In vitro digestion of high-lipid emulsions: towards a critical interpretation of lipolysis.

Investigating the gastrointestinal fate of food emulsions is critical to unveil their nutritional relevance. To this end, the protocol standardized by COST INFOGEST 2.0 is meaningful for guiding in vitro digestion experiments. In contrast with studies addressing emulsions with low dispersed phase volume fraction (φ 0.05-0.1), we presently raise some points for a proper interpretation of the digestibility of emulsions with high lipid content using the pH-stat method. Oil-in-water high internal phase emulsions (HIPEs) were submitted to gastric pre-lipolysis with the addition of rabbit gastric lipase (RGE). Commercial mayonnaise (φ 0.76) was systematically diluted (φ 0.025, 0.05, 0.1, 0.15, 0.25, 0.4, and 0.76) to cover a wide range of enzyme-to-lipid ratios (8.5-0.3 U per µmol for RGE and 565.1-18.6 U per µmol for pancreatin, in the gastric and intestinal phases, respectively). Lipolysis was tracked either by fatty acid titration (NaOH titration) or completed by analysis of lipid classes and fatty acid composition. Gastric lipase resulted in substantial lipid hydrolysis, reaching 20 wt% at low lipid fractions (φ 0.025 and 0.05). Likewise, the kinetics and extent of lipolysis during intestinal digestion were modulated by the enzyme-to-substrate ratio. A logarithmic relationship between lipid hydrolysis and lipid concentration was observed, with a very limited extent at the highest lipid content (φ 0.76). A holistic interpretation relying on FFA titration and further evaluation of all lipolytic products appears of great relevance to capture the complexity of the effects involved. Overall, this work contributes to rationally and critically evaluating the outcomes of static in vitro experiments of lipid digestion.

High internal phase emulsion stabilized by sodium caseinate:quercetin complex as antioxidant emulsifier.

High internal phase emulsion (HIPE) was produced and stabilized using a novel antioxidant emulsifier formed by the complexation between sodium caseinate (SC) and quercetin (Q). Colloidal complexes, produced via an alkaline process, showed great ability to reduce the interfacial tension between oil-water phases, promoting stabilization of the HIPEs even at low concentrations (1.5% w/v in the aqueous fraction). HIPEs at 0.80 volume fraction of dispersed phase presented remarkable viscosity due to the high-packing network of oil droplets surrounded by a thin liquid layer. Moreover, the emulsions showed a gel-like behavior and kinetic stability for 45-days at 25 °C. The approach of SC:Q complexes on HIPEs development is promising to reduce lipid oxidation, translated by the formation of hydroperoxides and malondialdehyde during storage, especially for the complex formed with the highest amount of the phenolic compound. In this study, the development of HIPEs with outstanding kinetic and oxidative stability is reported as a potential alternative for the development of healthier products with reduced saturated and trans-fat content.

Designing covalent sodium caseinate-quercetin complexes to improve emulsifying properties and oxidative stability.

The complexation of proteins with phenolic compounds has been considered a promising route to improve the oxidative stability of oil-in-water (O/W) emulsions. In this context, physicochemical and techno-functional properties of sodium caseinate (SC) chemically modified by the interaction with quercetin (Q) under alkaline conditions were evaluated using different molar ratios of the components (SC:Q). The formation of covalent complexes was analysed by the changes in SC structure and properties.. The results showed that the surface hydrophobicity of SC gradually decreased with increasing Q concentration. Whereas an increase in phenolic content and antioxidant activity by DPPH and FRAP was observed. The techno-functionality of the complexes was evaluated by their capacity of stabilizing oil-in-water emulsions. The emulsion stabilized by complexes and non-modified SC showed an average droplet size (D4.3) between 1,632 ± 0,068 and 1,945 ± 0,431 µm. After 21d of storage, no coalescence was observed, evidencing the formation of stable emulsions. Furthermore, the highest oxidative stability of the emulsion was observed at the highest concentration of Q, while the formation of hydroperoxides and aldehydes was greater in the emulsions stabilized with non-modified SC. The formation of primary lipid oxidation compounds was approximately 3x higher in emulsions stabilized only with SC compared to those stabilized with the SC:Q complex in a 1:1 ratio. These results suggest that modification of SC with Q is a potential approach tuning both chemical and techno-functional properties of SC.

