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Chemical and Functional Properties of Food Saccharides

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© 2004 by CRC Press LLC<br />

aqueous medium, to reach a low energy state. The two chains in the double helix<br />

can be arranged in either parallel or antiparallel orientation. 2,3,29 This recrystallization<br />

or aging process is known as retrogradation, which is responsible for bread staling<br />

<strong>and</strong> syneresis <strong>of</strong> gravy. Double helices <strong>of</strong> amylose chains are packed in a hexagonal<br />

unit that consists <strong>of</strong> six double helices <strong>and</strong> an empty channel at the center <strong>of</strong> the<br />

packing unit <strong>and</strong> has ca. 36 water molecules in each unit. This type <strong>of</strong> unit packing<br />

displays a B-type x-ray pattern. 2,3,30,31 Another type polymorph, the A-type x-ray<br />

pattern, is not found in retrograded native amylose.<br />

In the presence <strong>of</strong> many chemicals that consist <strong>of</strong> a hydrophobic moiety, such<br />

as alcohols <strong>and</strong> fatty acids (known as complexing agents), amylose molecules can<br />

form helical complexes with these chemicals by having the chemicals located inside<br />

<strong>of</strong> the hydrophobic cavity <strong>of</strong> the helix as inclusions. 32 Depending on the size <strong>of</strong> the<br />

cross-section <strong>of</strong> the complexing agent, amylose can form single helices <strong>of</strong> different<br />

sizes to accommodate the diameters <strong>of</strong> the complexing agents. It has been reported<br />

that sizes <strong>of</strong> amylose single helices <strong>of</strong> six, seven, <strong>and</strong> eight glucose units per turn<br />

are found when complexed with n-butyl alcohol (linear molecule), isobutyl alcohol<br />

(branched molecule), <strong>and</strong> α-naphthol (bulky molecule), respectively, by using electron<br />

microscopy <strong>and</strong> x-ray diffraction 33 <strong>and</strong> by enzymatic method. 34 X-ray diffraction<br />

<strong>of</strong> amylose single-helical complexes gives V-type patterns. 30<br />

7.2.2 AMYLOPECTIN<br />

Amylopectin is a highly branched molecule, consisting <strong>of</strong> α 1-4 linked D-glucopyranose<br />

chains that are connected by α 1-6 branch linkages. Amylopectin has a very<br />

high molecular weight, varying between hundreds <strong>of</strong> thous<strong>and</strong>s to tens <strong>of</strong> millions<br />

anhydroglucose units (Table 7.1). 35 Figure 7.1 shows a plot <strong>of</strong> the relationship<br />

between molecular weight <strong>and</strong> gyration radius <strong>of</strong> the amylopectin molecule. These<br />

analytical results show that molecular weights <strong>of</strong> waxy starch amylopectins are<br />

higher than those <strong>of</strong> normal starch counterparts.<br />

Branch chains <strong>of</strong> amylopectin molecules can be categorized to the A chains that<br />

are chains whose reducing ends attach to other B or C chains but do not carry any<br />

other chains; the B chains have reducing ends attached to other B or C chains <strong>and</strong><br />

also carry other A or B chains; the C chain is the only chain <strong>of</strong> the molecule carrying<br />

a reducing end. The A chains are generally short <strong>and</strong> extend within one cluster. The<br />

B chains have different chain lengths, B 1 chains have lengths that extend within one<br />

cluster, B 2 chains extend through two clusters, B 3 chains through three clusters, <strong>and</strong><br />

so on. 36 The bimodal branch-chain length distribution <strong>of</strong> amylopectin differs from<br />

the single modal distribution <strong>of</strong> glycogen 37 <strong>and</strong> phytoglycogen. 38 Branch chain<br />

lengths <strong>of</strong> amylopectin vary with botanical sources <strong>of</strong> the starch, which control the<br />

polymorphic forms <strong>of</strong> crystalline structure, 39 gelatinization, pasting, <strong>and</strong> retrogradation<br />

properties <strong>of</strong> the starch. 40<br />

Branch chains <strong>of</strong> amylopectin are arranged in clusters. 1 After native granular<br />

waxy maize starch was hydrolyzed by acid at room temperature, Yamaguchi et al., 41<br />

using transmission electron microscopy, observed worm-like cluster structures that<br />

resisted acid hydrolysis. The worm-like cluster is attributed to the crystalline structure<br />

<strong>of</strong> outer chains <strong>of</strong> amylopectin molecules. The amorphous structure <strong>of</strong> the waxy

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