Emulsions Stabilized by Inorganic Nanoclays and Surfactants: Stability, Viscosity, and Implications for Applications.

Pickering emulsions, or emulsions with solid particles at the interface, have attracted significant interest in Enhanced Oil Recovery (EOR) processes, cosmetics, and drug delivery systems due to their ability to resist coalescence. Here, a synthetic clay nanoparticle, laponite®, is utilized to create oil-in-water (o/w) emulsions, and the addition of small-molecule surfactants induces a more stable emulsion. In this study, the stability of laponite® Pickering emulsions with and without the surfactants (dodecyltrimethylammonium bromide (DTAB), Pluronic F68 (F68), and sodium dodecyl sulfate (SDS) is investigated using dynamic light scattering (DLS), ζ-potential, optical microscopy, and rheology. With laponite® and no added surfactants, the DLS and ζ-potential results show formation of emulsion droplets with a diameter of 3 µm and a ζ-potential of -90 mV. With the addition of surfactants, both the droplet diameter and ζ-potential increase, suggesting adsorption of surfactants on the surface of laponite® particle. Optical microscopy suggests that the Pickering emulsion without surfactant undergoes flocculation, while the emulsion becomes stable to coalescence and creaming with addition of surfactants due to formation of a network structure. Regardless of the formation of network structure, the laponite®-F68 emulsion rheologically behaves as a Newtonian fluid, while the laponite®-SDS and laponite®-DTAB emulsions display shear thinning behavior. The difference in the rheological behavior can be attributed to the weak adsorption of F68 on laponite® and electrostatic interactions between laponite® and charged surfactants at oil-water interface.

Extending viability of Lactobacillus plantarum and Lactobacillus johnsonii by microencapsulation in alginate microgels.

AIM: To investigate whether microencapsulation of Lactobacillus in alginate microbeads will lead to increased longevity during refrigerated storage or simulated digestion. MATERIALS AND METHODS: Microscopy was used to confirm that Lactobacillus plantarum ATCC BAA-793 and Lactobacillus johnsonii ATCC 33200 were immobilised within the microbeads and laser scattering analysis was used to determine the mean diameter of the microbeads. The number of viable cells were enumerated throughout refrigerated storage and simulated digestion experiments. RESULTS: Microencapsulation was shown to have differing effects on viability depending on the species, but led to extended viability during refrigerated storage and simulated digestion in L. johnsonii and L. plantarum respectively. CONCLUSION: Fermented functional foods contain microbes beneficial to human health. However, extended shelf storage and the harsh environment of the GI tract significantly reduces the number of viable microbes reaching the consumer. Microencapsulation allows beneficial microbes to reach the gut of the consumer in higher numbers, and thus confer greater health benefits.

What makes good antioxidants in lipid-based systems? The next theories beyond the polar paradox.

The polar paradox states that polar antioxidants are more active in bulk lipids than their nonpolar counterparts, whereas nonpolar antioxidants are more effective in oil-in-water emulsion than their polar homologs. However, recent results, showing that not all antioxidants behave in a manner proposed by this hypothesis in oil and emulsion, lead us to revisit the polar paradox and to put forward new concepts, hypotheses, and theories. In bulk oil, new evidences have been brought to demonstrate that the crucial site of oxidation is not the air-oil interface, as postulated by the polar paradox, but association colloids formed with traces of water and surface active molecules such as phospholipids. The role of these association colloids on lipid oxidation and its inhibition by antioxidant is also addressed as well as the complex influence of the hydrophobicity on the ability of antioxidants to protect lipids from oxidation. In oil-in water emulsion, we have covered the recently discovered non linear (or cut-off) influence of the hydrophobicity on antioxidant capacity. For the first time, different mechanisms of action are formulated in details to try to account for this nonlinear effect. As suggested by the great amount of biological studies showing a cut-off effect, this phenomenon could be widespread in dispersed lipid systems including emulsions and liposomes as well as in living systems such as cultured cells. Works on the cut-off effect paves the way for the determination of the critical chain length which corresponds to the threshold beyond which antioxidant capacity suddenly collapses. The systematic search for this new physico-chemical parameter will allow designing novel phenolipids and other amphiphilic antioxidants in a rational fashion. Finally, in both bulk oils and emulsions, we feel that it is now time for a paradigm shift from the polar paradox to the next theories.

