Linear polysaccharide

Mention has already been made of the numerous effects attendant upon chemical substitutions on the polysaccharide linear chain. Natural branches impart a dispersion stability to amylopectin that is not afforded amylose. One only has to compare cellulose ethers, deesterified chitin, and the lysis product of protopectin with the underivatized parent compound to appreciate the impact of chemical substituents on functionality. The loosening of compact, parallel structures with alkyl, hydroxyalkyl, and alkoxyl groups facilitates hydration and transforms insoluble, refractory polysaccharides to soluble, reactive polysaccharides. Not only do these substituents obstruct the crystallization tendency, they almost always confer secondary functionalities like q enhancement and foam, suspension, and freeze-thaw stabilization. 

The cellulose is the highest-molecular-weight polysaccharide, linear polymer of D-anhydroglucopyranose units linked together by jS-l,4-glucosidic bonds (Fig. 21.1). General formula of cellulose is described as (C6Hio05) = 10,000-15,000- where n depends on the cellulose source material [5, 6]. 

The distinctions between these homopolymers arise from the different ways in which the monomer units are hooked together in polyacetal chains. Starch (qv), plant nutrient material, is composed of two polysaccharides a-amylose and amylopectin. cx-Amylose is linear because of exclusive a (1 — 4) linkages, whereas amylopectin is branched because of the presence of a (1 — 6) as well as a (1 — 4) links. The terms linear and branched refer only to primary stmcture. 

Plant stmctural material is the polysaccharide cellulose, which is a linear P (1 — 4) linked polymer. Some stmctural polysaccharides iacorporate nitrogen iato thek molecular stmcture an example is chitin, the material which comprises the hard exoskeletons of kisects and cmstaceans. Chitki is a cellulose derivative whereki the OH at C-2 is replaced by an acetylated amino group (—NHCOCH ). Microbial polysaccharides, of which the capsular or extracellular (exopolysaccharides) are probably the most important class, show more diversity both ki monomer units and the nature of thek linkages. 

Normal com starch is composed of 20—30% of the linear polysaccharide amylose and 70—80% of the branched polysaccharide amylopectin. 

Like guaran, and the endosperm polysaccharides of other legumes, locust bean (carob)gum [9000-40-2] is also a galactomaiman. Like guaran, it has a linear backbone of (1 — 4)-1inked P-D-mannopyranosyl units. However, in locust bean gum, approximately one of every 3.9 P-D-mannopyranosyl units, on the average, is substituted with an a-D-galactopyranosyl unit attached at 0-6. 

An important characterization parameter for ceUulose ethers, in addition to the chemical nature of the substituent, is the extent of substitution. As the Haworth representation of the ceUulose polymer shows, it is a linear, unbranched polysaccharide composed of glucopyranose (anhydroglucose) monosaccharide units linked through thek 1,4 positions by the P anomeric configuration. 

However, fine grinding of iasoluble dietary fiber such as bran reduces WHC. In general, branched polysaccharides are more soluble than are linear polysaccharides because close packing of molecular chains is precluded. WHC is strongly kifluenced by the pentosan components of cell-waU dietary fiber and varies with the stmcture and source of these hemiceUuloses. 

Molecular Interactions. Various polysaccharides readily associate with other substances, including bile acids and cholesterol, proteins, small organic molecules, inorganic salts, and ions. Anionic polysaccharides form salts and chelate complexes with cations some neutral polysaccharides form complexes with inorganic salts and some interactions are stmcture specific. Starch amylose and the linear branches of amylopectin form inclusion complexes with several classes of polar molecules, including fatty acids, glycerides, alcohols, esters, ketones, and iodine/iodide. The absorbed molecule occupies the cavity of the amylose helix, which has the capacity to expand somewhat to accommodate larger molecules. The starch—Hpid complex is important in food systems. Whether similar inclusion complexes can form with any of the dietary fiber components is not known. 

TSK-GEL PW type columns are commonly used for the separation of synthetic water-soluble polymers because they exhibit a much larger separation range, better linearity of calibration curves, and much lower adsorption effects than TSK-GEL SW columns (10). While TSK-GEL SW columns are suitable for separating monodisperse biopolymers, such as proteins, TSK-GEL PW columns are recommended for separating polydisperse compounds, such as polysaccharides and synthetic polymers. 

Polysaccharides TSK-GEL GMPWxl TSK-GEL GSOOOPWxl -I- TSK-GEL G3000PWxi Large pore size, linear calibration curve, small particles, high resolving power... 

The macromolecules of cells are built of units—amino acids in proteins, nucleotides in nucleic acids, and carbohydrates in polysaccharides—that have structural polarity. That is, these molecules are not symmetrical, and so they can be thought of as having a head and a tail. Polymerization of these units to form macromolecules occurs by head-to-tail linear connections. Because of this, the polymer also has a head and a tail, and hence, the macromolecule has a sense or direction to its structure (Figure 1.9). 

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. 

Mutant YE-2 of Rhizobium meliloti excretes a mixture of soluble polysaccharides that include a complex succinoglycan having a branched octasaccharide repeat as well as a simple galactoglucan (22) having a linear disaccharide repeat.102 In contrast to the case of the succinoglycan, oriented fibers of the potassium salt of 22 have yielded good X-ray data and its three-dimensional structure has been established.39 The polymer forms a two-fold helix of pitch... 

This group includes a set of anionic polysaccharides secreted by unrelated bacteria. The common theme, however, is that their main chains have the same tetrasaccharide repeat. Although (high acyl) native gellan (42) and (deacylated) gellan (40,41) are linear polymers, welan (43) is a branched polymer in which a monosaccharide side chain is regularly attached to each repeat. Other members of this family, such as S-657 and rhamsan, are also branched, like welan."0... 

Arabinogalactans (AGs) are widely spread throughout the plant kingdom. Many edible and inedible plants are rich sources of these polysaccharides. AGs occur in two structurally different forms described as type I and type II, associated with the pectin cell-wall component by physical bonds and some of them are covalently linked to the complex pectin molecule as neutral side chains. Commercial pectins always contain AG 10-15%). AG of type I has a linear (1 4)-y0-o-Galp backbone, bearing 20-40% of of-L-Ara/ residues (1 5)-linked in short chains, in general at position 3. It is commonly found in pectins from citrus, apple and potato [6]. Recently, this AG type has been isolated from the skin of Opuntia ficus indica pear fruits [372]. 

Recent progress of basic and application studies in chitin chemistry was reviewed by Kurita (2001) with emphasis on the controlled modification reactions for the preparation of chitin derivatives. The reactions discussed include hydrolysis of main chain, deacetylation, acylation, M-phthaloylation, tosylation, alkylation, Schiff base formation, reductive alkylation, 0-carboxymethylation, N-carboxyalkylation, silylation, and graft copolymerization. For conducting modification reactions in a facile and controlled manner, some soluble chitin derivatives are convenient. Among soluble precursors, N-phthaloyl chitosan is particularly useful and made possible a series of regioselective and quantitative substitutions that was otherwise difficult. One of the important achievements based on this organosoluble precursor is the synthesis of nonnatural branched polysaccharides that have sugar branches at a specific site of the linear chitin or chitosan backbone [89]. 

---