Amylosic chain

Amylases are exoen2ymes that attack amylose chains and result in the successive removal of maltose units from the nonreducing end. In the case of amylopectin, the cleaving stops two to three glucose units from the a-1,6-branching points. ( -Amylase [9000-91-3] is used for the production of maltose symps and for adjunct processing in breweries. The most important commercial products are made from barley or soybeans. 

There are two types of glucose chains in starch. One is a simple chain called amylose, and the other is a complex branched form called amylopectin. In the starch grains in a plant, amylopectin makes up the bulk of the material, from 50 to 80 percent by weight, made up of several million amylopectin molecules per starch grain. The rest is a much larger number of the smaller amylose chains, made up of 500 to 20,000 glucose units in each chain. Amylopectin molecules are made of several million glucose units. 

As a thickener (as opposed to a gel), it is amylose that has the main function. The long water-soluble chains increase the viscosity, which doesn t change much with temperature. Amylose chains tend to curl up into helixes (spirals) with the hydrophobic parts inside. This allows them to trap oils, fats, and aroma molecules inside the helix. 

A) Circular amylose-GA-1 complex and (B) corresponding binding model the balls represent starch-binding domain (SBD) and the lines represent amylose chains (C) linear amylose-mutant GA-1 complex and (D) corresponding binding model. Image size ... 

Fig. 13. Projection view of Vh-amylose on the a, b plane. The amylose chains are packed in an antiparallel manner in space group />212121. Guest water molecules are represented as filled circles in the helical canals and in interstitial sites between the helices...

Fig. 14. The Vh-amylose polyiodide inclusion compound shown as a simplified projection on the a, b plane. Guest water molecules are shown as filled circles in the interstitial sites. The guest polyiodide chains are situated inside the helical amylose chains and their cross-sections are shown here as stippled circles...

Senti and Witnauer206 have reported studies on the fiber diagrams from various alkali-amyloses. Specimens were obtained by deacetylating clamped specimens of amylose acetate with the appropriate alkali. The positions of the alkali ions and the lateral packing of the amylose chains were determined with the aid of Patterson projections. In the A - and B -modifica-tions, the fiber period was 22.6 A. (extension of 6 D-glucose units), whilst in the V -modification it was 8.0 A. These authors have also studied in detail the addition compounds of amylose and inorganic salts with special reference to the structure of the potassium bromide-amylose compound.206 Oriented alkali fibers were treated with the appropriate salt solution. Stoichiometric compounds were formed. The x-ray patterns from these showed that the addition compounds with potassium salts crystallized in... 

Amylose complexes (wet precipitates) were prepared with fluoro-benzene, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrabromoethane, bromo-form, and ferf-butyl alcohol. The conformation and packing of the amylose chains complexed with halogen-substituted hydrocarbons are the same as found in the complex with tert-butyl alcohol, namely,... 

The space group is P2i2i2 . The unit cell is pseudotetragonal, with a = b = 19.17 A (1.917 nm), and c = 24.39 A (2.439 nm), with two antiparallel chains per cell. The amylose chain is a left-handed 6(—1.355) helix, with three turns per crystallographic repeat. One molecule of dimethyl sulfoxide for every three D-glucose residues is located inside the helix. An additional 4 molecules of dimethyl sulfoxide and 8 of water are located in the interstices. The interstitial dimethyl sulfoxide is the source of additional layer-lines that are not consistent with the 8.13 A (813 pm) amylose repeat. The overall R factor is 35%, and, for the layer lines with amylose contribution alone, it is 29%. 

Table I. Measured and Computed Room Temperature Characteristic Ratio and Temperature Coefficients for Cellulosic and Amylosic Chains...

Figure 12. Snapshot as in Fig. 7 for an amylosic chain trajectory based on the rigid residue maltose map of Fig. 11. 

Figure 14. Directional correlation function as in Fig. 8 for amylosic chains based on the rigid residue model (filled circles) and relaxed residue model (open circles).

Figure 15. The mean trajectories of amylosic chains based on the rigid residue (filled circles) and relaxed residue (open circles) models projected into the XY plane of a coordinate system attached to a terminal residue. Circles represent the mean positions of successive glycosidic oxygens in the primary sequence. The persistence vector (mean end-to-end vector) for a chain of x residues is the vector (not shown) connecting the origin and the mean position of the glycosidic oxygen separated from it along the chain by x virtud bonds.

Figure 5. Molecular drawings of a) one single strand of an amylosic chain in the left-handed conformation, having a six-fold symmetry, repeating in 2.1 nm. b) the double-helix generated by the association of two single strands, through two-fold symmetry operation, c) and d) Space-filling plots of the double helix, projected along and perpendicular to the fiber axis, respectively.

Even though the products are not block copolymer structures, the work of Kadokawa and colleagues should be mentioned here. In a process that the authors named vine-twining polymerization (after the way that a vine plant grow helically around a support rod), the enzymatic polymerization of amylose is performed in the presence of synthetic polymers in solution, and the authors showed that the grown amylose chains incorporate the polymers into its helical cavity while polymerizing [184-191]. 

The nonbonded energy (van der Waals) is computed for isolated helical amylose chains as a function of the dihedral angles (, relative orientations of the glucose residues in the polysaccharide chain. In conformity with x-ray data, different helical conformations ere proposed for different crystalline modifications of amylose. 

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