Structural stability of liposome-stabilized oil-in-water pickering emulsions and their fate during in vitro digestion.

Most current research on food-relevant Pickering emulsions has been conducted using inorganic or food-compatible organic particles as emulsifiers. A key challenge is maintaining a favourable structure while being able to resist displacement or destabilisation by surfactants and controlling transport of substrates during digestion. Liposome stabilised emulsions have demonstrated some potential for being smart, responsive delivery systems for poorly available bioactives and drugs. We developed a liposome-stabilized oil-in-water Pickering emulsion utilising macromolecular crowding- with polyethylene glycol (PEG). They were pH-controllable and had surfactant-dependent deformability whilst displaying dual delivery routes from both the liposome and oil phases. Dynamic light scattering, confocal microscopy and emulsion stability measurements indicated the liposomes containing 10% PEG at neutral pH remained intact at the interface for extended time. Various degrees of interfacial coverage still existed in the presence of PEG, under acidic environment and with added bile salts. Emulsions with added PEG maintained a more integrated structure after in vitro oral-gastric digestion, and showed greater lipolysis with more free fatty acids (14.7 ± 0.5% for with PEG vs. 12.7 ± 0.1% for without PEG) released during in vitro intestinal digestion. These Pickering emulsions could provide a flexible approach to controlled release under a broad range of conditions.

Fish Oil Emulsions Stabilized with Caseinate Glycated by Dextran: Physicochemical Stability and Gastrointestinal Fate.

Incorporation of fish oil containing ω-3 polyunsaturated fatty acids (PUFAs) into functional foods remains challenging. In this study, caseinate and glycoconjugates (CD6, CD40, CD70, CD100) of caseinate to dextrans of different molecular weights (D6, D40, D70, D100 kDa) were used to stabilize fish oil emulsions, and the impact on physicochemical stability and gastrointestinal fate was investigated. The glycoconjugate of CD6 exhibited significantly higher conjugation efficiency, lower surface hydrophobicity ( H0), and lower surface activity than other glycoconjugates. The glycoconjugate of CD70 displayed the best emulsifying activity and emulsion stability. Except CD6 stabilized emulsions, all other emulsions showed fine storage stability over 14 d at 22 ± 1 °C. The glycoconjugate stabilized emulsions exhibited significantly lower peroxide value (PV) ( P < 0.05) than that of the caseinate stabilized one. During in vitro gastrointestinal tract digestion, the glycation of caseinate with dextrans changed the ζ-potential, average particle size ( D32), and particle size distribution of the emulsions, which influenced flocculation and coalescence of droplets, as demonstrated by confocal microscopy. Caseinate after glycation with dextrans significantly retarded the release of free fatty acids from emulsions ( P < 0.05) during in vitro lipolysis. These results suggested that the dextrans attached to caseinate by glycation played a vital role in physicochemical stability and gastrointestinal fate of emulsions, mainly by its steric hindrance to effectively prevent flocculation and coalescence of droplets.

Temperature- and pH-Dependent Shattering: Insoluble Fatty Ammonium Phosphate Films at Water-Oil Interfaces.

We study the films formed by tetradecylamine (TDA) at the water-dodecane interface in the presence of hydrogen phosphate ions. Using Fourier transform infrared spectroscopy (FTIR), interfacial shear rheology, confocal fluorescence microscopy, cryo-scanning electron microscopy (cryo-SEM), and small-angle neutron scattering (SANS), we find that between pH 5 and 8 tetradecylammonium cations bind to hydrogen phosphate anions to form needle-shaped crystallites of tetradecylammonium hydrogen phosphate (TAHP). These crystallites self-assemble into films with a range of morphologies; below pH 7, they form brittle, continuous sheets, and at pH 8, they form lace-like networks that deform plastically under shear. They are also temperature-responsive: when the system is heated, the film thins and its rheological moduli drop. We find that the temperature response is caused by dissolution of the film in to the bulk fluid phases. Finally, we show that these films can be used to stabilize temperature-responsive water-in-oil emulsions with potential applications in controlled release of active molecules.