Encapsulation of Active Pharmaceutical Ingredients in Lipid Micro/Nanoparticles for Oral Administration by Spray-Cooling.

Nanoencapsulation via spray cooling (also known as spray chilling and spray congealing) has been used with the aim to improve the functionality, solubility, and protection of drugs; as well as to reduce hygroscopicity; to modify taste and odor to enable oral administration; and many times to achieve a controlled release profile. It is a relatively simple technology, it does not require the use of low-cost solvents (mostly associated to toxicological risk), and it can be applied for lipid raw materials as excipients of oral pharmaceutical formulations. The objective of this work was to revise and discuss the advances of spray cooling technology, with a greater emphasis on the development of lipid micro/nanoparticles to the load of active pharmaceutical ingredients for oral administration.

Hybrid oil-in-water emulsions applying wax(lecithin)-based structured oils: Tailoring interface properties.

This study addressed the impact of fruit wax(lecithin)-based oleogels as dispersed phase in formation and stability of oil-in-water emulsions. These hybrid emulsions were prepared above the melting point of the oleogels, using Tween 80 (T80) or whey protein isolate (WPI) as emulsifiers. Both mono- and mixed-component oleogels comprised of fruit wax (FW) or FW + lecithin (FWLEC), respectively, were studied as lipid phases. After hot-homogenization, emulsions were submitted to quiescent cooling and stored over 14 days at 5 or 25 °C, in such temperatures supposed to assist or hinder oleogelation, respectively. Time course promoted a slight decrease in zeta potential only for WPI-stabilized emulsions and particle size distribution was shifted to larger size values, but showing a lesser extent to those stored at 5 °C. The presence of oleogels improved kinetic stability of emulsions compared to liquid oil at both temperatures, disclosing the role of the combined effects of the type of emulsifier and oleogelator(s)-emulsifier interactions. These outcomes are associated with the interfacial activity played by both oleogelators, but mainly lecithin that led to lower values of interfacial tension. In addition FWLEC combined with WPI showed the lowest complex modulus from dilational rheology, which can be related with WPI-LEC complex formation. Overall, results suggest that oleogelators migrated to the O/W interface of dispersed droplets, no longer reflecting oleogel bulk properties and showing a more complex behavior. However, the formation of more complex structures at the interface favored greater stability of the emulsions. Thus, the new perspective of oleogel-inspired fat droplets in hybrid systems can expand the conventional approach of oil structuring to create mixed interfaces tailoring oil-in-water emulsions properties.

Tailoring Properties of Mixed-Component Oleogels: Wax and Monoglyceride Interactions Towards Flaxseed Oil Structuring.

The combination of oleogelators in oil structuring has an untapped potential, since effective pairs have usually been found by serendipity. The aim of this work was to evaluate the combination of berry (BEW) or sunflower wax (SHW) with glycerol monostearate (GMS) in flaxseed oil (FXO) at 5 and 25 °C. The thermal and mechanical properties, microstructure, and stability of oleogels were investigated. Self-standing and translucent gels were obtained from BEW in FXO. However, the mixture BEW:GMS resulted in a decrease of dynamic moduli. Moreover, changes in the crystal network and a reduction of oil binding capacity were noticed. Thus, the GMS prevented the complete organization of BEW in polyunsaturated chains of FXO. Conversely, a positive interaction was found for GMS:SHW, since both alone were not able to impart the structure in FXO. Interestingly, gel was formed with improved properties, even with a small addition of GMS, although an ideal ratio of 1:1 (GMS50:50SHW) was found. Oxidative stability analysis showed that all gels resembled the behavior of liquid oil (~12.00 meqO2/kg) over 30 days storage. Therefore, semi-solid systems with nutritional and techno-functional claims were created by using waxes and fatty-acid derivative oleogelator in a rational fashion; this opened the opportunity to tailor oleogel properties.

