The crystallization properties of triacylglycerols (TAGs) strongly determine the functional properties of natural lipids. The polymorphic and mixing phase behavior of TAG molecules have long been, and still are, a hot topic of research with special relevance for the cosmetic, pharmaceutical, and food industry. To avoid the difficulties arising from the study of whole real fats, studies at the molecular level on mixtures of a limited number of TAGs has become an indispensable tool to identify the underlying causes of the physical properties in lipid systems. In particular, phase diagrams of binary mixtures of TAGs exhibiting a different degree of heterogeneity (monoacid or mixed fatty acids; molecular symmetry; the presence of cis or trans double bonds) have resulted in a significant breakthrough in our knowledge about structure–interaction–function relationships. The present work aims to provide an overview of the main reports regarding binary and ternary TAG systems, from the early studies to the most recent developments.

Here is reported the anti Leishmania infantum activity of 48 hexane, CH₂Cl₂ and MeOH extracts from 16 macroalgae collected on the Iberian Coast. Seven hexane and CH₂Cl₂ Cystoseira baccata, Cystoseira barbata, Cystoseira tamariscifolia, Cystoseira usneoides, Dictyota spiralis and Plocamium cartilagineum extracts were active towards promastigotes (IC₅₀ 29.8–101.8 μg/mL) inducing strong morphological alterations in the parasites. Hexane extracts of C. baccata and C. barbata were also active against intracellular amastigotes (IC₅₀ 5.1 and 6.8 μg/mL, respectively). Fatty acids, triacylglycerols, carotenoids, steroids and meroterpenoids were detected by nuclear magnetic resonance (NMR), and gas chromatography in the Cystoseira extracts. These results suggest that Cystoseira macroalgae contain compounds with antileishmanial activity, which could be explored as scaffolds to the development of novel sources of antiparasitic derivatives.

Differential scanning calorimetry and X-ray diffraction were used to investigate the mixing behavior of triacylglycerol (TAG) mixtures of PPP/PPO (tripalmitoyl glycerol/1,2-dipalmitoyl-3-oleoyl-rac-glycerol) and PPP/MC_POP/PPO (where MC_POP/PPO is the equimolecular blend of 1,3-dipalmitoyl-2-oleoyl-glycerol and PPO forming a molecular compound) under metastable and stable conditions. During cooling and reheating treatments at moderate rates, the eutectic properties of the two systems examined were mainly governed by the crystallization, transformation, and melting behavior of structurally similar β′ forms. In addition, steric and kinetic effects determined the formation of solid solutions with up to 10% and 20% of mixed-acid components in PPP/PPO and PPP/MC_POP/PPO mixtures, respectively. These values increased to 30% and 35% when thermodynamically stable β crystalline phases were obtained. In PPP/MC_POP/PPO mixtures, the diffraction data suggested that POP and PPO acted as a single component by dissolving in similar amounts in the solid solution phases and forming molecular compound crystals in eutectic compositions. This fundamental research shows the important role of specific combinations of mixed-acid TAGs and their interaction with high-melting components on the solidification behavior of edible lipids.

Differential scanning calorimetry and X-ray diffraction were used to examine the mixing phase behavior of LLL (trilaurin or 1,2,3-trilauroyl-glycerol) and POP (1,3-dipalmitoyl-2-oleoyl-glycerol), PPO (1,2-dipalmitoyl-3-oleoyl-rac-glycerol), or the 50POP/50PPO blend able to form a molecular compound. This research aims to provide an insight into the molecular interactions ruling the physical behavior of fat blends of lauric (i.e., coconut oil) and non-lauric lipids (cocoa butter, palm oil, etc.). The results showed eutectic behavior and no mutual solubility of triacylglycerols in stable LLL/POP and LLL/PPO mixtures. Applying high-rate cooling treatments had a positive effect on miscibility, but the high incompatibility of the components due to differences in length and degree of unsaturation of fatty acids was still evident in metastable polymorphs. In ternary LLL/(50POP/50PPO) mixtures, on the other hand, molecular compound β-2L crystals formed by POP and PPO showed to favor the solubility of LLL as compared to the binary systems. Accordingly, promoting the presence of triacylglycerols forming molecular compound in specific fat blends may help reducing eutectic or incompatible interactions among triacylglycerol molecules in the solid state. These lead to phase separation and are a major cause of the restricted applicability of lauric oils in the confectionery and chocolate industries.