Food-grade microemulsions and nanoemulsions: Role of oil phase composition on formation and stability

Lemon oil is widely used as a flavoring component in beverages, foods, cosmetics, and household products. Lemon oil comes in a variety of chemical compositions depending on its biological origin, extraction methods, and purification procedures. At present, there is a relatively poor understanding of the influence of lemon oil composition on its functional properties. In this study, we examined the influence of lemon oil fold (1×, 3×, 5× and 10×) on the formation and properties of oil-in-water microemulsions and nanoemulsions. The concentration of both polar (high water solubility and low log P) and non-polar (low-water solubility and high log P) components increased with increasing oil fold. The nature of the colloid dispersions formed was established using an emulsion titration method that involved titrating lemon oil droplets into a surfactant micelle solution (1% Tween 80). Oil fold affected the rate and extent of solubilization, as well as the stability of lemon oil droplets to growth. The maximum amount of lemon oil that could be solubilized within the micelles increased with increasing oil fold, as did the stability of lemon oil droplets to growth. The results were interpreted in terms of the ability of different lemon oil molecules to be incorporated within water or surfactant micelles, and the influence of lemon oil polarity on Ostwald ripening. This study provides valuable information about the relationship between lemon oil composition and its performance in colloidal delivery systems suitable for use in the food and beverage industries.     

Encapsulation of functional lipophilic components in surfactant-based colloidal delivery systems: Vitamin E,vitamin D,and lemon oil

The fabrication and stability of surfactant-based colloidal delivery systems (microemulsions and emulsions) suitable for encapsulation of lipophilic active agents (vitamins and flavours) was investigated. An emulsion titration method was used to study the influence of surfactant type (Tween 20, 60 and 80) and oil type (Vitamin E, vitamin D₃ and lemon oil) on the incorporation of lipophilic components into surfactant micelles. Oil-in-water emulsions were formed and then different amounts were titrated into surfactant micelle solutions. The influence of surfactant-to-oil ratio (SOR) and oil type on the formation of colloidal dispersions was examined using dynamic light scattering and turbidity measurements. SOR, oil type, and surfactant type had a pronounced influence on the nature of the colloidal dispersions formed. Microemulsions could not be formed using vitamin D or E in 1% Tween solutions, due to the relatively large size of the lipophilic molecules relative to the hydrophobic interior of the surfactant micelles. On the other hand, microemulsions could be formed from lemon oil at relatively high SORs. There was not a major impact of non-ionic surfactant type (Tween 20, 60 or 80) on the formation and properties of the colloidal dispersions. However, Tween 20 micelles did appear to be able to solubilise less lemon oil than Tween 60 or 80 micelles, presumably due to their smaller dimensions. This study provides useful information for the rational design of food grade colloidal delivery systems for encapsulating flavour oils, oil-soluble vitamins, and other functional lipids for application in foods and beverages.     

Food-grade microemulsions,nanoemulsions and emulsions: Fabrication from sucrose monopalmitate & lemon oil

Sucrose monopalmitate (SMP) is a non-toxic, biodegradable, non-ionic surfactant suitable for use in foods and beverages. This study aimed to establish conditions where stable microemulsions, nanoemulsions or emulsions could be fabricated using SMP as a surfactant and lemon oil as an oil phase. Emulsions (r > 100 nm) or nanoemulsions (r < 100 nm) were formed at low surfactant-to-oil ratios (SOR < 1) depending on homogenization conditions, whereas microemulsions (r < 10 nm) were formed at higher ratios (SOR > 1). The impact of simple mixing, thermal treatment, and homogenization on the formation of the different colloidal systems was investigated. Blending/heating was needed to produce microemulsions or emulsions, whereas blending/heating/homogenization was needed to produce nanoemulsions. The impact of environmental stresses (pH, ionic strength, temperature) on the functional performance of nanoemulsions and microemulsions was examined. Relatively stable nanoemulsions could be formed at pH 6 and 7 and stable microemulsions at pH 5 and 6, but extensive particle growth/aggregation occurred at lower and higher pH values. Microemulsions were relatively stable to salt addition (0–200 mM NaCl), but nanoemulsions exhibited droplet aggregation/growth at ≥50 mM NaCl after 1 month storage at pH 7. Microemulsions formed gels at low temperatures (5 °C), were stable at ambient temperatures (23 °C), and exhibited particle growth at elevated temperatures (40 °C). Nanoemulsions were stable at refrigerator (5 °C) and ambient (23 °C) temperatures, but exhibited coalescence at elevated temperatures (40 °C). This study provides important information for optimizing the application of sucrose monoesters to form colloidal dispersions in food and beverage products.     