Formation and stability of W/O-high internal phase emulsions (HIPEs) and derived O/W emulsions stabilized by PGPR and lecithin.

Water-in-oil high internal phase emulsions (HIPEs) can provide interesting textures that could be used to reduce trans- and/or saturated fat content in food products. On the other hand oil-in-water emulsions can be found in a variety of food and beverages. Moreover, strategies aiming synthetic or semi-synthetic ingredients replacement by natural alternatives for food applications has been pursuit. For these purposes, the effect of partial replacement of PGPR by lecithin on properties of either W/O-HIPEs or O/W emulsions manufactured from the same initial composition but showing different volume fraction of dispersed phase were investigated aiming to understand the behaviour of emulsifiers' mixture in water-oil or oil-water interfaces. Firstly, water-in-oil HIPEs were produced using a rotor-stator device. At fixed total amount of emulsifier (2% w/w), W/O emulsions stabilized with LEC:PGPR ratios of 0.5:1.5 and 1.0:1.0 showed similar droplet size with a better kinetic stability compared to emulsions containing only PGPR. These results indicated good interaction between LEC and PGPR, which was also confirmed by dynamic interfacial tension profile and interfacial dilational rheology. In order to reduce the droplet size of W/O-HIPEs, these emulsions were subsequently subjected to high-pressure homogenization and interestingly phases inversion was observed. Confocal microscopy confirmed the phases inversion attributed to high input of energy leading to the formation of O/W emulsions. Then both W/O-HIPEs and O/W emulsions were investigated regarding LEC:PGPR mixtures as emulsifiers. All W/O-HIPEs showed shear thinning behavior and high viscosity at low shear rate whereas O/W emulsions showed low viscosity and Newtonian behavior. The increase of lecithin content in emulsifier mixture led to more stable O/W emulsions, whereas more stable W/O-HIPEs were produced by lecithin and PGPR mixtures ratio of 0.5:1.5 and 1.0:1.0.

Lecithin and phytosterols-based mixtures as hybrid structuring agents in different organic phases.

In this study the effect of lecithin (L) addition and solvent quality in a well-established oleogel system formed by ß-sitosterol and γ-oryzanol (BG) was investigated. Medium chain triglycerides (MCT) and sunflower oil (SFO) were used as triglycerides and hexadecane (HEX) as a model of linear hydrocarbon. Lecithin was proposed due to its natural and versatile properties, showing different functionalities such as emulsifier and co-oleogelator. A study based on hierarchical organization of structured oil was performed applying techniques for bulk, meso and nanoscale. Self-sustained structures could no longer be observed after 40 wt% of BG replacement by lecithin. Small-angle X-ray scattering showed that the formed nanostructures (building blocks) were dependent on type of solvent and BG:L ratio in the mixture of oleogelators. Differential scanning calorimetry showed that stability against temperature was improved decreasing the polarity of the oil, and a time-dependent self-assembly of hybrid systems was observed from thermal and rheological measurements. Microscopy images exhibited changes on typical fibril aggregation of BG as lecithin was added, which promoted to a certain extent the suppression of ribbons. Oscillatory shear and uniaxial compression measurements were influenced by BG:L ratio and solvent mainly at higher lecithin amount. The combination of BG and MCT appeared to be the most affected by lecithin incorporation whereas SFO rendered harder oleogels. These results could contribute to understand the role of both lecithin and solvent type influencing the host oleogelator structure. It was hypothesized that intermolecular BG complex formation is hindered by lecithin, besides this phospholipid also might coexist as a different phase, causing structural changes in the gel network. Addressing the role of co-oleogelator it can provide the opportunity to tune soft materials with adjusted properties.

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.