver or copper and oxygen (243), and noble metals with bismuth and oxygen (244). Specific oxidation is claimed with platinum at pH 6—10 ia water ia the presence of oxygen (245). Related patents to water-soluble carboxylated derivatives of starch are Hoechst s on the oxidation of ethoxylated starch and another on the oxidation of sucrose to a tricarboxyhc acid. AH the oxidations are specific to primary hydroxyls and are with a platinum catalyst at pH near neutraUty ia the presence of oxygen (246,247). Polysaccharides as raw materials ia the detergent iadustry have been reviewed (248). 

Every polysaccharide contains glycosyl units with unsubstituted hydroxyl groups available for esterification or etherification. Polysaccharide derivatives are described by their degree of substitution (DS), which is the average number of substituent groups per glycosyl unit. Because each monomeric unit of cellulose molecules has free hydroxyl groups at C-2, C-3, and C-6, the maximum DS for cellulose, and all polysaccharides composed exclusively of neutral hexosyl units, the majority of polysaccharides, is 3.0. 

FIGURE 7.21 Amylose and amylopectin are the two forms of starch. Note that the linear linkages are o (1 4), but the branches in amylopectin are o (1 6). Branches in polysaccharides can involve any of the hydroxyl groups on the monosaccharide components. Amylopectin is a highly branched structure, with branches occurring every 12 to 30 residues. 

Stevens and coworkers used their c.d. data on the various D-glucans to assign, tentatively, the bands to specific chromophores. They found that derivatives of these polysaccharides that have all of their hydroxyl groups acetylated still exhibit the 177-nm band. They assigned this band (which occurs at somewhat shorter wavelengths for the helical polymers) to the ether of the acetal chromophore. This assignment is essentially consistent with the results obtained by Johnson and coworkers on unsubstituted monosaccharides. 

Chondroitin is quite similar to hyaluronic acid, with the exception that the 4-hydroxyl group of the IV-acetylglycopyranosylamine is now axial instead of equatorial (see formula 13 for hyaluronic acid). This polysaccharide may be sulfated at C-6 of the IV-acetylgalactopyranosylamine, to form chondroitin 6-sulfate. Chondroitin and chondroitin 6-sulfate have... 

The plant cell wall contains different types of polysaccharides, proteins (structural glycoproteins and enzymes), lignin and water, as well as some inorganic components (1, 14-16). The plant cell suspensions, however, grow as a population of cells with a primary cell wall(17). The main components of these walls are cellulose-free polysaccharides and pectic polysaccharides in particular, which constitute 1/3 of their dry weight. (18). Some fragments, e g. methanol, acetic, ferulic and p-cumaric acids, are connected with the pectic polysaccharides by ester bonds with the carboxylic and hydroxylic groups. 

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