Oxidation of Methyl Linoleate in Oil-in-Water Micro- and Nanoemulsion Systems

Oxidation of methyl linoleate in O/W emulsions having droplets of median diameters ranging from 17 nm to 8.0 μm was carried out at 40°C. The oxidation process was analyzed on the basis of a kinetic equation of the autocatalytic type. The induction period was found to be shorter and the oxidation rate constant lower for emulsions with smaller oil droplets. The stoichiometry between methyl linoleate and oxygen was observed to be independent of both the size of oil droplet and the type of the surfactant and was found to be unity during the early stage of the oxidation. However, more oxgen was consumed in the oxidation of the methyl linoleate in the later half of the oxidation process.     

Aroma Release from Solid Droplet Emulsions: Effect of Lipid Type

Aroma compounds partition between the different phases of a food emulsion and the headspace but only those in the headspace are perceived. Phase transitions in the lipid droplets profoundly affect the position of the partitioning equilibria and hence headspace aroma concentration. The release of four volatile aroma compounds (ethyl butanoate, pentanoate, heptanoate and octanoate) from eicosane, hydrogenated palm fat or Salatrim^® emulsions stabilized with sodium caseinate were investigated as a function of fat crystallization, particle size and droplet concentration. For all compounds, the headspace aroma concentration in equilibrium with solid droplet emulsions was significantly higher than that in equilibrium with liquid droplet emulsions. The partitioning of volatile aroma compounds from emulsion does not depend on the type of liquid lipid, however, the interactions between solid lipid droplets and aroma compounds are significantly influenced by the nature of the crystalline fat. Notably, partitioning into the headspace was much lower for solid triglyceride droplet emulsions than for solid alkane emulsions. It was proposed that both residual liquid lipid in solid triglycerides and aroma co-crystallization with solid lipid could be responsible for higher aroma absorption by solid triglycerides.     

Improving the Oxidative Stability of Krill Oil-in-Water Emulsions

A positively charged protein (fish gelatin) or a negatively charged protein species (heat-treated milk protein–carbohydrate mixture) was added to a primary krill oil (KO) emulsion stabilized by the phospholipids inherent in KO, with the aim of improving the oxidative stability of KO-in-water emulsions at pH 8.0 (10 % KO). The positively charged fish gelatin deposited on the primary interface of the oil droplets in the primary KO-in-water emulsion improved the oxidative stability of the KO-in-water emulsion as evidenced by the higher eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) remaining and lower propanal produced after accelerated oxidation (40 °C, 25 days). The addition of the negatively charged heat-treated milk protein–carbohydrate mixture containing Maillard reaction products (MRP) to the bulk phase of the emulsion also enhanced the oxidative stability of the KO-in-water emulsion. The addition of MRP to the aqueous phase of phospholipids stabilized emulsion droplets offered more protection to EPA and DHA of the KO emulsions compared to the formation of an additional layer at the interface of the KO emulsion droplet. This suggests that interventions based on addition of antioxidant species to the formulation were more effective for arresting oxidation than increasing the thickness of the droplet interface. The addition of proteins into KO containing emulsion formulations is a promising strategy for protecting omega-3 marine phospholipids against oxidation.     

Oxidation of linoleic acid in emulsions: Effect of substrate, emulsifier, and sugar concentration

Linoleic acid oxidation in oil-in-water emulsions stabilized by a nonionic surfactant (Tween-20) was studied. The emulsion composition was varied at a constant oil droplet size. Lipid oxidation was measured as a function of time in the presence of a catalyst (FeSO₄ corbic acid) by two methods: gas chromatographic determination of residual substrate and ultraviolet-visible spectrophotometric determination of conjugated dienes. Rate of oxidation was influenced by the emulsion composition (relative concentrations of substrate and emulsifier) and especially by the partition of the emulsifier between the interface and water phase. Concentrations of emulsifier exceeding the critical micelle concentration protected the fatty acid against oxidation. Excess surfactant formed micelles and mixed micelles with linoleic acid, which retarded oxidation by diluting the substrate or perhaps by replacing linoleic acid at the interface, making it less accessible to radical attack. The addition of sucrose also had a protective effect, but only up to a certain concentration, indicating the effect may involve factors other than viscosity.     