Process optimization and stability of d-limonene nanoemulsions prepared by catastrophic phase inversion method

The aim of this study was to optimize the process and stability of d-limonene nanoemulsions. The nanoemulsions were prepared by catastrophic phase inversion method using Tween 80 as surfactant. According to the results, the SOR value would considerably affect the turbidity and the mean particle diameter of emulsions. At a high concentration of surfactant (S/O = 1.5), d-limonene nanoemulsions could be obtained. In addition, the formation of nanoemulsions may be primarily related to the viscosity of oil phase. When the oil phase contained less than 15% (w/w) olive oil, the nanoemulsions could be prepared. The turbidities and the mean particle diameters of d-limonene nanoemulsions with adding the same concentration of different plant oils were similar. Furthermore, it can be found that adding olive oil could enhance the stability of d-limonene nanoemulsion system and decrease Ostwald ripening rate, and the Ostwald ripening rate of d-limonene nanoemulsion at 4 °C was higher than that at 28 °C.     

Utilisation of spontaneous emulsification to fabricate lutein‐loaded nanoemulsion‐based delivery systems: factors influencing particle size and colour

Factors influencing the formation and properties of lutein‐loaded nanoemulsions fabricated using spontaneous emulsification (SE) were investigated. Nanoemulsion formation depended on oil type: small droplets (diameter ≈ 200 nm) with a narrow monomodal particle size distribution (polydispersity index ≈ 0.23) could be formed using medium‐chain triglycerides (MCT), but not long‐chain triglycerides. Nanoemulsion formation also depended on surfactant type and concentration, with Tween 80 being the most effective surfactant. Optimisation of lutein‐loaded nanoemulsions formed by SE led to systems with a final composition of 10 wt% oil phase (0.12 wt% lutein + 9.88 wt% MCT), 10 wt% Tween 80, and 80 wt% aqueous phase. The nanoemulsions were stable to droplet aggregation when stored at ambient temperature for up to 1 month; however, some colour fading occurred due to lutein degradation. This study indicated the potential of nanoemulsion‐based delivery system fabricated using a low‐energy method for encapsulation and protection of lutein.     

Optimization of lipid nanoparticle formation for beverage applications: Influence of oil type,cosolvents, and cosurfactants on nanoemulsion properties

The influence of flavor oil composition, cosolvents (glycerol and propylene glycol), and cosurfactant (lysolecithin) on the formation and stability of lemon oil nanoemulsions stabilized by sucrose monoesters was examined. At ambient temperature, nanoemulsions containing 1-, 3-, and 5-fold lemon oils were stable to droplet growth, whereas those containing 10-fold lemon oil were unstable. For 10-fold lemon oil nanoemulsions, the droplet growth rate increased with increasing temperature, cosolvent addition, and decreasing lysolecithin concentration, which was attributed to the influence of these factors on the phase inversion temperature. Clear nanoemulsions could be formulated that maintained small mean particle diameters (d ≈ 81 nm) during storage at ambient temperature for 1 month. The information generated in this study is useful for designing stable flavor nanoemulsions for applications in functional foods and beverages.     

Influence of chitosan and NaCl on physicochemical properties of low-acid tuna oil-in-water emulsions stabilized by non-ionic surfactant

An influence of low molecular weight (LMW) chitosan on physicochemical properties and stability of low-acid (pH 6) tuna oil-in-water emulsion stabilized by non-ionic surfactant (Tween 80) was studied. The mean droplet diameter, droplet charge (ζ-potential), creaming stability and microstructure of emulsions (5 wt% oil) were evaluated. The added chitosan was adsorbed on the surface of oil droplets stabilized by Tween 80 through electrostatic interactions. Such addition of chitosan at different concentrations (0–10 wt%) to emulsions showed slight effect on the mean droplet diameter. However, the degree of flocculation was a function of chitosan concentration assessed by emulsions' microstructure and creaming index. The impact of chitosan on the strength of the colloidal interaction between the emulsion droplets increased with increasing chitosan concentration. The mean diameter of droplet in emulsions increased with increasing NaCl because of the electrostatic screening effect. The addition of LMW chitosan could be performed to create tuna oil emulsions with low-acid to neutral character, as well as various physicochemical and stability properties suitable for health food products.     

