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10.4.3 INTERACTIONS OFAMYLOPECTIN ANDAMYLOSE
In a study in which retrogradation of gels from nongranular mixtures with
different amylose/amylopectin ratios were studied, synergistic interactions
were seen between amylopectin and amylose at a high amylose content [160].
Because the melting endotherm, as measured by the DSC method, has been
attributed to the recrystallization of the amylopectin fraction, one could expect
that the melting endotherm is proportional to the amount of amylopectin.
Gudmundsson and Eliasson [160], however, found unexpectedly high values
for the melting enthalpy of gels with very high amylose content (75 to 90%).
The possibility of limited cocrystallization has been proposed in relation to
retrogradation [161]. Such cocrystallization could be promoted when amylose
is found in high amounts. Schierbaum et al. [162] have found that linear
segments of amylopectin and amylose, or limit dextrins of certain critical
lengths, can interact in solution. Similar findings were reported by Seivert and
Würsch [159] in a study of the chain association of amylose and the effect of
amylopectin on that process in mixtures with different ratios of amylose to
© 2006 by Taylor & Francis Group, LLC
Starch: Physicochemical and Functional Aspects 419
amylopectin. They found that an increasing amount of amylopectin restricted
the chain association of amylose, and the authors attributed this finding to
either dilution or steric hindrance effects; however, the amylose and amylopectin in aqueous solution have been shown to be immiscible at moderate concentrations, and that encourages phase separation of the polymers [56]. Under
most circumstances, the interactions of amylose and amylopectin should be
limited in normal starch gels, as amylose is preferably leached out of the
granules, whereas the amylopectin is mainly retained within the granules.
10.4.4 STORAGETEMPERATURE ANDWATERCONTENT
Retrogradation is greatly affected by storage temperature. Storage of starch
gels with 45 to 50% water content at low temperatures but above the glass
transition temperature (Tg= –5.0°C) increases the retrogradation compared to
storage at room temperature, especially during the first days of storage. Storage
at freezing temperatures below the Tgvirtually inhibits recrystallization
[91,134]. Higher temperatures (above 32 to 40°C) effectively reduce retrogradation [134]. The Avrami equation has been frequently used to account for
the kinetics of the recrytallization process at different temperatures and water
contents [134,135,137]; however, the analysis of retrogradation kinetics
according to the Avrami equation requires thermodynamic equilibrium conditions, but that is not the case here and the method therefore has limited
applicability. Retrogradation is a nonequilibrium recrystallization process, as
indicated by the fact that at low temperatures (4 to 5°C) the crystallites formed
are less nearly perfect (i.e., they have lower melting temperature Tc) than
crystallites formed at higher storage temperatures [163,164]. A three-step
mechanism of initial nucleation (junction point of two or more starch molecules) followed by crystal growth and propagation and then crystal perfection
has been proposed [6].
Crystallization that follows such a mechanism is nucleation controlled
(i.e., the nucleation has to take place before the propagation can begin). Within
the range Tg
to Tc(e.g., –5.0 to 60°C for a gel with 50% water), both nucleation
and propagation exhibit an exponential dependence on temperature, such that
nucleation rate increases with decreasing temperature, down to the Tg, while
the propagation rate increases with increasing temperature, up to the Tc
[6].
This explains why crystallization occurs at low temperatures but only to a
limited degree at elevated temperatures (>30°C), because nucleation formation
is then retarded. For longer storage periods, the retrogradation should be
maximal at a temperature about midway between Tg
and Tc, as both nucleation
and propagation then take place at moderate rates. Both normal and waxy
starches seem to follow this mechanism; the rate of retrogradation was found
to increase during a 48-hour period with decreasing temperature in the interval
of 1 to 25°C [165]. Amylose gels stored at 6°C did not develop a staling
endotherm during 48 hours of storage [165], indicating that crystallinity melted
© 2006 by Taylor & Francis Group, LLC
420 Carbohydrates in Food
below 100°C is due to amylopectin. Results from NMR studies on the temperature dependence of retrogradation are consistent with these findings
[151,166].
Recrystallization of amylopectin is very sensitive to the water content in
starch gels. A starch content in the range of 10 to 80% is necessary for the
development of the DSC endotherm [137]. The maximum crystallization has
been measured at around 50% starch with DSC as well as with NMR [137,143,
145,151].
In contrast to a native starch suspensions, the gelatinized starch gel is
completely amorphous and its water is uniformly distributed. The recrystallization process depends on the temperature difference between the storage
temperature and the Tg
of the amorphous gel, as the mobility of the chains
determines their association rate. Because water is a plasticizer, it controls the
Tg
of the amorphous gel. At a very low water content, the Tgis above room
temperature, and the amorphous gel is in a highly viscous glassy state that
effectively hinders molecular mobility. Recrystallization increases with increasing water content until 45 to 50% water content is reached. Progressively more
effective plasticization (increased molecular mobility) is obtained, and finally
Tgis depressed below room temperature. Recrystallization then decreases with
a further increase in water content up to 90%, apparently due to dilution of the
crystallizable component in the plasticized amorphous matrix [6].
Due to their antiplasticizing effect, solutes (e.g., sugars) affect the retrogradation of starch gels compared to water alone [6]. They reduce the mobility
of the chains in the amorphous matrix by increasing the Tg
. As a consequence,
the rate of propagation can decline, decreasing the extent of retrogradation.
10.4.5 BOTANICALSOURCE
The botanical source is of great importance for the retrogradation of starch
gels [22,167–173]. This is true not only for starches with very different amylose content, but also for starches with similar amylose contents. Some of the
differences among, for example, cereal starches can be attributed to differences
in the amylose/amylopectin ratio and lipid contents; however, these factors
account for only some of the differences. Structural differences found in the
amylopectin molecule can explain some of the differences in the rate and
extent of recrystallization.
Some studies indicate that the rate, and sometimes the extent, of retrogradation increases with increasing amounts of amylose. Although the amylopectin is considered responsible for the long-term retrogradation, some
waxy starch types are reported to retrograde slowly, but pea and potato
starches with high amylose contents retrograde to a greater extent
[151,174,175]. It is possible that the initial rate of retrogradation could be
accelerated because of synergistic interactions between amylopectin and amylose, as discussed earlier. Other studies have failed to show this relation of
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