Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification

Chitosan without hydrophobic modification is not a good emulsifier itself. However, it has a pH-tunable sol-gel transition due to free amino groups along its backbone. In the present work, a simple reversible Pickering emulsion system based on the pH-tunable sol-gel transition of chitosan was developed. At pH > 6.0, as adjusted by NaOH, chitosan was insoluble in water. Chitosan nanoparticles or micrometer-sized floccular precipitates were formed in situ. These chitosan aggregates could adsorb at the interface of oil and water to stabilize the o/w emulsions, so-called Pickering emulsions. At pH < 6.0, as adjusted by HCl, chitosan was soluble in water. Demulsification happened. Four organic solvents (liquid paraffin, n-hexane, toluene, and dichloromethane) were chosen as the oil phase. Reversible emulsions were formed for all four oils. Chitosan-based Pickering emulsions could undergo five cycles of emulsification-demulsification with only a slight increase in the emulsion droplet size. They also had good long-term stability for more than 2 months. Herein, we give an example of chitosan without any hydrophobic modification to act as an effective emulsifier for various oil-water systems. From the results, we have determined that natural polymers with a stimulus-responsive sol-gel transition should be a good particulate emulsifier. The method for in situ formation of pH-responsive Pickering emulsions based on chitosan will open up a new route to the preparation of a wide range of reversible emulsions.     

An alkyl polyglucoside-mixed emulsifier as stabilizer of emulsion systems: the influence of colloidal structure on emulsions skin hydration potential

To be considered as a suitable vehicle for drugs/cosmetic actives, an emulsion system should have a number of desirable properties mainly dependent on surfactant used for its stabilization. In the current study, C(12-14) alkyl polyglucoside (APG)-mixed emulsifier of natural origin has been investigated in a series of binary (emulsifier concentration 10-25% (w/w)) and ternary systems with fixed emulsifier content (15% (w/w)) with or without glycerol. To elucidate the systems' colloidal structure the following physicochemical techniques were employed: polarization and transmission electron microscopy, X-ray diffraction (WAXD and SAXD), thermal analysis (DSC and TGA), complex rheological, pH, and conductivity measurements. Additionally, the emulsion vehicles' skin hydration potential was tested in vivo, on human skin under occlusion. In a series of binary systems with fixed emulsifier/water ratios ranging from 10/90 to 25/75 the predominance of a lamellar mesophase was found, changing its character from a liquid crystalline to a gel crystalline type. The same was observed in gel emulsions containing equal amounts of emulsifier and oil (15% (w/w)), but varying in glycerol content (0-25%). Different emulsion samples exhibited different water distribution modes in the structure, reflecting their rheological behavior and also their skin hydration capacity.     

Formulation,Rheology, and Hypolepidemic Activity of Vegetable Oil-Based Eggless and Low-Fat Food Emulsions

Common edible oils such as almond, safflower, soybean, and mustard oil were formulated in the form of eggless and low-fat oil-in-water emulsions using a blend of nonionic emulsifier Glycerol monostearate and amphoteric emulsifier soy lecithin. The emulsion parameters such as vegetable oil, emulsifier, additive content and hydrophilic-lipophilic balance number of emulsifier were optimized. The storage stability of formulated emulsions was monitored under accelerated storage stability conditions for six months. Rheological characterization of stable emulsion revealed pseudoplastic flow behavior. In vivo hypolepidemic activity of formulated emulsions in rats showed considerable reduction in total cholesterol and triglyceride level after 14 days as compared with the marketed product. The almond oil emulsion is found superior than safflower oil emulsion.     

Water-in-Oil Emulsions Stabilized by Asphaltenes Obtained from Venezuelan Crude Oils

W/O emulsions were studied using asphaltenes as surfactants. Asphaltenes were obtained from three Venezuelan crude oils: “Lago Cinco,” “Rosa Mediano,” and “Ayacucho.” They were extracted using n-heptane as a precipitanting agent. The following variables were studied: concentration of asphaltenes in the oleic phase and pH of the aqueous phase. An increase in asphaltene concentration in the oleic phase increases emulsion stability. On the other hand, the most stable emulsions correspond to an alkaline aqueous phase. Likewise, emulsion stability was higher for asphaltenes obtained from “Lago Cinco” crude oil and lowest from Rosa Mediano asphaltenes.     

Factors affecting the stability of O/W emulsion in BSA solution: stabilization by electrically neutral protein at high ionic strength

Bovine serum albumin (BSA) was used as an emulsifier to disperse corn oil in aqueous media with various protein concentration, pH, and ionic strength. Quantitative estimation was made on the homogenizing activity of BSA and dispersion stability of oil particles by measuring particle size, turbidity, and creaming rate. Dispersion stability strongly depended on pH and became a minimum around pH 5.0 which was the isoelectric point of BSA. The interfacial tension between BSA solution and corn oil was minimized at pH 5.0. Interesting results were obtained concerning the ionic-strength dependence of stability. When the ionic strength was set below 30 mM, the emulsions became more stable with the increase of BSA concentration at pH 6.7 but the opposite behavior (enhanced destabilization) was confirmed at pH 5.0 with the BSA content. In high ionic strength conditions (ca. > or = 80 mM NaCl), however, BSA-stabilized emulsions became fairly stable even at pH 5.0. These results suggested that BSA molecules having no net charge induced some attractive interactions (e.g., bridging or depletion) in low ionic strength but steric stabilization in high ionic strength, respectively.     

