Retrogradation of amylose. When heated to about 50 °C, in
the presence of water, the amylose in the granule swells; the crystalline
structure of the amylopectin disintegrates and the granule
ruptures. The polysaccharide chains take up a random configuration,
causing swelling of the starch and thickening of the surrounding
matrix such as, gelatinization—a process that renders
the starch easily digestible. On cooling/drying, recrystallization
(retrogradation) occurs. This takes place very fast for the amylose
moiety as the linear structure facilitates cross linkages by means of
hydrogen bonds. Figure 10 shows the formation of gel and micelle
on cooling of a concentrated solution of amylose (Belitz and
Grosch 1999). The branched nature of amylopectin inhibits its recrystallization
to some extent and it takes place over several days.
Retrograded amylose in peas, maize, wheat, and potatoes was
found to be highly resistant to amylolysis (Ring and others 1988).
The rate and extent to which a starch may retrograde after gelatinization
essentially depends on the amount of amylose present. Repeated
autoclaving of wheat starch may generate up to 10% RS.
The level obtained appeared to be strongly related to the amylose
content, and the retrogradation of amylose was identified as the
main mechanism for the formation of RS that can be generated in
larger amounts by repeated autoclaving (Berry 1986; Bjorck and
others 1990). During storage, the dispersed polymers of gelatinized
starch are said to undergo retrogradation to semicrystalline
forms that resist digestion by pancreatic -amylase. It forms a major
portion of RS in wheat bread and corn flakes (Englyst and
Cummings 1985), whereas only 25% of the RS in cooked, cooled
potatoes can be accounted for as retrograded amylose. The digestibility
of legume starch is much lower than that of cereal
starch, which is attributable to higher content of amylose in the
former. The digestibility of high amylose cereal starch is reported
to be significantly lower (Tharanathan and Mahadevamma 2003).
Native high-amylose starch is known to be high in type II RS (RS
2) (Berry 1986), which is defined as starch in its native granular
state that is resistant to digestion in the small intestine. This after
cooking and cooling gives high yields of type III RS (Berry 1986;
Sievert and Pomeranz 1989a) or retrograded starch (Englyst and