Of amylopectin

Amylase occurs in many plants, such as barley, wheat, rye, soy beans, and potatoes, where it is generally accompanied by some a-amylase. [ -Amylase initiates hydrolysis at the nonreducing end of an amylose or amylopectin chain, and removes maltose units successively until the reducing end of the molecule is encountered in amylose or a branch is met in amylopectin. ( -Amylase is used commercially in the preparation of maltose symps. After P-amylase hydrolysis of amylopectin there remains a P-amylase limit dextrin. ( -Amylase has been used as a probe of the fine stmcture of amylopectin (43-46). 

Starch acetates may have low or high DS. The industrial importance of low DS acetates results from their abiUty to stabilize aqueous polymer sols. Low DS acetates inhibit association of amylose polymers and reduce the association of the longer outer chains of amylopectin. These properties are important in food appHcations. Highly derivatized starches (DS 2—3) are useful because of their solubiHty in organic solvents and abiHty to form films and fibers. 

Molecular Interactions. Various polysaccharides readily associate with other substances, including bile acids and cholesterol, proteins, small organic molecules, inorganic salts, and ions. Anionic polysaccharides form salts and chelate complexes with cations some neutral polysaccharides form complexes with inorganic salts and some interactions are stmcture specific. Starch amylose and the linear branches of amylopectin form inclusion complexes with several classes of polar molecules, including fatty acids, glycerides, alcohols, esters, ketones, and iodine/iodide. The absorbed molecule occupies the cavity of the amylose helix, which has the capacity to expand somewhat to accommodate larger molecules. The starch—Hpid complex is important in food systems. Whether similar inclusion complexes can form with any of the dietary fiber components is not known. 

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. 

A 0.2-g sample of amylopectin was analyzed to determine the fraction of the total glucose residues that are branch points in the structure. The sample was exhaustively methylated and then digested, yielding 50 /tmol of 2,3-dimethylglucose and 0.4 /tmol of 1, 2, 3, 6-tetramethylglucose. 

The structure of amylopectin according to Meyer is shown in Fig. 65. The single reducing end group is indicated by A all other terminal units are attached at the 1-position only. 

Methods which can be used to determine the size and shape of polysaccharides have been reviewed.107 (A critical survey of these has recently been given by Sadron108 and by Ogston.109) Special problems exist in the case of the undegraded starch components. In view of the branched nature of amylopectin and the large size of the amylose molecule, chemical methods of estimating size are inadequate, and it is questionable whether results are valid.38 The free components may also aggregate in aqueous solution. Study of derivatives is therefore more convenient, and the preparation of these is an essential preliminary to estimations of molecular size. 

The acetylation of amylopectin with pyridine and acetic anhydride presents more difficulty, even when using freeze-dried material,26 and the most satisfactory method is that involving prior dispersion in formamide, after which esterification occurs readily at room temperature. 

The viscosity of polymer solutions has been considered theoretically by Flory,130 but although this theory has been applied to cellulose esters,131 no applications have yet been made in the case of the starch components. Theoretical predictions of the effect, on [17], of branching in a polymer molecule have been made,132 and this may be of importance with regard to the viscometric behavior of amylopectin. 

It has not yet been possible to obtain samples of amylopectin which do not show some slight evidence of uptake of iodine by linear material in the early stages of an accurate potentiometric titration. Although this effect is presumably due to contaminating amylose, the presence of some long branches in the amylopectin cannot be excluded. Anderson and Greenwood190 have shown that in 0.01 M iodide solution, for concentrations of total free iodine less than 1 X 10-6 M, the amount of iodine bound by... 

Amylo-1 —> 6-glucosidase obtained by Cori and Larner218 from rabbit muscles, and R-enzyme isolated by Hobson, Whelan and Peat219 from potatoes and broad beans, are typical debranching enzymes, which will hydrolyze the 6 — 1-a-D-glucosidic linkage rather than the normal 4 —> 1-a-D linkage. These enzymes will therefore be particularly important in determinations of the fine structure of amylopectin, if they can be sufficiently well purified. 

The only example of this technique applied to the amylose component is that already described, of the action of Z-enzyme on the /3-limit dextrin. In the case of amylopectin, enzymic methods enable a distinction to be made between the proposed laminated and highly ramified structures (I and III, in Fig. 1, page 352). The method used by Peat and coworkers101 involves the successive action of /3-amylase and R-enzyme on waxy maize starch. /3-Amylolysis will degrade A-chains down to two or three units from the 6 —> 1-a-D interchain linkages. These latter linkages will protect the... 

The Semicrystalline Structure of Amylopectin. Amylopectin crystallises according to a cluster molecule,25 as shown in Figure 8b. Within this structure there are crystalline and amorphous regions. An... 

Figure 8 The structure of amylopectin (a) organisation of the molecule (b) crystalline and amorphous regions (c) possible double helix structure...

The data19 summarized in Figure 1 show that the extent of the hydrolysis of soluble potato starch by barley beta amylase reaches a limit which is independent of the concentration of the amylase. The data are typical of the action of beta amylases on unfractionated starches, when the hydrolyses are carried out at or near pH 4.5.1 3 6 19 20 Under these conditions, the hydrolysis of unfractionated starches usually ceases when 60 to 64% of the maltose theoretically obtainable from the substrate has been formed. The exact value of the limit obviously will depend upon the concentration of amylopectin in the starch and upon its structure. 

Detection of the C-6 signal of the nonreducing end-group of amylopectin was possible for the 4,6-diphenylboronate derivative, which is associated with nonreducing end-groups and whose C-4 and C-6 signals are displaced99 upfield and downfield, respectively (see Fig. 7). 

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