Iodine reaction with amylopectin

Starches differ in their chemical composition and, except in rare instances, are mixtures of two structurally different polysaccharides, amylose and amylopectin. The proportions of these present in natural starches depend upon the source, although in most starches amylopectin is the main component, amounting to about 70-80 per cent of the total. An important qualitative test for starch is its reaction with iodine amylose produces a deep blue colour and amylopectin solutions produce a blue-violet or purple colour. 

The quantity of amylose may be determined in starches or other mixtures by a characteristic reaction with iodine. Amylose combines with iodine to form a deep-blue complex, which is responsible for the color of starch indicators. Amylopectin solutions are colored blue-violet or purple. The intensity of the amylose-iodine complex can be measured in a spectrophotometer, or titrimetric measurements can be made of the amount of iodine taken up in forming the amylose-iodine complex. 

A few other polysaccharides which have colour reactions with iodine, e.g. amylopectin and pectin B, also exhibit Cotton effects at about 600 nm. The weak peaks at about 350 nm are probably caused by iodine molecules associated outside the helix. 

To determine the amylose content of starch, the iodine reaction has been most commonly used because amylose and amylopectin have different abilities to bind iodine. The methods such as blue value (absorbance at 680 nm for starch-iodine complex using amylose and amylopectin standards), and potentiometric and amperometric titration have been used for more than 50 years. These procedures are based on the capacity of amylose to form helical inclusion complexes with iodine, which display a blue color characterized by a maximum absorption wavelength (kmax) above 620 nm. During the titration of starch with iodine solution, the amount (mg) of iodine bound to 100 mg of starch is determined. The value is defined as iodine-binding capacity or iodine affinity (lA). The amylose content is based on the iodine affinity of starch vs. purified linear fraction from the standard 100 mg pure linear amylose fraction has an iodine affinity of 19.5-21.0mg depending on amylose source. Amylopectin binds 0-1.2mg iodine per 100mg (Banks and Greenwood, 1975). The amylose content determined by potentiometric titration is considered an absolute amylose content if the sample is defatted before analysis. 

Both the amylose and amylopectin components of starch form complexes with iodine, but early studies showed that there is no connection between the iodine reaction and the reducibility of starch fractions.63 The complex of amylose is pure blue, whereas the complex of amylopectin is blue-violet.5864 Thus, the varying amylose-to-amylopectin ratio can be one of the factors responsible for the various shades of blue color exhibited by various varieties of starch. Amylopectin takes up less iodine than does amylose. Also the course of complex formation uptake is different, as is evident65 from Fig. 2. 

A method of determining airborne iodine has also been reported.241 Here, iodine is absorbed into 5% aqueous KI and spectrophotometrically determined at 590 nm in the form of its complex with starch. This method is selective with respect to bromine and chlorine, and the sensitivity of this method is 0.25 mg of I2 per m3 of air. The concentration of the, 31I isotope in water can be determined by a method involving isotope exchange in the starch-iodine complex.242 Flow-injection determination of ascorbic acid (0.1-40 mg/mL) has been proposed.243 Iodine is generated in the flow system as I3- ions, which are in turn exposed to starch to produce a steady signal at 350 and 580 nm. Ascorbic acid provides inversed maxima which are measured. This method is recommended for analysis of ascorbic acid in fruit juice, jam, and vitamin-C preparations. Use of the blue complex has also been reported for determination of sodium dichloro-isocyanurate in air.244 Obviously the blue reaction is applicable in the determination of amylose, amylopectin, and starch,245-252 as well as modified starches.245,253-255... 

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