Mixed,lipase-catalyzed inter-esterified fats and hemp oil as a fatty base of model emulsion products with different emulsifiers

The aim of the study was to perform modification of fats to obtain new products, which were used as a fatty basis of model emulsions. The second objective was to assess the stability of the prepared emulsions. For this purpose, turkey fat, chicken fat, and mutton tallow were used and enzymatically inter-esterified with hemp oil. Enzymatic interesterification was performed using a selective catalyst – Lipozyme IR RM. The obtained fat mixtures before and after interesterification were assessed by determining their acid value, peroxide value (PV), anisidine value (AV), polar fraction (PF), and slip melting point (SMP). Later, the fats were used as a fatty basis of emulsions. The variable component in the emulsions was the emulsifier. The emulsions were evaluated for droplet size and viscosity and by the Turbiscan test. It was concluded that the dispersion systems containing mutton tallow and the emulsifier formed during the enzymatic reaction, as well as the one containing the same fat and lecithin, showed the best stability. In the case of emulsions with enzymatically modified mutton tallow, the authors are planning to extend the range of usable properties under examination. In the authors’ opinion, the proposed systems can be used in the cosmetic and food industries.     

Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials

Hydroxyapatite (HAp) nanoparticles with spherical, rod-shaped or fiber-shaped morphologies were synthesized by wet chemical method in aqueous media. Scanning electron microscopy, dynamic light scattering, helium pycnometry, and aqueous electrophoresis techniques were used to characterize the nanoparticles in terms of their particle size and morphology, density and zeta potential, respectively. Stable "Pickering-type" emulsions were prepared using the HAp nanoparticles as a particulate emulsifier and methyl myristate as an oil phase above pH 7.7, but not below pH 6.1. These emulsions were characterized in terms of their emulsion type, mean droplet diameter and morphology using electrical conductivity, light diffraction and optical microscopy. Rapid demulsification could be induced by lowering the solution pH: addition of acid led to dissolution of the HAp nanoparticles attached on oil-water interface and the emulsion was destabilized. HAp nanoparticles precipitated by addition of base to the aqueous phase after demulsification and the HAp particles precipitated worked as an effective particulate emulsifier. This emulsification-demulsification cycle was reversible. Sintering of methyl myristate-in-water emulsion stabilized with the HAp nanoparticles led to a porous HAp material.     

Droplet surface properties and rheology of concentrated oil in water emulsions stabilized by heat-modified beta-lactoglobulin B

Effects of substituting native beta-lactoglobulin B (beta-lactoglobulin) with heat-treated beta-lactoglobulin as emulsifier in oil in water emulsions were investigated. The emulsions were prepared with a dispersed phase volume fraction of Phi=0.6, and accordingly, oil droplets rather closely packed. Native beta-lactoglobulin and beta-lactoglobulin heated at 69 degrees C for 30 and 45 min, respectively, in aqueous solution at pH 7.0 were compared. Molar mass determination of the species formed upon heating as well as measurements of surface hydrophobicity and adsorption to a planar air/water interface were made. The microstructure of the emulsions was characterized using confocal laser scanning microscopy, light scattering measurements of oil droplet sizes, and assessment of the amount of protein adsorbed to surfaces of oil droplets. Furthermore, oil droplet interactions in the emulsions were quantified rheologically by steady shear and small and large amplitude oscillatory shear measurements. Adsorption of heated and native beta-lactoglobulin to oil droplet surfaces was found to be rather similar while the rheological properties of the emulsions stabilized by heated beta-lactoglobulin and the emulsions stabilized by native beta-lactoglobulin were remarkably different. A 200-fold increase in the zero-shear viscosity and elastic modulus and a 10-fold increase in yield stress were observed when emulsions were stabilized by heat-modified beta-lactoglobulin instead of native beta-lactoglobulin. Aggregates with a radius of gyration in the range from 25 to 40 nm, formed by heating of beta-lactoglobulin, seem to increase oil droplet interactions. Small quantities of emulsifier substituted with aggregates have a major impact on the rheology of oil in water emulsions that consist of rather closely packed oil droplets.     

