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amylose content to retrogradation [91,145,160]. For DSC measurements, in
particular, the extent of retrogradation should be greater for waxy starches
because the DSC measures the recrystallization of amylopectin [91,142,160].
It is thus safe to say that the relation between the amylose/amylopectin ratio
and retrogradation is not straightforward, as other factors are involved.
If retrogradation is to take place, the chains must first aggregate, but a
minimum requirement for the aggregation of chains to occur has been shown
to be 8 to 10 glucose units [47,176]. The short chains of amylopectin have been
shown to be responsible for crystallization in the amylopectin molecule [177],
and chains with less than 15 glucose units do not take part in the crystallization
[158,177]. If the external chains of the amylopectin molecule are removed by
β-amylolysis, no retrogradation at all occurs [178a,b]. Amylopectin from
potato, tapioca, and kuzu starches, which are B-starches, retrograde to a different extent, which has been related to differences in average chain length
[178]. Amylopectin from cereals has also been shown to retrograde to a lesser
extent than pea, potato, and canna amylopectin, which has been attributed to
shorter average chain length in the cereal amylopectin [167,173]. The length
of the external chains in the amylopectin molecule is also of relevance [178a,b].
The transition temperature, Tc, at which the melting of the recrystallized
starch occurs is nearly the same for all the cereal starches (with the exception
of amylomaize), despite differences in gelatinization temperatures of up to
24°C [171]. The gelatinized starches are fully hydrated, and the recrystallized
(retrograded) starch melts according to its melting temperature at the existing
water content. The similar Tc
values of cereal starches indicate that their
crystallites have similar stability and are therefore of similar short chain
lengths. A higher melting temperature Tchas been reported for B-starches with
longer short chains [173]. The structural differences in cereal amylopectins
related to retrogradation can be related to differences in the amorphous regions
or differences in the ratio of short chains to long chains and the ratio of A
chains to B chains. A greater amount of short chains over 15 glucose units
and an increased ratio of A chains to B chains probably promote retrogradation.
It has also been reported that very short chains (6 to 9 glucose units) can
inhibit or retard retrogradation of starch gels [179,180].
10.5 RHEOLOGICAL BEHAVIOR
OF THE STARCH GEL
The events occurring during gelatinization of a starch suspension, especially
the swelling and leaking of amylose/amylopectin, will dramatically change the
rheological properties of the starch suspension. The subsequent retrogradation
will then further modify the rheological properties. Perhaps the most common
method for studying starch properties is to study the changes in viscosity during
a programmed heating–cooking–cooling cycle. The measurements are carried
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