In this study, the effect of lecithin (LEC) on the crystallization and gelation of fruit wax (FW) with sunflower oil was researched. A synergistic effect on the gel strength was observed at FW : LEC ratios of 75 : 25 and 50 : 50, compared to the corresponding single component formulations (100 : 0 and 0 : 100). Even below the critical gelling concentration (Cg) of FW, the addition of lecithin enabled gel formation. Lecithin affected the thermal behavior of the structure by delaying both crystallization and gel formation. The phospholipid acted as a crystal habit modifier changing the microstructure of the oleogel, as was observed by polarized light microscopy. Cryo-scanning electron microscopy revealed a similar platelet-like arrangement for both FW as a single oleogelator and FW in combination with LEC. However, a denser structure could be observed in the FW : LEC oleogelator mixture. Both the oil-binding capacity and the thixotropic recovery were enhanced upon lecithin addition. These improvements were attributed to the hydrogen bonding between FW and LEC, as suggested by Raman spectroscopy. We hypothesized that lecithin alters the molecular assembly properties of the FW due to the interactions between the polar moieties of the oleogelators, which consequently impacts the hydrophobic tail (re)arrangement in gelator-gelator and solvent-gelator interactions. The lipid crystal engineering approach followed here offered prospects of obtaining harder self-standing structures at a lower oleogelator concentration. These synergistic interactions provide an opportunity to reduce the wax concentration and, as such, the waxy mouthfeel without compromising the oleogel properties.
Protic ionic liquids (PILs) have emerged as promising compounds and attracted the interest of the industry and the academy community, due to their easy preparation and unique properties. In the context of green chemistry, the use of biocompounds, such as fatty acids, for their synthesis could disclose a possible alternative way to produce ILs with a low or nontoxic effect and, consequently, expanding their applicability in biobased processes or in the development of bioproducts. This work addressed efforts to a better comprehension of the complex solid-[liquid crystal]-liquid thermodynamic equilibrium of 20 new PILs synthesized by using fatty acids commonly found in vegetable oils, as well as their rheological profile and self-assembling ability. The work revealed that their phase equilibrium and physical properties are significantly impacted by the structure of the ions used for their synthesis. The use of unsaturated fatty acids and bis(2-hydroxyethyl)ammonium for the synthesis of these biobased ILs led to a drastic decreasing of their melting temperatures. Also, the longest alkyl chain fatty acids promoted higher self-assembling and more stable mesophases. Besides their sustainable appeal, the marked high viscosity, non-Newtonian profile, and very low critical micellar concentration values of the PIL crystals here disclosed make them interesting renewable compounds with potential applications as emulsifiers, stabilizers, thickeners, or biolubricants.