Polysaccharide of starch

FIGURE 7-15 Amylose and amylopectin, the polysaccharides of starch, (a) A short segment of amylose, a linear polymer of o-glucose residues in (ctl —>4) linkage. A single chain can contain several thousand glucose residues. Amylopectin has stretches of similarly linked residues between branch points, (b) An (ctl —>6) branch point of amylopectin. (c) A cluster of amylose and amylopectin like that believed... 

Amylose, a linear, high molecular weight (l- -U)-a-D-glucan, is one of the principal polysaccharides of starch. Because of the longstanding utility of starch as a raw material, and its widespread botanical availability, its structure and properties have been studied for centuries. Since the more recent realization that almost all varieties of starch are composed of two polysaccharides - the linear amylose and the branched amylopectin - a significant share of interest has shifted to the study of these components. Of particular interest has been the observation that both components occur naturally in crystalline form in the starch granule. 

Starch is a polysaccharide found in many plant species. Com and potatoes are two common sources of industrial starch. The composition of starch varies somewhat in terms of the amount of branching of the polymer chains (11). Its principal use as a flocculant is in the Bayer process for extracting aluminum from bauxite ore. The digestion of bauxite in sodium hydroxide solution produces a suspension of finely divided iron minerals and siUcates, called red mud, in a highly alkaline Hquor. Starch is used to settle the red mud so that relatively pure alumina can be produced from the clarified Hquor. It has been largely replaced by acryHc acid and acrylamide-based (11,12) polymers, although a number of plants stiH add some starch in addition to synthetic polymers to reduce the level of residual suspended soHds in the Hquor. Starch [9005-25-8] can be modified with various reagents to produce semisynthetic polymers. The principal one of these is cationic starch, which is used as a retention aid in paper production as a component of a dual system (13,14) or a microparticle system (15). 

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). 

Since polysaccharides are the most abundant of the carbohydrates, it is not surprising that they comprise the greatest part of industrial utiliza tion (9,22). Most of the low molecular weight carbohydrates of commerce are produced by depolymerization of starch. Polysaccharide materials of commerce can be thought of as falling into three classes cellulose, a water-insoluble material starches, which are not water-soluble until cooked and water-soluble gums. 

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. 

Unlike many of the catalysts that chemists use in the laboratory, enzymes are usually specific in their action. Often, in tact, an enzyme will catalyze only a single reaction of a single compound, called the enzyme s substrate. For example, the enzyme amylase, found in the human digestive tract, catalyzes only the hydrolysis of starch to yield glucose cellulose and other polysaccharides are untouched by amylase. 

Nitrostarch (NS) is a nitrate ester (more properly a mixt of several nitrate esters) of starch, which is a plant-product polysaccharide of the general formula (CgHujOj) The general molecular formula for NS is [C6H7(OH)x-(0NO2)y]n where x + y - 3, The following empirical relation, similar to that used for NC... 

A polysaccharide such as xanthan gum is a chain of sugars. Some familiar polysaccharides are starch and cellulose. The backbone of xanthan gum is similar to cellulose, but the trisaccharide side chains of mannose and glucuronic acid make the molecule rigid, and allow it to form a right-handed helix. These features make it interact with... 

The main hurdle for the use of starch as a reinforcing phase is its hydrophillicity leading to incompatibility with polymer matrix and poor dispersion causing phase separation. Two strategies have been adopted to improve the performance of polysaccharides. 

A similar procedure was adopted for synthesis of nanoparticles of cellulose (CelNPs). The polysaccharide nanoparticles were derivatised under ambient conditions to obtain nanosized hydrophobic derivatives. The challenge here is to maintain the nanosize even after derivatisation due to which less vigorous conditions are preferred. A schematic synthesis of acetyl and isocyanate modified derivatives of starch nanoparticles (SNPs) is shown in scheme 3. The organic modification was confirmed from X-ray diffraction (XRD) pattern which revealed that A- style crystallinity of starch nanoparticles (SNPs) was destroyed and new peaks emerged on derivatisation. FT-IR spectra of acetylated derivatives however showed the presence of peak at 3400 cm- due to -OH stretching indicating that the substitution is not complete. 

Biopolymers have diverse roles to play in the advancement of green nanotechnology. Nanosized derivatives of polysaccharides like starch and cellulose can be synthesized in bulk and can be used for the development of bionanocomposites. They can be promising substitutes of environment pollutant carbon black for reinforcement of rubbers even at higher loadings (upto SOphr) via commercially viable process. The combined effect of size reduction and organic modification improves filler-matrix adhesion and in turn the performance of polysaccharides. The study opens up a new and green alternative for reinforcement of rubbers. 

A combination of graded calcium carbonate particle sizes, a nonionic polysaccharide of the scleroglucan type, and a modified starch, has been claimed for use as a fluid loss formulations [915]. It is important that the calcium carbonate particles are distributed across a wide size range to prevent filtration... 

Carbohydrates are classified based upon the products formed when they are hydrolyzed. Monosaccharides are simple sugars that cannot be broken down into simpler sugars upon hydrolysis. Examples of monosaccharides are glucose, ribose, deoxyribose, and fructose. Disaccharides contain two monosaccharide units and yield two monosaccharides upon hydrolysis. Examples of disaccharides are lactose, maltose, and sucrose. Polysaccharides are polymers of monosaccharide units and yield many individual monosaccharides upon hydrolysis. Examples of polysaccharides are starch, glycogen, and cellulose. 

Saliva begins the process of chemical digestion with salivary amylase. This enzyme splits starch molecules into fragments. Specifically, polysaccharides, or starches, are broken down into maltose, a disaccharide consisting of two glucose molecules. Salivary amylase may account for up to 75% of starch digestion before it is denatured by gastric acid in the stomach. 

Cultures of B. subtilis were introduced into the stems of young potato plants by Suit and Hibbert104 in an attempt to bring about replacement of starch by another polysaccharide. Sections of some of the resulting potatoes gave little or no color with iodine, and were provisionally designated starchless potatoes. However, based on analogy with recent developments in starch chemistry, it seems probable that the starchless potato was free from amylose, and contained only amylopectin. 

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. 

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