Cannabidiol and Intestinal Motility: a Systematic Review.

Cannabidiol (CBD) is a non-intoxicating cannabinoid extracted from the cannabis plant that is used for medicinal purposes. Ingestion of CBD is claimed to address several pathologies, including gastrointestinal disorders, although limited evidence has been generated thus far to substantiate many of its health claims. Nevertheless, CBD usage as an over-the-counter treatment for gastrointestinal disorders is likely to expand in response to increasing commercial availability, permissive legal status, and acceptance by consumers. This systematic review critically evaluates the knowledge boundaries of the published research on CBD, intestinal motility, and intestinal motility disorders. Research on CBD and intestinal motility is currently limited but does support the safety and efficacy of CBD for several therapeutic applications, including seizure disorders, inflammatory responses, and upper gastrointestinal dysfunction (i.e., nausea and vomiting). CBD, therefore, may have therapeutic potential for addressing functional gastrointestinal disorders. The results of this review show promising in vitro and preclinical data supporting a role of CBD in intestinal motility. This includes improved gastrointestinal-related outcomes in murine models of colitis. These studies, however, vary by dose, delivery method, and CBD-extract composition. Clinical trials have yet to find a conclusive benefit of CBD on intestinal motility disorders, but these trials have been limited in scope. In addition, critical factors such as CBD dosing parameters have not yet been established. Further research will establish the efficacy of CBD in applications to address intestinal motility.

Impact of free fatty acid concentration and structure on lipid oxidation in oil-in-water emulsions.

Free fatty acids are strong prooxidants in both bulk and emulsified oils. Addition of oleic acid to an oil-in-water emulsions increased lipid hydroperoxide and hexanal formation at free fatty acid concentrations as low as 0.1% of the lipid. The prooxidant effect of free fatty acids was dependent on fatty acid type with lipid oxidation rates being in the order of linolenic

Impact of Polyunsaturated Fatty Acid Dilution and Antioxidant Addition on Lipid Oxidation Kinetics in Oil/Water Emulsions.

As consumers increasingly demand "cleaner" labels, one available strategy is diluting oils high in unsaturated fatty acids into more stable, more saturated oils, thus delaying lipid oxidation by decreasing free-radical propagation reactions between oxidized fatty acids and unsaturated lipids. The effect of diluting fish oil into medium-chain triglycerides (MCTs) on oxidative stability was investigated using lipid hydroperoxides and gas chromatography headspace analysis. Dilutions up to 1 in 20 of fish oil in MCT extended propanal formation from 1 to 6 days in Tween-80-stabilized oil-in-water emulsions. This protective effect was not observed in emulsions wherein the two oils were in separate droplets. Fish oil blended with high oleic sunflower oil (HOSO) also demonstrated a protective effect when the oils were in the same emulsion droplets but not in separate emulsion droplets. The present study indicates that dilution can be used to increase the oxidative stability of polyunsaturated fatty acids in oil-in-water emulsions.

Ability of Sodium Dodecyl Sulfate (SDS) Micelles to Increase the Antioxidant Activity of α-Tocopherol.

As emulsifiers become saturated on the surface of an emulsion droplet, any additional emulsifier migrates to the aqueous phase. Continuous phase surfactants have been shown to increase α-tocopherol efficacy, but it is unclear if this is the result of chemical or physical effects. The addition of α-tocopherol to an oil-in-water emulsion after homogenization resulted in a 70% increase of α-tocopherol in the continuous phase when sodium dodecyl sulfate (SDS) was at levels that were greater than the SDS critical micelle concentration. Conversely, when α-tocopherol was dissolved in the lipid before emulsification, continuous phase SDS concentrations did not increase. When SDS concentration led to an increase in the aqueous phase α-tocopherol, the oxidative stability of oil-in-water emulsions increased. Data indicated that the increased antioxidant activity was the result of surfactant micelles being able to decrease the prooxidant activity of α-tocopherol. Considering these results, surfactant micelles could be an important tool to increase the effectiveness of α-tocopherol.