Formulation of a cosurfactant-free O/W microemulsion using nonionic surfactant mixtures

ABSTRACT:  A cosurfactant-free O/W microemulsion composed of oil, a mixture of hydrophilic and hydrophobic surfactants, and water has been developed using food-grade components as a nutrient delivery system. We started our investigation to monitor the phase behavior of this system based on a hydrophilic surfactant (Tween 80). From a phase diagram, the weight ratio of 5.4:33.8:60.8 = oil:surfactant:water was selected as a combination ratio for the O/W microemulsion system. We also investigated the combination effect of different hydrophobic surfactants to Tween 80 on microemulsion formation. Use of hydrophobic surfactants with Tween 80 produced smaller droplets than Tween 80 alone. Rheological studies showed that all microemulsions followed shear-thinning behavior. The turbidity of microemulsions did not change after accelerated stability tests, indicating that this microemulsion system was stable under the given harsh conditions. When docosahexaenoic acid (DHA) oil was applied to this microemulsion system, the particle size and the turbidity were not significantly changed. Dilution with a different aqueous medium, either water or acidic fluid, did not significantly change the microemulsion turbidity. DHA oil incorporated in microemulsion showed higher oxidation stability than free DHA oil.     

Fabrication of Food Grade Vitamin E Nanoemulsion by Low Energy Approach,Characterization and Its Application

The present study was carried out to fabricate the food grade vitamin E acetate nanoemulsion using edible mustard oil and to evaluate its improved bioactivities. A food-grade vitamin E acetate nanoemulsion was fabricated using the edible mustard oil and surfactant Tween-80. Flocculation was not observed for 15 days. The nanoemulsion was characterized for droplet morphology and size distribution using atomic force microscope and zetasizer, respectively. We observe a stable nanoemulsion of spherical morphology and a size distribution of 86.45 ± 3.61 nm. Further, the high-performance liquid chromatography method was used to determine the vitamin E acetate concentration and encapsulation efficiency for the stable nanoemulsion. These nanoemulsions showed improved bioactivity, antioxidant, and antimicrobial activity and could be potentially used to increase the shelf life of fruit juice.     

Antimicrobial activity of a food-grade fully dilutable microemulsion against Escherichia coli and Staphylococcus aureus

Microemulsions are colloidal nanodispersions of oil and water stabilized by an interfacial film of surfactant molecules, typically in conjunction with a cosurfactant. There is a limited number of reports in the literature on microemulsion use for antimicrobial purposes. The physicochemical characterization of a food-grade fully dilutable microemulsion system with glycerol monolaurate (GML) as oil, organic acids as cosurfactant, Tween 80 as surfactant, and the antimicrobial activities against Escherichia coli and Staphylococcus aureus have been studied in this paper. The influence of organic acids on oil solubilization was clearly reflected in the phase behavior of these systems. Propionic acid demonstrated the greatest capability to improve the oil solubilization among the tested linear and nonlinear chain organic acids and contributed to the formation of U-type microemulsion systems. One microemulsion formulation with an average particle size of 8 nm was selected, the composition is GML/propionic acid/Tween 80/water = 3:9:8:12. The kinetics of killing experiments demonstrated that the undiluted microemulsion caused a complete loss of viability of E. coli or S. aureus cells in 1 min and still had effective bactericidal effects even when diluted, more than 99% viable E. coli cells were killed within 15 min and a complete loss of viability was achieved at 45 min while more than 99% viable S. aureus cells were killed within 30 min and a complete loss of viability was achieved at 60 min in the presence of the 10-fold diluted microemulsion. The fast killing kinetics of the ten-fold serial dilutions of microemulsions were in good agreement with the mode of action studies, indicating that the interaction between the antimicrobial microemulsions and bacterial membranes significantly decreased the bacterial cell surface hydrophobicity and induced the quick release of 260 nm absorbing materials. This work suggests the potential use of food-grade fully dilutable microemulsions for antimicrobial purposes in beverages or seafood products.     

