Molecular amylopectin

Com and rice starches have been oxidized and subsequently cyanoethylated (97). As molecular size decreases due to degradation during oxidation, the degree of cyanoethylation increases. The derivatized starch shows pseudoplastic flow in water dispersion at higher levels of cyanoethylation the flow is thixotropic. Com and rice starches have been oxidized and subsequently carboxymethylated (98). Such derivatives are superior in the production of textile sizes. Potato starch has been oxidized with neutral aqueous bromine and fully chemically (99) and physically (100) characterized. Amylose is more sensitive to bromine oxidation than amylopectin and oxidation causes a decrease in both gelatinization temperature range and gelatinization enthalpy. 

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. 

Molecular Structure. Most starches consist of a mixture of two polysaccharide types amylose, an essentially linear polymer, and amylopectin, a highly branched polymer. The relative amounts of these starch fractions in a particular starch are a major factor in determining the properties of that starch. 

Cellulose is a high molecular weight polymer of D-glucose with fi( 1 -4)-glycosidic bonds, found in plant fibres it is the major component of most plant tissues. Starch is another common polysaccharide, containing two polymers of glucose, amylose and amylopectin. It was used in some paint preparations and in the production of paper. Acid treatment of starch produces dextrins, which are used as adhesives and additives in water colour paintings. 

The labile nature of the components necessitates that, for fundamental investigations, the starch should preferably be extracted from its botanical source, in the laboratory, under the mildest possible conditions.26 Industrial samples of unknown origin and treatment should not be used. The characterization of the starch would appear to entail (1) dissolution of the granule without degradation, (2) fractionation without degradation, (3) complete analysis of the finer details of structure of the separated components (including the possibilities of intermediate structures between the extremes of amylose and amylopectin), and (4) the estimation of the size, shape, and molecular-weight distribution of these fractions. 

Methods which can be used to determine the size and shape of polysaccharides have been reviewed.107 (A critical survey of these has recently been given by Sadron108 and by Ogston.109) Special problems exist in the case of the undegraded starch components. In view of the branched nature of amylopectin and the large size of the amylose molecule, chemical methods of estimating size are inadequate, and it is questionable whether results are valid.38 The free components may also aggregate in aqueous solution. Study of derivatives is therefore more convenient, and the preparation of these is an essential preliminary to estimations of molecular size. 

The Results of Molecular-Weight Determinations on Amylopectin and its Derivaiives... 

Further measurements appear necessary before the molecular weights of the amylopectin component of starches can be adequately characterized, and it may well be that light-scattering is the only method which can be satisfactorily applied to these polysaccharides of very high molecular weight. Certainly, it is the only method which enables studies of very dilute solutions to be made with high accuracy, particularly in the case of aqueous solutions. 

These synthetic linear and branched molecules may be important as type polymers, particularly if the interconversion of amylose to amylopectin is intramolecular, in which case the initial molecular weight and molecular-weight distribution would be retained. There is the possibility that the in vitro synthesis may even result in a truly three-dimensional structure, as distinct from that of the natural component. 

Amylose has a lower molecular weight than amylopectin but forms linear chains while amylopectin has a higher molecular weight but forms more compact molecules. While both molecules have a structure mainly based on a-(l - 4)-D-glucose units, the amylopectin structure is branched at the a-(l - 6)-D-glucose units. 

Figure 8.4 Molecular structure of the amylose and amylopectin components of starch.

Pea starch granules are oval, sometimes fissured, with a diameter of 20-40 ym (13). Molecular and structural characteristics of the two main components of field pea starch—amylose and amylopectin—are important in determining functional properties (25,26). Smooth field pea starch concentrate contains 97.2% starch of which 30.3-37.8% is amylose (9,23,25-27), and wrinkled pea starch concentrate contains 94.8% starch, which is 64% amylose (26). The gelatinization temperature of smooth pea starch is between 64 to 69 C, and that of wrinkled pea starch is greater than 99 C to 115 C. Gelatinization temperature depends on maturity of field pea seed and amylose content (26,27). 

As described earlier in this book, the dendritic architecture is perhaps one of the most pervasive topologies observed at the macro and micro-dimensional length scales (i.e. jum-m). At the nanoscale (molecular) level there are relatively few natural examples of this architecture. Most notable are probably the glycogen and amylopectin hyperbranched structures that Nature uses for energy storage. 

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