Factors influencing the chemical stability of carotenoids in foods.

In recent years, a number of studies have produced evidence to suggest that consuming carotenoids may provide a variety of health benefits including a reduced incidence of a number of cancers, reduced risk of cardiovascular disease, and improved eye health. Evolving evidence on the health benefits of several carotenoids has sparked interest in incorporating more carotenoids into functional food products. Unfortunately, the same structural attributes of carotenoids that are thought to impart health benefits also make these compounds highly susceptible to oxidation. Given the susceptibility of carotenoids to degradation, particularly once they have been extracted from biological tissues, it is important to understand the major mechanisms of oxidation in order to design delivery systems that protect these compounds when they are used as functional food ingredients. This article reviews current understanding of the oxidation mechanisms by which carotenoids are degraded, including pathways induced by heat, light, oxygen, acid, transition metal, or interactions with radical species. In addition, several carotenoid delivery systems are evaluated for their potential to decrease carotenoid degradation in functional food products.

Application of flow cytometry as novel technology in studying lipid oxidation and mass transport phenomena in oil-in-water emulsions.

Flow cytometry was used to determine if lipid oxidation products could transfer between individual emulsion droplets. Medium chain triacyclglycerol oil-in-water emulsions containing an oxidizable fluorescent dye, BODIPY665/676, was blended with a soybean oil-in-water emulsion. Results showed that when the concentration of sodium dodecyl sulfonate (SDS) were lower than critical micelle concentration (CMC), lipid oxidation products of triacylglycerols were not able to escape out until emulsions were extremely oxidized. With surfactant micelles, oxidation of BODIPY665/676 was observed. In the presence of free fatty acids, the transfer of prooxidants between droplets was observed even when surfactant concentration was lower than CMC. The decomposition product, 2,4,-decadienal, was also found to be transferred between droplets. The effect of surfactant concentration on prooxidant transfer was investigated using the lipid-soluble radical generator, AMVN. Results showed that surfactants promoted AMVN-triggered degradation of fluorescence at low concentrations but inhibited degradation at high concentration. The CMC of SDS was decreased by NaCl thus affecting the transfer phenomenon. With flow cytometry, the phenomenon of mass transfer between individual droplets was revealed which provides a better understanding of lipid oxidation in emulsion system.

Application of Flow Cytometry As Novel Technology in Studying the Effect of Droplet Size on Lipid Oxidation in Oil-in-Water Emulsions.

Despite several published studies, the impact of emulsion droplet size on lipid oxidation rates is unclear. This could be because oil-in-water emulsions are typically polydisperse and the oxidation rate of individual droplets is difficult to discern. Flow cytometry is a technique for studying individual cells and their subpopulations using fluorescence technologies, which is possible to be used in studying individual emulsion droplets. Typical emulsion droplets are too small to be visualized by flow cytometer so emulsions were prepared to have droplets >2 µm that were stabilized by weighting agent and xanthan gum to minimize creaming during storage. A radical-sensitive fluorescence probe (BODIPY665/676) was added to the lipid used to prepare the emulsion so that the susceptibility of individual emulsion droplets could be determined. The results showed that in a polydisperse emulsion system, small droplets were oxidized faster than large droplets. A conventional method was also carried out by blending two emulsions with different droplet sizes and oil densities, and results were in agreement with the observation obtained from flow cytometry. As a new approach, flow cytometry could be utilized in emulsion studies to reveal insights of lipid oxidation mechanisms in individual droplets.

Influence of Protein Type on the Antimicrobial Activity of LAE Alone or in Combination with Methylparaben.