Effect of droplet size on lipid oxidation rates of oil-in-water emulsions stabilized by protein

In emulsions lipid oxidation is mainly influenced by the properties of the interface. The aim of this work was to investigate the effects of droplet size and interfacial area on lipid oxidation in protein-stabilized emulsions. Emulsions, made of stripped sunflower oil (30% vol/vol) and stabilized by BSA were characterized by surface area values equal to 0.7, 5.1, and 16.3 m²·cm⁻³ oil. The kinetics of O₂ consumption and conjugated diene (CD) formation, performed on emulsions and nonemulsified controls, showed that emulsification prompted oxidation at an early stage. On condition that oxygen concentration was not limiting, the rates of O₂ consumption and CD formation were higher when the interfacial area was larger. Protein adsorbed at the interface probably restrained this pro-oxidant effect. Once most of the O₂ in the system was consumed (6–8 h), CD remained steady at a level depending directly on the ratio between oxidizable substrate and total amount of oxygen. At this stage of aging, the amounts of primary oxidation products were similar whatever the droplet size of the emulsion. Hexanal and pentane could be detected in the headspace of emulsions only at this stage. They were subsequently produced at rates not depending on oil droplet size and interfacial area.     

Emulsifier type,metal chelation and pH affect oxidative stability of n‐3‐enriched emulsions

Recent research has shown that the oxidative stability of oil‐in‐water emulsions is affected by the type of surfactant used as emulsifier. The aim of this study was to evaluate the effect of real food emulsifiers as well as metal chelation by EDTA and pH on the oxidative stability of a 10% n‐3‐enriched oil‐in‐water emulsion. The selected food emulsifiers were Tween 80, Citrem, sodium caseinate and lecithin. Lipid oxidation was evaluated by determination of peroxide values and secondary volatile oxidation products. Moreover, the zeta potential and the droplet sizes were determined. Tween resulted in the least oxidatively stable emulsions, followed by Citrem. When iron was present, caseinate‐stabilized emulsions oxidized slower than lecithin emulsions at pH 3, whereas the opposite was the case at pH 7. Oxidation generally progressed faster at pH 3 than at pH 7, irrespective of the addition of iron. EDTA generally reduced oxidation, as evaluated by volatiles formation in all emulsions, irrespective of pH and emulsifier type, except in the lecithin and caseinate emulsions where a pro‐oxidative effect was observed for some volatiles. The different effects of the emulsifier types could be related to their ability to chelate iron, scavenge free radicals, interfere with interactions between the lipid hydroperoxides and iron as well as to form a physical barrier around the oil droplets.     

Antioxidant and Prooxidant Activity Behavior of Phospholipids in Stripped Soybean Oil-in-Water Emulsions

Phospholipids have been reported to inhibit lipid oxidation in bulk oils, but very little is known about their influence on oxidation in oil-in-water emulsions. In the present study, the impact of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) on lipid oxidation was studied in 1% stripped soybean oil-in-water (O/W) emulsions as a function of DOPC concentration and pH (3 and 7). At pH 7.0, DOPC inhibited lipid oxidation in O/W emulsions, while DOPC was prooxidative at pH 3.0. DOPC did not affect emulsion droplet charge or size at either pH 3.0 or 7.0. The antioxidant activity at pH 7.0 was observed in a series of phospholipids (PL) that varied in fatty acid unsaturation level and chain length as well as type of phosphate head group. Overall, phosphatidylcholine with either oleic or palmitic acid were the most effective at inhibiting lipid hydroperoxide and hexanal formation of all of the PL tested. Antioxidant mechanism of PL could not be ascribed to their ability to decompose lipid hydroperoxides. It might be possible that, at pH 7.0, the PL antioxidant activity is related to their ability to form structures within the lipid phase of the emulsions droplets or to chelate metals.     

