Modulating the crystallization of phytosterols with monoglycerides in the binary mixture systems: mixing behavior and eutectic formation.

Phytosterols (PSs) are insoluble in water and poorly soluble in oil, which hampers their potential as cholesterol level regulator in human. To mitigate this problem, monoglycerides (MGs) were used to modulates the crystallization behavior of PSs. Therefore, the understanding on mixing behavior provides the insight into different aspects of crystallization and the resultant effects. The effects on thermal, morphology, diffraction, and spectroscopy behavior were investigated for binary mixtures of 11 different ratios (100:0 to 0:100 MGs:PSs). The phase behavior of binary mixtures of commercial MGs and PSs exhibited complexity with the formation of eutectic mixtures at 90:10 and 80:20 (MGs:PSs) combinations. These combinations revealed a single melting profile and reduced melting enthalpy, though after a month of storage at 5 °C. Conversely, two separate melting regions were observed in others. Furthermore, powder X-ray diffraction (PXRD) analysis of selected combinations revealed a change in crystalline forms with changes in the peaks located between 18-19° (2θ) and 25-26° (2θ). Accordingly, Raman spectroscopy results revealed changes in intensities and peak shape. Therefore, the change in crystalline forms or behavior correlated well to the change in thermal properties. Overall, the characterizations revealed the formation of eutectic mixtures between MGs and PSs at 90:10 and 80:20 (MGs:PSs) in which MGs modified the crystallization of PSs and changed the crystal forms thus, thermal behaviors. This study provides new insight into the mixing behavior of MGs and PSs which supports other research. Therefore, the results of this study are beneficial for the improvement of formulation of phytosterols in food and pharmaceutical products. Nonetheless, this study reveals a simple technique to alter crystal forms of phytosterols through simple complexation with monoglycerides.

Relating crystallization behavior of monoacylglycerols-diacylglycerol mixtures to the strength of their crystalline network in oil.

Diacylglycerols (DAGs) are interesting oil structuring molecules as they are structurally similar to triacylglycerols (TAGs), but are metabolized differently which results in weight loss and improved blood cholesterol levels upon dietary replacement of TAGs with DAGs. Many commercial products consist of a mixture of monoacylglycerols (MAGs) and DAGs, yet the effect of MAGs on the crystallization behavior of DAGs is still to be unraveled. Two types of commercial MAGs, one originating from hydrogenated palm stearin and one of hydrogenated rapeseed oil, were added in concentrations 1, 2 and 4% to 20% DAGs derived from hydrogenated soybean oil. Using differential scanning calorimetry, it was shown that the presence of MAGs delayed the onset of DAG crystallization. Rheological analysis revealed that MAGs also hindered crystal network development. Synchrotron X-ray diffraction analysis demonstrated that the addition of MAGs suppressed the formation of the ß form and stimulated the development of the ß' form. Likely, MAGs mainly hindered the crystallization of 1,3-DAGs, which are responsible for the development of the ß form, and stimulated the crystallization of the 1,2-DAGs, which can crystallize in the α and ß' forms. The presence of two polymorphic forms resulted in a decrease of the crystal network strength, as was derived from oscillatory rheological measurements. This research implies a different effect of monoacylglycerols on both the nucleation and crystal growth of 1,2- and 1,3-DAG isomers. This insight is not only relevant for oleogelation research, but also for emulsifying agents which often contain blends of MAGs, 1,2-DAGs and 1,3-DAGs.

Crystallization behavior of emulsified fats influences shear-induced partial coalescence.

Emulsion stability is desired during production, storage and transportation. However, controlled destabilization by partial coalescence is requisite in the production of e.g. whipped cream, vegetable toppings and ice cream. Partial coalescence in recombined cream (RC) implies the presence of a semisolid fat. Three types of fat, i.e. anhydrous milk fat (AMF), palm oil (PO) and palm kernel oil (PKO), were used in the production of RC. Partial coalescence was initiated by the application of shear and assessed at three temperatures, namely 15, 20 and 25 °C to investigate the relation between solid fat content (SFC) and shear-induced partial coalescence. Despite differences in SFC, shear-induced partial coalescence occurred fastest at 20 °C. On the contrary, a nearly equal SFC at 25 °C resulted in significantly different behavior amongst the fats. This demonstrates that not only SFC determines instability but also fat crystal microstructure, which is dependent on fat composition and on processing conditions. However, SFC could be related to the type of network formed by the partially coalesced fat droplets. The fat crystallization properties, studied in bulk and emulsion, point out a divergent effect of emulsification on the crystallization of the fats which could be explained by differences in crystal morphology.

Correction: Food-grade monoglyceride oil foams: the effect of tempering on foamability, foam stability and rheological properties.