Effect of substituent pattern and molecular weight of cellulose ethers on interactions with different bile salts.

Some known mechanisms proposed for the reduction of blood cholesterol by dietary fibre are: binding with bile salts in the duodenum and prevention of lipid absorption, which can be partially related with the bile salt binding. In order to gain new insights into the mechanisms of the binding of dietary fibre to bile salts, the goal of this work is to study the main interactions between cellulose derivatives and two types of bile salts. Commercial cellulose ethers: methyl (MC), hydroxypropyl (HPC) and hydroxypropylmethyl cellulose (HPMC), have been chosen as dietary fibre due to their highly functional properties important in manufactured food products. Two types of bile salts: sodium taurocholate (NaTC) and sodium taurodeoxycholate (NaTDC), have been chosen to understand the effect of the bile salt type. Interactions in the bulk have been investigated by means of differential scanning calorimetry (DSC) and linear mechanical spectroscopy. Results show that both bile salts have inhibitory effects on the thermal structuring of cellulose ethers and this depends on the number and type of substitution in the derivatised celluloses, and is not dependent upon molecular weight. Concerning the bile salt type, the more hydrophobic bile salt (NaTDC) has greater effect on these interactions, suggesting more efficient adsorption onto cellulose ethers. These findings may have implications in the digestion of cellulose-stabilised food matrices, providing a springboard to develop new healthy cellulose-based food products with improved functional properties.

Structural characterisation of parotid and whole mouth salivary pellicles adsorbed onto DPI and QCMD hydroxyapatite sensors.

In this study we investigated the differences in the properties of pellicles formed from stimulated parotid saliva (PS), which contains little or no mucin; and stimulated whole mouth saliva (WMS), which contains mainly two types of mucin: MUC5B and MUC7. By contacting WMS and PS with quartz-crystal microbalance with dissipation monitoring (QCM-D) and dual polarisation interferometer (DPI) hydroxyapatite (the main component of enamel) coated sensors, we observed the formation and structure of the respective salivary pellicles. As this was the first time that DPI hydroxyapatite sensors have been used to measure salivary pellicle adsorption; the techniques combined allowed us to measure the hydrated mass, dry mass, thickness and viscoelastic properties of the pellicle; but also to record the density of the PS and WMS formed pellicles. Subsequently, the PS pellicle was shown to form a denser layer than WMS pellicle; which would suggest that the proteins present in PS are also responsible for forming the dense basal layer of the acquired enamel pellicle. Whereas proteins present in the WMS are more likely to help form the softer outer layer of the pellicle. The data presented help to further define the mechanisms leading to the multi-layered structure of the salivary pellicle and demonstrate that salivary composition has an important effect on the structural properties of the adsorbed pellicle.

Adsorption of bile salts and pancreatic colipase and lipase onto digalactosyldiacylglycerol and dipalmitoylphosphatidylcholine monolayers.

It is increasingly recognized that changes in the composition of the oil-water interface can markedly affect pancreatic lipase adsorption and function. To understand interfacial mechanisms determining lipase activity, we investigated the adsorption behavior of bile salts and pancreatic colipase and lipase onto digalactosyldiacylglycerol (DGDG) and dipalmitoylphosphatidylcholine (DPPC) monolayers at the air-water interface. The results from Langmuir trough and pendant drop experiments showed that a DGDG interface was more resistant to the adsorption of bile salts, colipase, and lipase compared to that of DPPC. Atomic force microscopy (AFM) images showed that the adsorption of bile salts into a DPPC monolayer decreased the size of the liquid condensed (LC) domains while there was no visible topographical change for DGDG systems. The results also showed that colipase and lipase adsorbed exclusively onto the mixed DPPC-bile salt regions and not the DPPC condensed phase. When the colipase and lipase were in excess, they fully covered the mixed DPPC-bile salt regions. However, the colipase and lipase coverage on the mixed DGDG-bile salt monolayer was incomplete and discontinuous. It was postulated that bile salts adsorbed into the DPPC monolayers filling the gaps between the lipid headgroups and spacing out the lipid molecules, making the lipid hydrocarbon tails more exposed to the surface. This created hydrophobic patches suitable for the binding of colipase and lipase. In contrast, bile salts adsorbed less easily into the DGDG monolayer because DGDG has a larger headgroup, which has strong intermolecular interactions and the ability to adopt different orientations at the interface. Thus, there are fewer hydrophobic patches that are of sufficient size to accommodate the colipase on the mixed DGDG-bile salt monolayer compared to the mixed DPPC-bile salt regions. The results from this work have reinforced the hypothesis that the interfacial molecular packing of lipids at the oil-water interface influences the adsorption of bile salts, colipase, and lipase, which in turn impacts the rate of lipolysis.