The kinetics of methyl linoleate emulsion autoxidation in the presence of polyhydroxy compounds

The kinetics of the autoxidation of methyl linoleate emulsions activated by carbohydrates likely to be present in meat, with special reference to the effects of functional groups, number of carbon atoms and configuration have been investigated by the rate of oxygen uptake. On the basis of equimolar concentrations of aldoses in the system, oxidation rate of methyl linoleate increases as the number of carbon atoms in the sugar molecule decreases, reaching a maximum in the presence of glyceraldehyde. Configuration of the aldose has a slight effect on the oxidation rate of methyl linoleate emulsions. At comparable molar ratios of hexose to methyl linoleate, the rate of oxidation was found to be: ketohexose > aldohexose > hexahydroxy alcohol. Replacement of the primary alcohol group in an aldohexose with a methyl group decreases the oxidation rate of methyl linoleate emulsion. An opposite effect is observed when the primary alcohol group is substituted with a carboxyl group, i.e., in the presence of sodium glucuronate. 2-Deoxy-D-glucose and 2-deoxy-D-ribose exhibit a lesser effect on the autoxidation of methyl linoleate emulsion than glucose and ribose, respectively. Oxidation rates in the presence of reducing disaccharides, maltose, lactose and cellobiose, are more rapid than in the presence of the non-reducing disaccharide sucrose. Presented at the AOCS Meeting, Toronto, 1962. American Meat Institute Foundation Journal Paper No. 254.     

Characterization of fish oil-in-water emulsions using light-scattering,nuclear magnetic resonance,and gas chromatography-headspace analyses

The effect of the molecular environment on the physical and oxidative properties of homogenized or microfluidized fish oil-in-water emulsions (5% w/w tuna oil in pH 7 phosphate buffer) stabilized by whey protein isolate (WPI, 1 or 5% w/w) or lecithin (2.5% w/w) was examined. Laser light-scattering measurements showed that WPI-stabilized emulsions had smaller particle sizes than lecithin-stabilized emulsions, and that higher pressures reduced the particle size. WPI afforded more protection against oil oxidation than did lecithin, as evidenced by the lower headspace propanal of emulsions as measured by GC-headspace analysis, despite the larger interface in WPI-stabilized emulsions. Reducing the concentration of WPI in emulsions from 5 to 1% decreased the oxidative stability of WPI-stabilized emulsions. The ¹H NMR transverse relaxation times (T ₂) of FA chains in emulsion droplets stabilized by the same surfactants made by homogenization or microfluidization were different and not always related to particle size. The higher mobility (i.e., longer T ₂) of the unsaturated parts of the FA chains within an oil droplet, compared with the saturated parts, suggests that the unsaturated components tended to stay in the core of the oil droplets. This experimental result supports the hypothesis reported in other literature that the more unsaturated FA are buried in the oil core of oil-in-water emulsions. The lack of a universal correlation between particle size and oxidation suggests that the mobility of particles in an emulsion has an influence on the rate of oxidation.     

Physico-chemical properties of heavy crude oil-in-water emulsions stabilized by mixtures of ionic and non-ionic ethoxylated nonylphenol surfactants and medium chain alcohols

This work describes the formulation and evaluation of concentrated, heavy oil-in-water emulsions stabilized by mixtures of ethoxylated surfactants and normal alcohols. The rheology, stability and droplet size of these emulsions were investigated as functions of the emulsification process parameters. The parameters investigated for this study include emulsifier agent composition, presence of additives, pH and salinity of the continuous aqueous phase, emulsification temperature, oil content and emulsion aging. The produced emulsions had viscosities ranging from 30 to 150 mPa s and represent a 30-fold reduction of the crude oil viscosity. Sauter mean diameters of the droplets ranged from 10 to 50 μm. The emulsions were produced by mixing the oil with an aqueous solution containing medium normal-chain alcohols and small quantities of a mixture of ethoxylated nonylphenol and ethoxylated amine surfactants. The presence of these alcohols led to a sharp decrease in the droplet size of the emulsion. This size decrease had a direct impact on the emulsions’ stability and apparent viscosity. The rheological parameters of the aged emulsions were also essentially constant over a 42-day period.     

RHEOLOGICAL PROPERTIES OF EMULSIONS OF OIL IN AQUEOUS NON-NEWTONIAN POLYMERIC MEDIA

The viscous flow behaviour of emulsions of oil in non-Newtonian Ellis model fluids (aqueous solutions of sodium carboxymethyl cellulose) has been studied experimentally. The addition of oil droplets to a non-Newtonian aqueous suspending media leads to an increase in the apparent viscosity of the emulsion system. The shape of the emulsion flow curves (apparent viscosity versus shear-stress plots) is found to be similar to that of the suspending media; consequently, the emulsion flow curves at various oil concentrations (0 to 70% by volume) are described adequately by the Ellis model. The relative viscosities of the emulsions of oil in non-Newtonian aqueous suspending media are significantly lower than those exhibited by emulsions of oil in Newtonian media.     

