Phase Behavior and Polymorphism of Saturated and Unsaturated Phytosterol Esters.

This study investigated how the physicochemical characteristics of phytosterol esters are influenced by the chain length and degree of unsaturation of the fatty acid ester moiety. Saturated and unsaturated phytosterol esters (PEs) were synthesized by the esterification of different types of fatty acids (stearic, palmitic, lauric, oleic, and linoleic acid) to ß-sitosterol. The non-isothermal crystallization and melting behavior of the pure PEs were analyzed. It was proven by X-ray diffraction that saturated ß-sitosteryl esters and ß-sitosteryl oleate formed a bilayer crystal structure. The lamellar spacings of the bilayer structure decreased with decreasing fatty acid chain length and with an increasing degree in unsaturation. The degree of unsaturation of the fatty acid chain of the ß-sitosteryl esters also influenced the type of subcell packing of the fatty acid moieties in the bilayer structure, whether or not a metastable or stable liquid crystalline phase was formed during cooling. Furthermore, it was found that the melting temperature and enthalpy of the ß-sitosteryl esters increased with an increasing fatty acid chain length while they decreased with an increasing degree of unsaturation. The microscopic analyses demonstrated that ß-sitosteryl oleate formed much smaller spherulites than their saturated ß-sitosteryl analogues.

Isothermal Crystallization Kinetics of Palm Oil as Influenced by Addition of a Commercial Phytosterol Ester Mixture.

In literature there is good agreement on the health-promoting effects of phytosterols. However, addition of phytosterol esters (PEs) to lipid (containing food products) may influence its crystallization behavior. This study investigated the crystallization kinetics of palm oil (PO) after addition of PEs in high concentrations (≥10%). The isothermal crystallization of the PE-PO blends was analyzed at a temperature of 20 °C and at a supercooling of 18.7 °C using differential scanning calorimetry and time-resolved synchrotron X-ray diffraction. At increasing PE concentrations, PO crystallization at an isothermal temperature of 20 °C started later and was slower and a smaller amount of crystals were formed. Furthermore, a delay in polymorphic transition from α to ß' was observed. When the blends were isothermally crystallized at a supercooling of 18.7 °C, only two of these effects remained: the delay in polymorphic transition and the decrease in crystalline content.

The effect of adding a commercial phytosterol ester mixture on the phase behavior of palm oil.

The objective of this study was to investigate in depth the non-isothermal crystallization and melting behavior of binary blends of palm oil (PO) with a commercial, multi-component phytosterol ester (PE) mixture. DSC and time-resolved synchrotron X-ray diffraction (XRD) experiments were conducted on blends with a PE concentration from 0 to 100% at intervals of 10% for DSC and 20% for XRD. Based on XRD, two different ordered structures were identified in pure the PEs. The structure designated as PEx was truly crystalline and needed a very high degree of supercooling for its nucleation from the melt. The structure designated PEy formed without supercooling and showed long-range order with multiple reflections at small angles but only one broad reflection at high angle, typical of liquid crystalline samples. Furthermore, PEy had a high tolerance for molecules of different chemical nature. In the PE-PO blends no other ordered structures were formed other than the ones observed in the pure PEs and PO. The peaks in the DSC runs of the PE-PO blends were linked to transitions of the different polymorphic forms. All structural information of the binary blends as a function of concentration and temperature was collected in morphology maps. The binary blends exhibited eutectic characteristics visualized in the morphology maps with a eutectic point at 40% PEs.