Modulating pancreatic lipase activity with galactolipids: effects of emulsion interfacial composition.

It is widely known that the interfacial quality of lipid emulsion droplets influences the rate and extent of lipolysis. The aim of this work was to investigate the effect of two galactolipids, monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG), adsorbed at the interface on in vitro digestibility of olive oil by porcine pancreatic lipase. The experiments were performed under simulated duodenal conditions in the presence of phosphatidylcholine (lecithin) and bile salts. It was found that emulsions prepared with DGDG had a longer lag phase prior to lipase activation with a decrease in lipolysis rate. In contrast, no inhibitory effect on lipase kinetics was observed in emulsions prepared with MGDG. We postulated that the larger headgroup and more tightly packed molecular organization of DGDG at the interface gave rise to steric hindrance that retarded colipase and lipase adsorption onto the substrate surfaces and hence delayed and reduced lipolysis. It was noted that the lag phase and lipolysis rate strongly depended on the DGDG/lecithin molar ratio in the systems: the higher the molar ratio, the longer the lag phase followed by a reduced lipolysis rate. The ability of DGDG to inhibit bile salt adsorption/displacement was also investigated. The results showed that bile salts did not completely displace DGDG from the interface, explaining the reason why DGDG still possessed inhibitory activity even in the presence of bile salts at a physiological relevant concentration. The results provide interesting insights into the influence of the galactolipid headgroup and lecithin on the emulsion interfacial quality which in turn regulates the lipolysis. The findings potentially could lead to the production of generic foods and drugs designed for regulating dietary fat absorption in the prevention and treatment of obesity and related disorders.

Interfacial characterization of beta-lactoglobulin networks: displacement by bile salts.

The competitive displacement of a model protein (beta-lactoglobulin) by bile salts from air-water and oil-water interfaces is investigated in vitro under model duodenal digestion conditions. The aim is to understand this process so that interfaces can be designed to control lipid digestion thus improving the nutritional impact of foods. Duodenal digestion has been simulated using a simplified biological system and the protein displacement process monitored by interfacial measurements and atomic force microscopy (AFM). First, the properties of beta-lactoglobulin adsorbed layers at the air-water and the olive oil-water interfaces were analyzed by interfacial tension techniques under physiological conditions (pH 7, 0.15 M NaCl, 10 mM CaCl2, 37 degrees C). The protein film had a lower dilatational modulus (hence formed a weaker network) at the olive oil-water interface compared to the air-water interface. Addition of bile salt (BS) severely decreased the dilatational modulus of the adsorbed beta-lactoglobulin film at both the air-water and olive oil-water interfaces. The data suggest that the bile salts penetrate into, weaken, and break up the interfacial beta-lactoglobulin networks. AFM images of the displacement of spread beta-lactoglobulin at the air-water and the olive oil-water interfaces suggest that displacement occurs via an orogenic mechanism and that the bile salts can almost completely displace the intact protein network under duodenal conditions. Although the bile salts are ionic, the ionic strength is sufficiently high to screen the charge allowing surfactant domain nucleation and growth to occur resulting in displacement. The morphology of the protein networks during displacement is different from those found when conventional surfactants were used, suggesting that the molecular structure of the surfactant is important for the displacement process. The studies also suggest that the nature of the oil phase is important in controlling protein unfolding and interaction at the interface. This in turn affects the strength of the protein network and the ability to resist displacement by surfactants.