Fat Crystals Influence Methylcellulose Stabilization of Lipid Emulsions

Oil-in-water emulsions stabilized with methylcellulose (MC) varied in stability depending on the composition of the fat phase. When droplets were composed entirely of liquid oil, MC was able to form a continuous, protective film around the droplets. Therefore, when two liquid oil droplets were brought into contact, they underwent extreme shape deformation but did not coalesce, even when excess force was used. Subsequently, interfacial crystals extending into the aqueous phase from palm kernel oil droplets were aimed into an entirely liquid oil droplet. The MC-coated droplet would deform wherever the crystal contacted; however, the protruding crystals could not penetrate into the liquid oil droplet. Conversely, when the target droplet was composed of a small amount of solid fat that resulted in localized crystalline regions and the interfacial crystals of the second droplet were aimed at this region, they then easily pierced the droplet. This demonstrates that MC is an excellent stabilizer for liquid oil droplets but internal lipid crystals within fat globules can alter MC surface conformation to allow for crystal penetration and arrested coalescence.     

Water-in-triglyceride oil emulsions. Effect of fat crystals on stability

The influence of low concentrations (0.1-5%) of fat crystals on the stability of water-in-soybean oil emulsions was examined by light scattering and sedimentation experiments. Both the initial flocculation/coalescence rate and long-term stability against water separation were determined. The initial flocculation/coalescence rate increased upon addition of small amounts of fat crystals. When the crystal concentration was increased above a critical concentration (specific to a system), a decrease in the flocculation/coalescence rate occurred. The increased flocculation/coalescence rate is likely the effect of bridging of water droplets by fat crystals. Fat crystal wetting by water is an important criterion for this phenomenon to occur. Emulsion stabilization for crystal concentrations above critical is caused by a mechanical screening of water droplets. The presence of considerable amounts of crystals in oil also lowered the density difference between droplet and medium, and enhanced viscosity. The degree of increase in viscosity depended upon the emulsifier. Both a decrease in density difference and an increase in viscosity play a role in hindering flocculation/coalescence of droplets. In long-term studies of water separation, all concentrations of fat crystals stabilized the water-in-oil emulsions. The droplet size of these emulsions increased until the critical droplet size was approached where the screening effect of crystals on the droplets no longer stabilized the emulsions. The stabilizing effect for emulsions with monoolein was continuously improved by increasing the amount of crystals up to 5%. For lecithin-stabilized emulsions, an optimal effect was achieved for fact crystal concentrations of 1–2%.     

Influence of oil phase concentration on droplet size distribution and stability of oil‐in‐water emulsions

The objective of this study was to investigate the effect of oil phase concentration, at different emulsification conditions concerning homogenization time and emulsifier content, on droplet size distribution and stability of corn oil‐in‐water emulsions. Emulsions were prepared with 3, 5, 10, and 20% w/w triethanolamine oleate (calculated on oil amount), 0.53% w/w carboxymethylcellulose (calculated on water amount), and 5, 10, 20, 30, or 40% w/w oil, and homogenized 5, 10, 20, and 60 min. It was found that increase in oil phase concentration led to decrease in specific surface area and increase in polydispersity of emulsion at lower emulsifier concentration and less intense homogenization. At emulsifier concentrations ≤10% and homogenization time ranges of 20–60 min the non‐monotonous variation in droplet size parameters with oil concentration was observed, as a result of the interaction between triethanolamine oleate and carboxymethylcellulose, which were confirmed by viscosity measurements. However, at emulsifier concentration of 20% an increase in specific surface area and decrease in polydispersity with the increase in oil concentration occurred due to an increase in equilibrium concentration of emulsifier in the continuous phase. Further, influence of oil concentration on emulsion creaming stability was found to be independent on emulsifier concentration and homogenization time. Therefore, a decrease in creaming with increase in oil concentration was observed in all the examined triethanolamine oleate (TEAO) concentration and homogenization time ranges. Practical applications: Emulsions are colloidal systems which can be encountered in different industrial sectors, such as food, pharmaceutical, cosmetics, oil industry, etc. Determination of the droplet size of emulsion is probably the most important way of their characterization, since it influences the properties of emulsion such as rheology, texture, shelf life stability, appearance, taste, etc. The size of the droplets depends on a wide range of parameters. One of them is certainly the concentration of the oil phase. However, since the impact of one parameter is often influenced with the intensity of the other variable involved in the emulsion generation, the aim of the present work was to examine the effect of corn oil concentration on droplet size parameters and stability of oil‐in‐water emulsions at different emulsification conditions. Therefore a step toward creation of emulsions with desired final properties was made.     

