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Food Lipids: Chemistry, Nutrition, and Biotechnology

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where A = B = C <strong>and</strong> all are saturated or trans-unsaturated, the form is �-2;<br />

where A = C <strong>and</strong> are saturated <strong>and</strong> B is cis-unsaturated or has 4 or more carbons<br />

less than A <strong>and</strong> B, the form is �-3;<br />

where, in mixed saturated/unsaturated systems, A = B or B = C (asymmetrical),<br />

the form is ��-3;<br />

where, in mixed saturated/unsaturated systems, A = C (symmetrical), the form<br />

is �-3.<br />

The packing requirements for �� are less stringent than for �; therefore, mixed<br />

fatty acid triacylglycerols, such as those in lauric fats, tend to be ��-stable [28].<br />

B. Phase Behavior<br />

Timms [24,28] provided a complete review of the phase behavior of fats. A phase<br />

is a physical state of matter that is homogeneous <strong>and</strong> separated from other phases<br />

by a definite boundary. Therefore, if only the solid <strong>and</strong> liquid states of matter are<br />

considered, solid–solid, liquid–solid, <strong>and</strong> liquid–liquid phases can exist. Triacylglycerol<br />

mixtures are ideally miscible when liquid <strong>and</strong> therefore show no heat or<br />

volume changes when mixed. As a consequence, distinct liquid–liquid phases are<br />

not apparent. Many natural fats clearly exhibit several distinct solid phases with<br />

partial miscibility, which leads to compound crystals <strong>and</strong> solid solutions. Identification<br />

of these solid solutions with X-ray powder diffraction is effective, particularly<br />

with fats in equilibrium or relatively stable metastable forms. Thermal analysis using<br />

differential scanning calorimetry (DSC) provides for observation of the effect of<br />

changing temperature [28].<br />

An idealized set of DSC thermograms is depicted in Figure 10. Melting profiles<br />

can be correlated to definitive X-ray determination, which allows subsequent estimation<br />

of polymorphic form using DSC alone. However, polymorph analysis using<br />

Figure 10 Schematic representation of polymorph identification by means of differential<br />

scanning calorimetry. [Reproduced with permission from The Physical <strong>Chemistry</strong> of <strong>Lipids</strong><br />

(D. M. Small, ed.), Plenum Press, New York, 1986.]<br />

Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.

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