Polymorphic influences on the phase behavior of three types of binary mixtures of saturated monoacid triacylglycerols (TAGs), trilaurin/trimyristin (LLL/MMM), trilaurin/tripalmitin (LLL/PPP), and trilaurin/tristearin (LLL/SSS), were examined by small- and wide-angle X-ray scattering (SAXS/WAXS) using synchrotron radiation. The carbon numbers (C-n) for the fatty acid chains of the three TAGS are 12 (LLL), 14 (MMM), 16 (PPP), and 18 (SSS). In the LLL/MMM system, miscible phase behavior occurred in metastable alpha and beta' forms, whereas the most stable beta form exhibited a eutectic phase. On the other hand, LLL/PPP and LLL/SSS mixtures showed immiscible phases for alpha, beta, and beta forms. Therefore, the TAG binary mixtures were miscible in metastable polymorphs of alpha and beta' forms when C-n differed by 2, whereas the immiscible mixtures were constructed in all polymorphic forms when C-n differed by 4 and 6.
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