Polysaccharides, modification polymers

Chapter 15, written by H. N. Cheng and Qu-Ming Gu, discusses the application of biotransformations to polysaccharides modification. Polysaccharides are natural materials ideally suited for enzymatic modifications. The chapter introduces Upase-catalyzed and j8-galactosidase-catalyzed modifications of carbohydrate polymers. 

While the chemical structure of a polysaccharide is complex, most are composed of components with similar characteristics, which allow simultaneous manipulation of the entire polymer. Almost all polysaccharide modifications involve either cleaving an oxygen-carbon linkage between monomers or a reaction at a hydroxyl group. Reactivity at hydroxyls is reported either as the degree of substitution (DS), which is the average number of substitutions per monomer, or molar substitution (MS), which is the average number of moles of substituent per monomer. 

Alginate is a polymer composed of uronic acid monomers. While this acidic polysaccharide can be recovered from bacteria, the commercial source is brown seaweed. Both propylene glycol esterification and acetylation of the polymer cause an increase in the thickening capabilities of the gum. The acetylation of alginate by pseudomonal species demonstrates alternative biochemical methods for polysaccharide modification. 

McCormick C.L., Lichatowich D.K., Pelezo J.A., Anderson K.W., Homogeneous solirtion reactions of cellulose, chitin, and other polysaccharides, Modification of Natural Polymers, ACS Symposiitm Series No. 121, 1980, pp. 371-380. 

PolysuWde Process. One modification to the kraft process being appHed commercially is the polysulfide process (38). Under alkaline conditions and relatively low temperature (100—120°C), polysulfides oxidize the active end group of the polysaccharide polymer to an alkaH-stable aldonic acid. This reaction, known for many years (39), was not produced on a commercial scale until the development of an efficient method for in situ generation of the polysulfide in kraft white Hquor. 

Above we have shown the attractiveness of the so-called green nanocomposites, although the research on these materials can still be considered to be in an embryonic phase. It can be expected that diverse nano- or micro-particles of silica, silicates, LDHs and carbonates could be used as ecological and low cost nanofillers that can be assembled with polysaccharides and other biopolymers. The controlled modification of natural polymers can alter the nature of the interactions between components, affording new formulations that could lead to bioplastics with improved mechanical and barrier properties. 

Since sialic acid is a frequent terminal sugar constituent of the polysaccharide trees on glycoproteins, this method selectively forms reactive aldehydes on the most accessible parts for subsequent modifications. The carbohydrate polymer of a protein provides a long spacer arm that can be used to conjugate another large macromolecule, such as a second protein, with little steric problems. 

Due to the extreme variety of xylan structures, it is obvious that many kinds of enzymes are needed for their complete hydrolysis in nature. Xylanases (EC 3.2.1.8.) are the polysaccharide hydrolases responsible for the attack of the polymer backbone itself. The total hydrolysis or modification of heteroxylans requires in addition several different exo-glycosidases and esterases. The present knowledge of these enzymes is reviewed in this paper. 

The major polymers that make up the wall are polysaccharides and lignin. These occur together with more minor but very important constituents such as protein and lipid. Water constitutes a major and very important material of young, primary walls (2). The lignin is transported in the form of its building units (these may be present as glucosides) and is polymerized within the wall. Those polysaccharides which make up the matrix of the wall (hemicelluloses and pectin material) are polymerized in the endomembrane system and are secreted in a preformed condition to the outside of the cell. Further modifications of the polysaccharides (such as acetylation) may occur within the wall after deposition. Cellulose is polymerized at the cell surface by a complex enzyme system transported to the plasma membrane (3). 

Polysaccharides that have been modified chemically, or altered physically, have been used as adsorbents for affinity chromatography. The modification of the structure of polysaccharides has been achieved by introducing cross-linkages between the chains of the polymer and bifunctional reagents. The alteration of the properties of polysaccharides by physical means can be effected by embedding the polysaccharide in a network of the support material. The molecular in-... 

A modification of the monosaccharide units of polysaccharides may obviously be effected at different stages of the biosynthesis of a polymer (a) prior to formation of the activated form of a monosaccharide, (b) at the level of glycosyl nucleotides, (c) at the stage of formation of oligosaccharide intermediates, and (d) after the synthesis of a polymeric chain. 

Like with the KDO containing K-polysaccharides, one can observe also in this group of polysaccharides antigen modification by O-acetylation the K1 antigen and the K2 antigen occur in non acetylated and in acetylated forms (14, 18). Bacteria with the non acetylated polymers (Klac" and K2a) seem to be more pathogenic. 

Abstract Carbohydrates have been investigated and developed as delivery vehicles for shuttling nucleic acids into cells. In this review, we present the state of the art in carbohydrate-based polymeric vehicles for nucleic acid delivery, with the focus on the recent successes in preclinical models, both in vitro and in vivo. Polymeric scaffolds based on the natural polysaccharides chitosan, hyaluronan, pullulan, dextran, and schizophyllan each have unique properties and potential for modification, and these results are discussed with the focus on facile synthetic routes and favorable performance in biological systems. Many of these carbohydrates have been used to develop alternative types of biomaterials for nucleic acid delivery to typical polyplexes, and these novel materials are discussed. Also presented are polymeric vehicles that incorporate copolymerized carbohydrates into polymer backbones based on polyethylenimine and polylysine and their effect on transfection and biocompatibility. Unique scaffolds, such as clusters and polymers based on cyclodextrin (CD), are also discussed, with the focus on recent successes in vivo and in the clinic. These results are presented with the emphasis on the role of carbohydrate and charge on transfection. Use of carbohydrates as molecular recognition ligands for cell-type specific dehvery is also briefly... 

Advances in polymer synthesis, characterization and conjugation chemistry have stimulated the development of drug macromolecularization technology. In this regard, a variety of studies on insulin modification with polysaccharides, polyvinyls and polyethylene glycols have been carried out. 

There have been numerous investigations into the subsequent modification of bacterial and wood nanocelluloses. The additives range from other polysaccharides, albuminoids such as gelatine, different types of monomers and synthetic polymers, to metals, metal oxides, and inorganic fibers. On the... 

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