Iodine complexes of amylose

The starch-iodine complex of amylose. The amylose helix forms a blue charge-transfer complex with molecular iodine. 

The Interaction of Sodium Dodecyl Sulfate, a Competing Ligand, with Iodine Complexes of Amylose and Amylopectin... 

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. 

Figure 16-6 (a) Schematic structure of the starch-iodine complex. The amylose chain forms a helix around l6 units. [Adapted from A T. Calabrese and A. Khan, "Amylose-lodine Complex Formation with Kl Evidence for Absence of Iodide Ions Within the Complex." J. Polymer Sci. 1999, A37,2711.] (fc>) View down the starch helix. Showing iodine inside the helix.8 [Figure kindly provided by R. D. Hancock, [rower Engineering, Sett Lake City.]... 

Structure of the helical complex of amylose with iodine (I2). The amylose forms a left-handed helix with six glucosyl residues per turn and a pitch of 0.8 nm. The iodine molecules (I2) fit inside the helix parallel to its long axis. 

Using results of these kinds of studies, the characteristic structure of amylose can be differentiated from that of amylopectin. Amylose has a small number of branches and crystallizes and precipitates when complexed with 1 -butanol. The iodine affinity of amylose is much greater (i.a. 18.5 to 21.1) than that of amylopectin (i.a. 0.0 to 6.6),79,152-158,163,169-174 and the iodine affinity of amylose (3-limit dextrin is similar to that of the parent amylose. The average chain length of amylose (3-limit dextrins is much larger than that of the amylopectin (3-limit dextrin.160... 

Inclusion complexes of amylose are rather well defined, and a consistent theory of such complexes is available that explains amylose complexes with iodine, fatty acids, alcohols, and other guest molecules.4,5 This subject is surveyed in this article because of the growing interest and importance of such complexes in pharmacology and in the food industry. It is probable that starch in its biological sources (tubers, granules) exists in the form of native complexes with proteins, lipids, mineral salts, and water. 

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. 

Amylose is a unique polysaccharide which forms a helical blue-coloured complex with iodine (I5). It also forms helical complexes with a variety of organic compounds such as 1-butanol, 1-pentanol, cyclohexanol, SDS etc. The interaction of SDS, a competing ligand with iodine (I ) complexes of amylose and amylopectin is studied spectrophotometrically. It is observed that the reduction in absorbance at 640 nm accompanied by the blue shift (640-570 nm) in the absorption spectrum is governed by the sequence of addition of the reagents, implying that this Interaction is closely associated with the coil—>hellx transition of the polymer chain. Perturbation of this complex with sodium thiosulphate and urea has revealed that the transition from helix—>coil is rather sluggish and hydrophobic interactions play an important role in the stability of this complex. 

The Neoamylose forms with iodine and analogous compounds molecular complexes. X-ray diffractograms show the same intensity distribution with scattering angle as complexes of amylose from native potato starch. In these molecular complexes amylose formes V-helices. The binding ciq>acity for iodine was higher for the new polymer. 

From measurements of the dichroism of flow of amylose-iodine solutions,161 and from studies of the optical properties of crystalline amylose platelets and iodine-stained platelets,163 it was shown, following the suggestion of Hanes, that a helical configuration of the amylose in this complex is probable. This was later confirmed by x-ray measurements (see p. 378) the iodine atoms were shown to be situated in the core of helically-oriented amylose molecules. 

Although the dipolar and resonating nature of the interaction of amylose and iodine is well established, Schlamowitz173 regards the iodine in a starch complex as being in a predominantly non-polar form, and Meyer and Bern-feld174 refute the helix theory and consider that adsorption of iodine occurs on colloidal micelles in amylose solutions. Most of the experimental facts which Meyer presents can, however, be satisfactorily explained on the helical model. 

Rundle and coworkers166 found that the wave length of maximum absorption (Amflx) of the amylose-iodine complex is related to the chain length... 

Starch consists of two main components amylose (insoluble in cold water) and amylopectin (soluble in cold water). Amylose, which accounts for about 20 per cent by weight of starch, has an average molecular weight of over 10. It is a polymer of glucopyranose units linked together through a l,4 -linkages in a linear chain. Hydrolysis of amylose produces maltose. Amylose and iodine form a colour complex, which is blue/black. This is the colour reaction of iodine in starch, a confirmatory test for the presence of starch. 

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