The cationic surfactant Lauric arginate (LAE) has gained approval for utilization in meat products (limit: 200 mg/kg). However, as for other antimicrobials, its activity is reduced when applied to complex food matrices. The current study therefore aims to better understand protein-antimicrobial agent-interactions and their influence on the antimicrobial activity of (i) LAE and (ii) methylparaben against Listeria innocua and Pseudomonas fluorescens in defined model systems (pH 6). Antimicrobials were utilized alone or in combination with nutrient broth containing either no protein or 2% bovine serum albumin, whey protein isolate, or soy protein hydrolysate. LAE was found to form complexes with all proteins due to electrostatic attraction, determined using microelectrophoretic and turbidity measurements. Minimal lethal concentrations of LAE were remarkably increased (4-13 fold) in the presence of proteins, with globular proteins having the strongest impact. Combinations of LAE (0-200 µg/mL) with the less structure-sensitive component methylparaben (approved concentration 0.1%) remarkably decreased the concentrations of LAE needed to strongly inhibit or even kill both, L. innocua and P. fluorescens in the presence of proteins. The study highlights the importance of ingredient interactions impacting microbial activity that are often not taken into account when examining antimicrobial components having different structure sensitivities.

Headspace Characterization and Quantification of Aromatic Organosulfur Compounds in Garlic Extracts Using Surface-Enhanced Raman Scattering with a Mirror-in-a-Cap Substrate.

BACKGROUND: Surface-enhanced Raman scattering (SERS) has been deployed in the analysis of food at solid and aqueous states. However, its capability has not been fully explored in headspace profiling. OBJECTIVE: To develop an innovative SERS method for analyzing headspace volatile compounds in foods. METHODS: A volatile-capture device was developed by depositing a film of silver nanoparticles in a vial cap to capture the volatiles released from a model flavor compound (garlic). RESULTS: SERS peaks at 1632, 1400, 1291, 1191, 731, and 577 cm-1 were identified in the headspace of the garlic sample, which was representative of an organosulfur compound (diallyl disulfide), and its concentration was determined at 135 ppm, which was comparable to the value determined using GC. Preparation and analysis could be carried out in <10 min for the SERS method. The sensitivity of the SERS method (10 ppm), however, was slightly less than that of the GC method (5 pm). CONCLUSIONS: The SERS method was able to quantify the concentration of diallyl disulfide in the headspace of a raw garlic ethanolic extract. Compared to GC, the SERS method had a much shorter analysis time and simpler sample preparation procedure than GC when analyzing large numbers of samples. HIGHLIGHTS: The innovative "mirror-in-a-cap" substrate was simpler and faster than other reported SERS substrates used for this purpose. Additionally, SERS has much better portability and the potential for real-time monitoring of changes in the garlic headspace concentration during manufacturing and processing.

Recent advances in edible coatings for fresh and minimally processed fruits.

The development of new edible coatings with improved functionality and performance for fresh and minimally processed fruits is one of the challenges of the post harvest industry. In the past few years, research efforts have focused on the design of new eco-friendly coatings based on biodegradable polymers, which not only reduce the requirements of packaging but also lead to the conversion of by-products of the food industry into value added film-forming components. This work reviews the different coating formulations and applications available at present, as well as the main results of the most recent investigations carried out on the topic. Traditionally, edible coatings have been used as a barrier to minimize water loss and delay the natural senescence of coated fruits through selective permeability to gases. However, the new generation of edible coatings is being especially designed to allow the incorporation and/or controlled release of antioxidants, vitamins, nutraceuticals, and natural antimicrobial agents by means of the application of promising technologies such as nanoencapsulation and the layer-by-layer assembly.

Impact of surface-active compounds on physicochemical and oxidative properties of edible oil.