Correction for 'Food-grade monoglyceride oil foams: the effect of tempering on foamability, foam stability and rheological properties' by Robbe Heymans et al., Food Funct., 2018, DOI: 10.1039/c8fo00536b.

Food-grade monoglyceride oil foams: the effect of tempering on foamability, foam stability and rheological properties.

Foams with a continuous oil phase may be stabilized using crystalline particles. Those systems are compelling because of their potential in edible oil structuring, modifying sensorial properties and creating healthier food products. This study aimed to relate oleogel (unwhipped state) properties to oil foam (whipped state) properties using a monoglyceride-sunflower oil model system. The properties of crystal-oil mixtures were influenced by time and temperature during preparation and storage. Therefore, oleogels were prepared using different tempering protocols and their resulting microstructure was investigated with rheology, differential scanning calorimetry and X-ray diffraction. The corresponding oil foams were characterized in terms of foamability and foam stability. The properties of both systems were studied immediately after preparation as well as after 4 weeks of storage. We demonstrated that there is a large influence of the time-temperature history on the foam properties. Partially crystallized mixtures were shown to form weaker structures which capture more air because of their lower viscosity and as crystallization would preferentially take place at the interface. They were characterized by larger bubbles and were less stable and firm. It is proposed that their rheological properties are mainly dominated by interfacial contributions. Fully crystallized and stored monoglyceride-oil mixtures were seen to form stronger gel networks which included less air, contained smaller air bubbles and were stable during storage. It is hypothesized that these samples also included an important bulk gelation contribution.

Synergistic interactions between lecithin and fruit wax in oleogel formation.

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.

Physical compatibility between wax esters and triglycerides in hybrid shortenings and margarines prepared in rice bran oil.

BACKGROUND: Wax esters contribute to the transformation of liquid oils into solid-like oleogel systems, which can act as alternatives for trans- and/or saturated fats in food products. The use of solely waxes reduces the solid content, consistency and sensory quality in the final products. Therefore, a combination of sunflower wax and palm fat in rice bran oil was created to accomplish the hybrid low-saturated shortenings and margarines with a compatible structure and lower amounts of saturated fats. RESULTS: During cooling of the hybrid shortenings, sunflower wax crystallized first and acted as nucleation sites for the crystallisation of palm fat. At 5 °C, a mixture of different crystal morphologies (α, ß', and ß crystals) existed in the hybrid shortening. In margarine processing, the hybrid samples were subjected to a simultaneous cooling-emulsification, in which sunflower wax crystallised first at the interface and adsorbed onto the water droplets. Based on the hardness measurements, the maximum amount of palm fat replaceable by 1.0%wt sunflower wax was up to 40% in shortenings and 25% in margarines. A higher amount of sunflower wax (2.5%wt) reduced up to 40% of saturated fats in the hybrid emulsions. CONCLUSION: The addition of 1.0%wt sunflower wax enhanced the solid content and network strength of hybrid palm-based shortenings. Sunflower wax helped to stabilise the water droplets inside the wax-based crystalline network without flocculation during shear-cooling. This research provides fundamental insight into the structuring of hybrid systems containing waxes, which could be interesting for the production of low-saturated fat products in the food industry. © 2017 Society of Chemical Industry.

Phytosterols-induced viscoelasticity of oleogels prepared by using monoglycerides.

Monoglycerides (MGs) and phytosterols (PS) are known to form firm oleogels with liquid oil. However, the oleogels are prone to undergo polymorphic transition over time that lead to crystals' aggregation thus, compromises physical properties. Thus, we combined MGs with PS to control the crystallization and modify the morphology of the combination oleogels, as both components are reported to interact together. The oleogels were prepared at different ratio combinations and characterized in their rheological, thermal, morphology, and diffraction properties. The results showed that the 8:2 MGP:PS exhibited higher storage modulus (G') than the MGP mono-component. The combination oleogels exhibited effects on the crystallization and polymorphic transition. Consequently, the effects led to change in the morphology of the combination oleogels which was visualized using optical and electron microscope. The resultant effect on the morphology is associated with crystal defect. Due to observable crystals of MGP and PS, it is speculated that the combination oleogels formed a mixed crystal system. This was confirmed with diffraction analysis in which the corresponding peaks from MGP and PS were observed in the combination oleogels. However, the 8:2 oleogel exhibited additional peak at 35.41Å. Ultimately, the 8:2 was the optimum combination observed in our study. Interestingly, this combination is inspired by nature as sterols (phytosterols) are natural component of lipid membrane whilst MGP has properties similar to phospholipids. Hence, the results of our study not only beneficial for oil structuring, but also for the fields of biophysical and pharmaceutical.