Stability of emulsions for parenteral feeding: Preparation and characterization of o/w nanoemulsions with natural oils and Pluronic f68 as surfactant

For hydrophobic bioactive compounds, poor water solubility is a major limiting factor for their use in different applications in the field of food industry or pharmacy. For this reason they are administrated as emulsions, in which the substance is dissolved in an organic compound, which is dispersed in an aqueous phase as droplets stabilized by a surfactant. It has been demonstrated that the colloidal stability of the nanoemulsion formulations can be precisely controlled by the chemical structure of the interface. In this paper, a promising delivery system has been studied. As surfactant, we have used the amphiphilic uncharged tri-block copolymer Pluronic F68, and natural oils from soybean, sesame and olive as the organic phase. The nanoemulsions were prepared by ultrasonication, and their stability at different synthesis conditions such as ultrasound power and surfactant concentration has been studied by monitoring backscattering using a Turbiscan. The more stable emulsions have been characterized by DLS, and their droplet size was below 500 nm, which has resulted very appropriate for parenteral administration. A destabilization of the system always takes place above certain surfactant concentration. This phenomenon was described as a depletion–flocculation effect caused by non-adsorbed micelles. This destabilization was modelled by adding to the DLVO interaction energy a contribution addressing the force between two spherical particles in the presence of non-adsorbing spherical macromolecules.     

Rheology and microstructure of myofibrillar protein-plant lipid composite gels: Effect of emulsion droplet size and membrane type

Composite gels were prepared from 2% myofibrillar protein (MP) with 10% imbedded pre-emulsified plant oils (olive and peanut) of various particle sizes at 0.6 M NaCl, pH 6.2. Dynamic rheological testing upon temperature sweeping (20-70 °C at 2 °C/min) showed substantial increases in G′ (elastic modulus) of MP sols/gels with the addition of emulsions, and the G′ increases were inversely related to the emulsion droplet size. Furthermore, gels containing emulsified olive oil had a greater (P < 0.05) hardness than those containing emulsified peanut oil. Regardless of oil types, MP-coated oil droplets exhibited stronger reinforcement of MP gels than Tween 80-stablized oil droplets; the latter composite gels had considerable syneresis. Light microscopy with paraffin sectioning revealed a stable gel structure when filled with protein-coated oil droplets, compared to gels with Tween 80-treated emulsions that showed coalesced oil droplets. These results suggest that rheological characteristics, hardness, texture, and water-holding capacity of MP gels were influenced by type of oils, the nature of the interfacial membrane, and the size of emulsion droplets.     

Solubilization Kinetics of Triacyl Glycerol and Hydrocarbon Emulsion Droplets in a Micellar Solution

Solubilization of oil molecules in surfactant micelles can have pronounced effects on the physicochemical properties of oil-in-water emulsions, e.g., reaction rates, distribution of nonpolar ingredients, emulsion stability and controlled flavor release. Static light-scattering was used to compare the solubilization kinetics of corn oil droplets with those of n-hexadecane droplets (ø= 0.02 wt%, d₃₂= 0.3 μm) in a micellar surfactant solution (2 wt% Tween 20). The n-hexadecane droplets were completely solubilized by the micelles within 5 days, but no change was observed in the corn oil emulsíon Possible reasons for the observed differences in solubilization kinetics were related to the molecular geometry and size of the oil molecules.     

Formation of nanoemulsions stabilized by model food-grade emulsifiers using high-pressure homogenization: Factors affecting particle size

Nanoemulsions are finding increasing utilization in the food and beverage industries for certain applications because of their unique physicochemical and functional properties: high encapsulation efficiency; low turbidity; high bioavailability; high physical stability. In this study, we examined the impact of system composition and homogenization conditions on the formation of nanoemulsions using a high-pressure homogenizer (microfluidizer). The mean particle diameter decreased with increasing homogenization pressure and number of passes, with a linear log–log relationship between mean particle diameter and homogenization pressure. The minimum droplet diameter that could be produced after 6 passes at 14 kbar depended strongly on emulsifier type and concentration: SDS < Tween 20 < β-lactoglobulin < sodium caseinate. Small-molecule surfactants formed smaller droplets than proteins, which was attributed to their ability to rapidly adsorb to the droplet surfaces during homogenization. The impact of phase viscosity was examined by using different octadecane-to-corn oil ratios in the oil phase and different glycerol-to-water ratios in the aqueous phase. The minimum droplet size achievable decreased as the ratio of disperse phase to continuous phase viscosities (η_D/η_C) decreased for SDS-stabilized emulsions, but was relatively independent of η_D/η_C for β-lactoglobulin-stabilized emulsions. At low viscosity ratios, much smaller mean droplet diameters could be achieved for SDS (d ∼ 60 nm) than for β-lactoglobulin (d ∼ 150 nm). The information reported in this study will facilitate the rational design of food-grade nanoemulsions using high-pressure homogenization methods.     