The physical properties of lipids can have a major influence on lipid oxidation reactions. Edible oils contain surface-active compounds and water that can form physical structures such as reverse micelles. This study used the fluorescence probe, 5-dodecanoylaminofluorescein (DAF), to study both the physical and the chemical properties of stripped corn oil containing oleic acid and phosphatidylcholine. The fluorescence intensity of DAF increased with increasing water concentration in the edible oil. The addition of oleic acid decreased DAF fluorescence due to the ability of the free fatty acid to decrease the pH of the aqueous phase of the bulk oil. Phosphatidylcholine increased DAF fluorescence due to its ability to increase DAF exposure to the aqueous phase. Oleic acid had no impact on interactions between DAF and water-soluble peroxyl radicals, while phosphatidylcholine decreased peroxyl radical degradation of DAF. These results suggest that DAF could be a useful analytical tool to study the impact of the aqueous environment of bulk oil on lipid oxidation.

Factors affecting lycopene oxidation in oil-in-water emulsions.

Evidence that dietary lycopene decreases the risk for a number of health conditions has generated new opportunities for the addition of lycopene to functional foods. This work examined the potential of oil-in-water emulsions as a lycopene delivery system for foods. Oil-in-water emulsions containing lycopene were prepared using different kinds of surfactant (cationic, anionic, and nonionic) and oil types (corn oil, stripped corn oil, and hexadecane). The formation of fatty acid oxidation products and the degradation of lycopene and tocopherol were then monitored. Fatty acids and lycopene had greater stability in oil-in-water emulsions stabilized by cationic dodecyltrimethylammonium bromide (DTAB) or nonionic polyoxyethylene (23) lauryl ether than by anionic sodium dodecyl sulfate (SDS). Oxidative stability in the corn oil-in-water emulsions stabilized by SDS was in the following order: tocopherolhexadecane>tocopherol-stripped corn oil. Lycopene degradation rates were similar in emulsions with and without fatty acids, suggesting that lycopene loss was independent of the presence of fatty acids. These results suggest that the stability of lycopene in oil-in-water emulsions could be inhibited by altering the emulsion droplet interface and by the presence of tocopherols.

Impact of Phospholipids and Tocopherols on the Oxidative Stability of Soybean Oil-in-Water Emulsions.

Phospholipids have been shown to act synergistically with tocopherols and delay lipid oxidation in bulk oil. The synergistic activity between phospholipids and tocopherols is due to the ability of amino-group-containing phospholipids (e.g., phosphatidylethanolamine (PE) and phosphatidylserine (PS)) to convert oxidized tocopherol back into tocopherols. This study shows the effect of PE and PS on the antioxidant activity of different tocopherol homologues in oil-in-water emulsions. Effect of emulsifier type on the interaction between tocopherols and phospholipids was also studied. δ-Tocopherol and PE exhibited greater antioxidant activity as compared to α-tocopherol and PE. PS displayed 1.5-3 times greater synergism than PE with Tween 20 as emulsifier whereas both PE and PS had a similar antioxidant activity in the presence of α-tocopherol when bovine serum albumin was used as the emulsifier. This study is the first to show that PE and PS can act synergistically with tocopherols to inhibit lipid oxidation in oil-in-water emulsions and can present a new clean label antioxidant strategy for food emulsions.

Effects of conjugated linoleic acid (CLA) on fat accumulation, activity, and proteomics analysis in Caenorhabditis elegans.

Conjugated linoleic acid (CLA) has been reported to reduce fat storage in cell culture and animal models. In the current study, the effects of CLA on the fat accumulation, activities, and proteomics were investigated using Caenorhabditis elegans. 100 µM CLA-TG nanoemulsion significantly reduced fat accumulation by 29% compared to linoleic acid (LA)-TG treatment via sir-2.1 (the ortholog of Sirtuin 1), without altering the worm size, growth rate, and pumping rate of C. elegans. CLA significantly increased moving speed and amplitude (the average centroid displacement over the entire track) of wild type worms compared to the LA group and these effects were dependent on aak-2 (AMPKα ortholog) and sir-2.1. Proteomics analysis showed CLA treatment influences various proteins associated in reproduction and development, translation, metabolic processes, and catabolism and proteolysis, in C. elegans. We have also confirmed the proteomics data that CLA reduced the fat accumulation via abs-1 (ATP Synthase B homolog). However, there were no significant effects of CLA on brood size, progeny numbers, and hatchability compared to LA treatment.