Effects of droplet size on the oxidative stability of oil-in-water emulsions

The effects of droplet size and emulsifiers on oxidative stability of polyunsaturated TAG in oil-in-water (o/w) emulsions with droplet sizes of 0.806±0.0690, 3.28±0.0660, or 10.7±0.106 μm (mean ± SD) were investigated. Hydroperoxide contents in the emulsion with a mean droplet size of 0.831 μm were significantly lower than those in the emulsion with a mean droplet size of 12.8 μm for up to 120 h of oxidation time. Residual oxygen contents in the headspace air of the vials containing an o/w emulsion with a mean droplet size of 0.831 μm were lower compared with those of the emulsion with a mean droplet size of 12.8 μm. Hexanal developed from soybean oil TAG o/w emulsions with smaller droplet size showed significantly lower residual oxygen contents than those of the larger droplet size emulsions. Consequently, oxidative stability of TAG in o/w emulsions could be controlled by the size of oil droplet even though the origins of TAG were different. Spin-spin relaxation time of protons of acyl residues on TAG in o/w emulsions measured by ¹H NMR suggested that motional frequency of some acyl residues was shorter in o/w emulsions with a smaller droplet size. The effect of the wedge associated with hydrophobic acyl residues of emulsifiers was proposed as a possible mechanism to explain differences in oxidative stability between o/w emulsions with different droplet sizes.     

Experimental characterization of emulsion formation and coalescence by nuclear magnetic resonance restricted diffusion techniques

Nuclear magnetic resonance (NMR) is explored as a technique for noninvasively monitoring emulsion droplet formation and destabilization. The method makes use of the fact that the diffusion of oil molecules within oil-in-water emulsion droplets results in attenuation of a coherent magnetic signal that emanates from those molecules. If oil diffusion is limited by the size of the droplet, the shape of a plot of attenuation over time is directly affected by the droplet radius. We use this approach to determine noninvasively the effect of surfactant type, surfactant concentration, pH, and ionic strength on droplet sizes within a 40 wt% octane and water emulsion, stabilized by Tween 20 or β-lactoglobulin (β-Lg). We find that addition of the low-molecular-weight Tween 20 forms finer emulsion droplets than does addition of the protein, and that the Tween 20 emulsion is sensitive to surfactant concentration below a threshold “saturation” concentration. The droplet sizes in β-Lg-containing emulsions increase as pH increases above the isoelectric point and as ionic strength increases. The fact that the NMR technique does not mistake clusters of droplets for single large droplets makes the analysis of these effects unambiguous. We further extend the use of NMR diffusion techniques to monitor the effect of surfactant type, surfactant concentration, and convection on the rate of droplet coalescence. The ability of NMR methods to distinguish between large single droplets and droplet clusters makes it well-suited to monitor coalescence processes independently from flocculation.     

De-emulsification of 2-ethyl-1-hexanol/water emulsion using oil-wet narrow channel combined with low-speed rotation

Low-speed rotation of disc in an internal circulation of a novel de-emulsification with rotation-dise horizental contactor (RHC-D) realized de-emulsification for O/W emulsions due to repeated coalescence in oil-wet narrow channels at a low rotation speed. For three emulsions included ethanol/water/2-ethyl-1-hexanol, ethanol/water/2-ethyl-1-hexanol/SDS (Sodium Dodecyl Sulfonate) and 2-ethyl-1-hexanol/water/SDS emulsion, deemulsification ratios of oil phase could reach 1, 1 and 0.67 respectively at 170 r·min^-1, and de-emulsification ratios increased obviously after agitating 10 min. De-emulsification experiment in the seam indicated that oil droplet sizes in O/W emulsion became larger after de-emulsification. The main de-emulsification mechanism in RHCD was the coalescence of oil droplets in oil-wet narrow channels. With increase of the rotation speed, oil droplets dispersed better in the aqueous phase. However, de-emulsification effect enhanced due to the increase of the coalescence rate at a bit higher rotation speed. In addition, internal circulation made those O/W emulsions to be broken repeatedly, consequently de-emulsification ratio increased. Repeated de-emulsification through internal circulation might make continuous extraction of ethanol come true at a low rotation speed.     

