Butanol, complex with amylose, structure

Organic molecules such as 1-butanol form a similar complex with amylose in which the 1-butanol molecules are complexed in the hydrophobic interior of the helix. These complexes have crystalline properties and produce X-ray diffraction patterns called a V-pattem [19] (see Fig. 6.6). Electron microscopy and electron diffraction studies have indicated that the complex is a folded helical chain with a lamellar structure [20-24]. The helical chain folds every 100 A, giving an antiparallel structure in which the helices are 13 A in diameter (see Fig. 6.4C). 

The unit cell dimensions of all crystalline amyloses that have been determined in some detail, are listed in Table I. Also included are some intermediate forms between the va and Vjj amyloses (Ji.) and some V-amylose complexes with n-butanol, which, although not yet completely determined, have been added to illustrate the range of variability in unit cell dimensions. In the case of the Va-BuOH complex, a doubling of one unit cell axis was detected after a careful study of electron diffraction diagrams of single crystals ClO). A consequence of the doubling is that the unit cell now contains four chains, instead of the two normally found in amylose structures. Cln a strict sense, the A- and B-amyloses should also be considered as four-chain unit cells, but their double-helical structure still results in only two helices per cell) (13,1 ). 

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... 

It should be noted that the different structures of amylose and amylopectin confer distinctive properties to these polysaccharides (Table II). The linear nature of amylose is responsible for its ability to form complexes with fatty acids, low-molecular-weight alcohols, and iodine these complexes are called clathrates or helical inclusion compounds. This property is the basis for the separation of amylose from amylopectin when starch is solubilized with alkali or with dimethylsulfoxide, amylose can be precipitated by adding 1-butanol and amylopectin remains in solution. 

X-ray diffraction analysis754 of a series of amylose complexes with lower and higher fatty acids revealed that the crystal structures depend on whether amylose was complexed in the dry or wet state. Both the 6, and 7i helical conformations of amylose were found in these complexes. The conformation appears to depend on the length of the hydrophobic moiety. Dry amylose forms crystalline complexes with a unit cell identical to that of the anhydrous 1-butanol-starch complex (lattice parameters a = b = 25.6 A). An orthorhombic unit cell was proposed for the 7i -helical structure of the wet complexes of monobasic acids (acetic, butanoic, pentanoic, hexanoic,... 

Fourier-Transform infrared (FTIR) second-derivative spectra of TPS and vinyl alcohol copolymer systems with a droplet-like structure, in the range of starch ring vibrations between 960 and 920 cm provide an absorption peak at about 947 cm (Figure 8.7), as observed for amylose when complexed (V-type complex) with low MW molecules such as butanol and fatty acids. 

Partial hydrolysis with alpha amylase (EC 3.2.1.1), followed by gel chromatography, has been used to study aspects of the physical structures of the amylose complexes formed with such organic compounds as 1-butanol, and of retrograded amylose. Differences were detected.387b... 

The starch-iodine(iodide) complex has been known for centuries. The presence of iodide, iodine and a sufficient amount of water [58] is necessary for the formation of the deep blue complex. Bundle [59] studied its structure by X-ray diffraction, and his results suggest a sixfold symmetrical helical conformation. Starch forms helical complexes not only with triiodide but also with many organics such as butanol or fatty acids, and this property can be used to separate amylose, which forms the helical complex, from other polycarbohydrates (amilopectins) which do not. Without complexing agents the helical conformation of amylose, called amylose-V, is stable only in the crystalline state. The structural parameters of the amylose-iodine(triiodide) complex were determined by Saenger etal. [60,61] in experiments on several model compounds. They found that six monomer units form a turn of the... 

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