Incorporation of soybean oil improves the dilutability of essential oil microemulsions

Plant essential oils (EOs) have strong antimicrobial and antioxidant activities. However, their water insolubility and volatility limit their practical application. Microemulsions are thermodynamically stable delivery systems for hydrophobic bioactive compounds but can be destabilized after dilution by the polar phase. In the present study, soybean oil (SBO) was studied for the impacts on formation and dilutability of EO microemulsions comprised of polysorbate 80 (Tween™ 80) as a surfactant and equal mass of water and propylene glycol as the polar phase. The oil phase contained EO (cinnamon bark oil, eugenol, or thymol) and SBO at 1:0, 2:1 or 4:1 mass ratios. Pseudo-ternary phase diagrams were constructed after titrating the polar phase into Tween™ 80–oil mixture at 1:1 to 9:1 mass ratios. Blending SBO with EO expanded the regimes of microemulsions and reduced the droplet dimensions that were stable over 90 days. Viscosity and electrical conductivity data indicated the transition from W/O to O/W microemulsions as the content of polar phase increased from 10% to 90% w/w. The enhanced dilutability of microemulsions after blending with SBO can broaden the application of EOs.     

Physicochemical characteristics of mixed colloidal dispersions: Models for foods containing fat and starch

Mixed colloidal dispersions, consisting of starch granules and lipid droplets, were used as model systems to represent commercial food products, such as sauces, desserts, and soups. Colloidal dispersions were prepared by mixing unheated modified starch (3.5 or 5.0 wt%) and lipid droplets (2.5, 5.0 or 8.0 wt% oil) together and then heating (90 °C for 5 min) to promote starch gelatinization. The lipid droplets were stabilized by a food-grade surfactant consisting of a mixture of diacetyl tartaric acid ester of mono-diglycerides (DATEM) and mono-diglycerides. The influence of thermal processing and composition (starch, lipid, surfactant content) on the particle size, microstructure, lightness, and shear viscosity of the model sauces was examined. There was a pronounced increase in shear viscosity upon heating, which was attributed to the swelling of the starch granules leading to a close-packed particle suspension. The shear viscosity and lightness of the colloidal dispersions increased with increasing starch and fat content, with fat droplets dominating lightness and starch granules dominating viscosity. The amount of surfactant present also influenced the rheology of the mixed colloidal dispersions, which was attributed to its ability to modify starch granule interactions. Overall, these results have important implications for designing high quality emulsion-based food products, such as soups, sauces, desserts, and beverages.     

Impact of lemon oil composition on formation and stability of model food and beverage emulsions

Lemon oil is a complex organic compound isolated from citrus peel, which is commonly used as a flavouring agent in beverages, foods, cosmetics, and household products. We have studied the influence of lemon oil fold (1×, 3×, 5× and 10×) on the formation and properties of oil-in-water emulsions. Initially, the composition, molecular characteristics, and physicochemical properties of the four lemon oils were established. The main constituents in single-fold lemon oil were monoterpenes (>90%), whereas the major constituents in 10-fold lemon oil were monoterpenes (≈35%), sesquiterpenes (≈14%) and oxygenates (≈33%). The density, interfacial tension, viscosity, and refractive index of the lemon oils increased as the oil fold increased (i.e., 1× < 3× < 5× < 10×). The stability of oil-in-water emulsions produced by high pressure homogenisation was strongly influenced by lemon oil fold. The lower fold oils were highly unstable to droplet growth during storage (1×, 3×, and 5×) with the growth rate increasing with increasing storage temperature and decreasing oil fold. Droplet growth was attributed to Ostwald ripening, i.e., diffusion of lemon oil molecules from small to large droplets. The highest fold oil (10×) was stable to droplet growth, which was attributed to the presence of an appreciable fraction of constituents with very low water-solubility that inhibited droplet growth through a compositional ripening effect. This study provides important information about the relationship between lemon oil composition and its performance in emulsions suitable for use in food and beverage products.     