Microencapsulation of Flaxseed Oil by Spray Drying: Effect of Oil Load and Type of Wall Material

The objective of this work was to evaluate the effect of the type of wall material and the oil load on the microencapsulation of flaxseed oil by spray drying. Gum arabic, whey protein concentrate, and a modified starch were used to produce the microcapsules, each with four oil concentrations (10, 20, 30, and 40% oil, w/w, with respect to total solids), for a total of 12 tests. Initially, the feed emulsions were characterized for stability, viscosity, and droplet size. Then they were dried in a laboratory-scale spray dryer and the resulting particles were analyzed for encapsulation efficiency, lipid oxidation, moisture content, and bulk density. The increase in oil concentration led to the production of emulsions with larger droplets and lower viscosity, which directly affected powder properties, resulting in lower encapsulation efficiency and higher lipid oxidation. Among the three wall materials evaluated, the modified starch showed the best performance, with the highest encapsulation efficiency and lowest peroxide values.     

Stabilization of liquid water-in-oil emulsions by modifying the interfacial interaction of glycerol monooleate with aqueous phase ingredients

Glycerol monooleate (GMO)-stabilized liquid water-in-vegetable oil emulsions are difficult to stabilize due to the desorption of GMO from the water-vegetable oil interface toward the oil phase. This work improved the stability of GMO-stabilized liquid 20 wt% water-in-canola oil (W/CO) emulsion by modifying the dispersed aqueous phase composition with hydrogen bond-forming agents. As a control, 20 wt% water-in-mineral oil (W/MO) emulsion was also utilized. Different concentrations of hydrogen bond-forming agents (citric acid (CA), ascorbic acid (AA), low methoxyl pectin (LMP)) with and without salts (sodium chloride (S) or calcium chloride (Ca)) were added to the aqueous phase before emulsification, which enhanced emulsifier binding to the water–oil interface. W/CO emulsion without any aqueous phase additive destabilized instantly, whereas W/MO emulsion stayed stable during the week-long observation. The addition of hydrogen bond-forming agents and salts significantly improved emulsion stability. LMP, with many hydrogen bond-forming groups, was able to provide the highest emulsion stability after 7 days in both oils compared to AA, CA and their mixtures with S. Emulsions with both oils formed weak gels due to the formation of an extensive network of water droplet aggregates. Overall, the hydrogen bond-forming agents interacted with GMO at the interface, thereby favoring their presence at the water droplet surface and significantly improving the stability of liquid W/CO emulsions. The knowledge developed in this research can be useful in utilizing GMO to stabilize liquid water-in-oil emulsions without using any fat crystal network.     

Influence of Coagulant Salt Addition on the Treatment of Oil‐in‐Water Emulsions by Centrifugation,Ultrafiltration, and Vacuum Evaporation

Abstract

Droplet size is a key factor in the treatment of oil‐in‐water (O/W) emulsions, because of its influence on emulsion properties. The addition of a coagulant salt generally causes emulsion destabilization, increasing the droplet size, and enhancing coalescence between oil droplets, which helps its further treatment. The influence of CaCl₂ addition on droplet size distribution of a commercial O/W emulsion used in machining processes was studied in order to facilitate oil removal and to improve its further treatment by centrifugation, ultrafiltration (UF) and vacuum evaporation. The critical coagulation concentration (CCC) was observed at a CaCl₂ concentration of 0.05 M. The quality of the final aqueous effluent, expressed as its chemical oxygen demand (COD) value, was compared for all treatments. The highest COD values were obtained for centrifugation, while the COD of the UF permeate was approximately constant for all UF trials. The best effluent quality was obtained by vacuum evaporation. A combination of these techniques should be appropriate for most industrial treatments of O/W emulsions, depending on the subsequent use of the resulting aqueous effluent.