Amylose with iodine, structure

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. 

Starches can be separated into two major components, amylose and amylopectin, which exist in different proportions in various plants. Amylose, which is a straight-chain compound and is abundant in potato starch, gives a blue colour with iodine and the chain assumes a spiral form. Amylopectin, which has a branched-chain structure, forms a red-purple product, probably by adsorption. 

Largely because the 0-6 hydroxyls of all six residues of one helix turn are in equivalent positions in the V, V -iodine and vDMS0 structures gg in Vh and Vh-iodine, gt in VDMsq)> thus forming symmetric intramolecular hydrogen bonds, all residues in these structures are equivalent. However, in Va-amylose, with its mixture of 0-6 positions, molecular sixfold symmetry is not present in the helix and instead, a 2q screw axis along the helix axis exists, thus combining three residues of one half-turn into the asymmetric unit. Nonetheless, the helix backbone still resembles a six-fold helix. 

Starch is composed of macromolecular components, a-amylose and (i-aim -lose. The former reacts irreversibly with iodine to form a red adduct. (i-Aim losc. on the other hand, reacts with iodine forming a deep blue complex. Because this reaction is reversible, [3-amyl0sc is an excellent choice for the indicator. The undesired alpha fraction should be removed from the starch. The soluble starch that is commercially available, principally consists of (3-amylose. (3-Amylose is a polymer of thousands of glucose molecules. It has a helical structure into which iodine is incorporated as I5. ... 

Since several synthetic polymers also develop a blue color upon reaction with iodine, it is likely that they have a helical structure similar to that of amylose. Therefore it is probable that the aforementioned complexes of synthetic polymers with starch can exist in the form of a double helix. 

Solid-state cellulose can also be noncrystalline, sometimes called amorphous. Intermediate situations are also likely to be important but not well characterized. One example, nematic ordered cellulose has been described [230]. In most treatments that produce amorphous cellulose, the whole fiber is severely degraded. For example, decrystallization can be effected by ball milling, which leaves the cellulose as a fine dust. In this case, some crystalline structure can be recreated by placing the sample in a humid environment. Another approach uses phosphoric acid, which can dissolve the cellulose. Precipitation by dilution with water results in a material with very little crystallinity. There is some chance that the chain may adopt a different shape (a collapsed, sixfold helix) after phosphoric acid treatment. This was concluded because the cellulose stains blue with iodine (see Figure 5.12), similar to the sixfold amylose helix in the starch-iodine complex. 

Our earlier studies on the ligand Induced structural changes in amylose partially complexed with iodine have shown that competing ligand produces a... 

Amylose. A component (20-30%) of starch surrounded by amylopectin. A. is a linear a-l,4-glucan, Mr 50000-200000 (see figure at starch). Crystalline A. occurs in various polymorphic forms (A, B, C, and V-A.), that differ in conformation and crystal packing. A. is soluble in water and gives the characteristic blue color with iodine-potassium iodide solution (Lugol s solution) (formation of inclusion compounds, traces of iodide ions are necessary for occurrence of the blue color, formation of I5 ions I -1 I I -1). Because of its predominately unbranched structure, A. can be degraded to oligosaccharides both by a- and by /S-amylase. The screw-like (helical) conformation also allows the formation of inclusion compounds with alcohols. 

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. 

Polycrystalline and well-oriented specimens of pure amylose have been trapped both in the A- and B-forms of starch, and their diffraction patterns84-85 are suitable for detailed structure analysis. Further, amylose can be regenerated in the presence of solvents or complexed with such molecules as alcohols, fatty acids, and iodine the molecular structures and crystalline arrangements in these materials are classified under V-amylose. When amylose complexes with alkali or such salts as KBr, the resulting structures86 are surprisingly far from those of V-amyloses. 

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