Stability and characterisation of phospholipid-based curcumin-encapsulated microemulsions

The ternary phase diagram of a curcumin-encapsulated O/W microemulsion system using food-acceptable components, lecithin and Tween 80 as the surfactants and ethyl oleate as the oil phase, was constructed. The stability and characterisation of curcumin in microemulsion were investigated. The results indicated that a composition of curcumin microemulsion (DI water: surfactants (the mole ratio of lecithin/Tween 80 was 0.3): EO = 10:1.7:0.4 in wt ratio) was stable for 2 months with an average diameter of 71.8 ± 2.45 nm, as detected by UV–Vis spectra and diameter distributions. The microemulsion possesses an ability to be diluted with aqueous buffer without destroying its structure for 48 h. A skin permeation study for testing the penetration effect of various curcumin loading in the microemulsions with different particle diameters was also performed and discussed in this contribution.     

Antioxidant and emulsifying properties of potato protein hydrolysate in soybean oil-in-water emulsions

The efficacy of a previously developed antioxidative potato protein hydrolysate (PPH) for the stabilisation of oil droplets and inhibition of lipid oxidation in soybean oil-in-water (O/W) emulsions was investigated. Emulsions (10% lipid, pH 7.0) with PPH-coated oil droplets were less stable than those produced with Tween 20 (P < 0.05). However, the presence of PPH, whether added before or after homogenisation with Tween 20, retarded emulsion oxidation, showing reduced formation of peroxides up to 53.4% and malonaldehyde-equivalent substances up to 70.8% after 7-d storage at 37 °C (P < 0.05), when compared with PPH-free emulsions. In the emulsions stabilised by PPH + Tween 20, 8–15% of PPH was distributed at the interface. Adjustment of the pH from 3 to 7 markedly increased ζ-potential of such emulsions (P < 0.05). Inhibition of lipid oxidation by PPH in soybean O/W emulsions can be attributed to both chemical and physical (shielding) actions.     

Influence of droplet size on the efficacy of oil-in-water emulsions loaded with phenolic antimicrobials

In this study we investigated the effect of droplet size on the antimicrobial activity of emulsions containing two essential oil compounds that are known for their antimicrobial effectiveness: carvacrol and eugenol. Coarse emulsions were prepared by blending a triacylglyceride (Miglyol 812N) containing various concentrations of carvacrol or eugenol (5, 15, 30, 50 wt%) at an oil droplet mass fraction of 10 wt% with an aqueous phase containing 2 wt% Tween 80(?). Premixes were then further dispersed using a high shear blender, a high pressure homogenizer at different pressures or an ultrasonicator to produce droplets with a variety of mean diameters. Microscopy and light scattering storage stability studies over 10 days indicated that manufactured emulsions were stable, i.e. that no aggregation, creaming or other destabilization mechanisms occurred and droplet size distributions remained unchanged. The antimicrobial activity of emulsions was assessed against two model microorganisms, the Gram negative Escherichia coli C 600 and the Gram positive Listeria innocua, by determining growth over time behavior. The analysis yielded the unexpected result that emulsions with larger droplet sizes were more effective at inhibiting growth and inactivating cells than smaller ones. For example, emulsions with a mean oil droplet size of 3000 nm at a concentration of 800 ppm carvacrol completely inhibited L. innocua, while for 80 nm emulsions, only a delay of growth could be observed. Measurements of the concentration of the antimicrobial compounds in the aqueous phase indicated that concentrations of eugenol and carvacrol decreased with decreasing oil droplet sizes. Determination of interfacial tension further showed that eugenol and carvacrol are preferentially located in the oil-water interfaces. Theoretical calculations of Tween 80(?) concentrations needed to saturate interfaces suggested that in small emulsions for the given formulation less Tween 80(?) micelles are present in the aqueous phase. We therefore attribute the fact that antimicrobial nanoemulsions are less active than macroemulsions due to an increased sequestering of antimicrobials in emulsion interfaces and a decreased solubilization in excess Tween 80(?) micelles.