Spray-dried multilayered emulsions as a delivery method for omega-3 fatty acids into food systems.

Emulsion can be produced with electrostatic layer-by-layer deposition technologies to have cationic, thick multilayer interfacial membranes that are effective at inhibiting the oxidation of omega-3 fatty acids. This study investigated the stability of spray-dried multilayer emulsion upon reconstitution into an aqueous system. The primary (lecithin) and multilayered secondary emulsions (lecithin and chitosan) were spray-dried with corn syrup solids (1-20 wt %). The lecithin-chitosan multilayer interfacial membrane remained intact on the emulsion droplets upon reconstitution into an aqueous system. Reconstituted secondary (lecithin-chitosan) emulsions were more oxidatively stable than reconstituted primary (lecithin) emulsions. A minimum of 5 wt % corn syrup solids was needed to microencapsulate the secondary emulsion droplets. Maximum oxidative stability of both the powder and the reconstituted secondary emulsions was observed in samples with 5% and 20% corn syrup solids. Addition of EDTA (25 microM) inhibited oxidation of reconstituted primary and secondary emulsions. These studies suggest that a microencapsulated multilayered emulsion system could be used as a delivery system for omega-3 fatty acids in functional foods.

Properties of low-moisture viscoplastic materials consisting of oil droplets dispersed in a protein-carbohydrate-glycerol matrix: effect of oil concentration.

The influence of oil concentration and baking on the properties of low-moisture composites consisting of oil droplets dispersed in a protein-carbohydrate-glycerol matrix was investigated. These composites were produced by blending canola oil, whey protein concentrate (WPC), corn syrup, and glycerol together using a high-speed mixer. The resulting system consisted of oil droplets dispersed in a polar matrix. Some composites were analyzed directly after preparation, while others were analyzed after being heated at 176 degrees C for 10 min to simulate baking. The "lightness" of the composites was greater before baking (higher L value), but the color was more intense after baking (higher a and b values). The lightness and color intensity of the composites decreased as the oil concentration increased, with the effects being more pronounced in the baked samples. The zeta potential of the oil droplets (measured after dilution at pH 6) was highly negative (approximately -40 mV), indicating that whey protein was adsorbed to the droplet surfaces. The mean particle diameter (measured after dilution at pH 6) increased appreciably after baking, which was attributed to droplet flocculation. The rheological properties of the unbaked and baked materials were characterized by squeezing flow viscometry, which showed that the measurements associated with consistency and yield stress increased with increasing oil concentration and with baking.

Preparation and characterization of water/oil and water/oil/water emulsions containing biopolymer-gelled water droplets.

The purpose of this study was to create water-in-oil (W/O) and water-in-oil-in-water (W/O/W) emulsions containing gelled internal water droplets. Twenty weight percent W/O emulsions stabilized by a nonionic surfactant (6.4 wt % polyglycerol polyricinoleate, PGPR) were prepared that contained either 0 or 15 wt % whey protein isolate (WPI) in the aqueous phase, with the WPI-containing emulsions being either unheated or heated (80 degrees C for 20 min) to gel the protein. Optical microscopy and sedimentation tests did not indicate any significant changes in droplet characteristics of the W/O emulsions depending on WPI content (0 or 15%), shearing (0-7 min at constant shear), thermal processing (30-90 degrees C for 30 min), or storage at room temperature (up to 3 weeks). W/O/W emulsions were produced by homogenizing the W/O emulsions with an aqueous Tween 20 solution using either a membrane homogenizer (MH) or a high-pressure valve homogenizer (HPVH). For the MH the mean oil droplet size decreased with increasing number of passes, whereas for the HPVH it decreased with increasing number of passes and increasing homogenization pressure. The HPVH produced smaller droplets than the MH, but the MH produced a narrower particle size distribution. All W/O/W emulsions had a high retention of water droplets (>95%) within the larger oil droplets after homogenization. This study shows that W/O/W emulsions containing oil droplets with gelled water droplets inside can be produced by using MH or HPVH.