Phase Transitions in Emulsions Formed by Aqueous Emulsifier and its Action on Improving Mobility in Oil Recovery

Transition from oil-in-water (O/W) emulsions to water-in-oil (W/O) emulsions and its action on enhanced oil recovery was investigated by viscosity, morphology, and simulated flooding experiments. This transition can be realized by increasing the volume ratio of oil to water or decreasing the emulsifier concentration. At a mass concentration of 0.3 wt%, the self-developed emulsifier FJ-1 mainly forms O/W emulsions at a volume ratio (oil to water) of 1:1. The emulsions behave as O/W emulsions with a low viscosity when the volume ratio of oil to water is below 2:1. Above 2:1, increasing volume ratio leads to the O/W emulsions transferring into W/O emulsions with high viscosity. For example, at a volume fraction of 4:1, the viscosity of W/O emulsions reaches 229.1 mPa · s, and separated water can hardly be detected. Transition from O/W emulsions to W/O emulsions with high viscosity can also be realized by decreasing the concentration of emulsifier to 0.05 wt% or lower at a volume ratio of 1:1. These may be the critical factors leading to transition from O/W emulsions to W/O emulsions at core conditions. Simulated flooding experiments show that emulsifier fluids can act as an in situ mobility improver and make an improvement of oil recovery even by 20.4%. The results indicate that the water-in-crude-oil emulsions possess great potential in enhancing oil recovery.     

Effect of hydrophobic modification of hydroxypropyl methylcellulose on silicone oil emulsions

To study the effect of hydrophobic modification of the emulsifier on the relationship between emulsion stability and polymer emulsifier concentration, silicone oil emulsions were prepared using hydroxypropyl methylcellulose (original HPMC) and HPMC stearoxy ether (hydrophobic HPMC) at concentrations around their overlap concentrations. Both HPMC types completely emulsified the silicone oil. However, the volume fraction of silicone oil in the emulsion prepared using hydrophobic HPMC was less than that that by the original HPMC, and the average oil droplet size in the former emulsion was less than that in the latter emulsion. Increasing HPMC concentration led to increase in both the amount of adsorbed polymer emulsifier and the storage moduli in the linear region, irrespective of which HPMC was used. Stress-strain sweep curves obtained by a rheo-optical method showed that emulsions stabilized by the hydrophobic HPMC flowed slowly, even beyond the yield stress, whereas emulsions prepared using the original HPMC flowed quickly beyond the yield stress. The storage moduli of the emulsions prepared by the hydrophobic HPMC were larger than those prepared using the original HPMC.     

Formulating Neem Oil Emulsion as Potent Agrochemicals Using a Binary Emulsifier System

Neem oil is a natural pesticide and has excellent insecticidal properties. Hence, in this study the efforts have been made to formulate the Neem oil emulsions which would be used as agrochemicals. In order to formulate stable Neem oil emulsions, a binary emulsifier system of Hydol-6 (Polyoxyethylene Alkyl Ether-6 moles of ethylene oxids) and Hydol-10 (Polyoxyethylene Alkyl Ether-10 moles of ethylene oxids) were employed. Stability of Neem oil emulsions as a function of concentration of Neem oil, Hydol-6, Hydol-10, the amount of water, homogenization speed, and homogenization time was studied in depth. Apart from this, it was observed that the nature of water also affects the stability of the emulsions. The concentration of Neem oil in the stable emulsions was also found to exhibit the varying effects on the properties like dispersibility, spreading power, and droplet size of the emulsions. Larvasidal effects of stable Neem oil emulsions were examined.     

Impact of Tween 60 on physicochemical properties and stability of Pistacia lentiscus fruit oil-in-water emulsion at a semi-low temperature

This study shows the effects of the Tween 60 emulsifier at different concentrations on the aqueous emulsion containing 5% of Pistacia lentiscus fruit oil. The rheological behavior and the droplet size distribution of cosmetic oil-in-water emulsions were investigated. This investigation was carried out by analyzing the shear flow and dynamic oscillatory followed by microscopic analysis and physical stability study for 24?hours and 4 months. During the period of 4 months, the emulsions were stored in a refrigerator at a semi-low temperature 12?°C. The physical stability test showed that the sample not emulsified yielded a creaming process after a short aging time. Flow curves of emulsions prepared with TW 60 exhibited a non-linear relationship between the shear stress σ and shear rate γ ?, which implies that the Herschel–Bulkley rheological model was the appropriate model for the shear flow. The increase of emulsifier quantities leading to an increase in the internal structure coherence, whereas the excess quantity affects the structure. Therefore, the optimal quantity proposed was 3.47%. Furthermore, the storage time at a semi-low temperature performed the stability and maintain the structure of emulsions.     

EFFECT OF PREMIX CONDITION,SURFACTANT CONCENTRATION,AND OIL LEVEL ON THE FORMATION OF OIL-IN-WATER EMULSIONS BY HOMOGENIZATION

Oil-in-water emulsions were prepared on a homogenizer from good premixes and poor premixes. The quality of the emulsions was determined by measuring the droplet size distribution using spectroturbidimetry. A good premix to the homogenizer produces a better emulsion than a poor premix. Premix conditions become less important when the concentration of emulsifier is increased in relation to the amount of oil. Increasing oil concentration results in a poorer final emulsion. Large amounts of emulsifier negate the advantage of using the homogenizer, but greater mechanical energy input can compensate for reduced emulsifier concentration, a cost saving when formulating an emulsion.     

Influence of droplet characteristics on the formation of oil-in-water emulsions stabilized by surfactant-chitosan layers

The objective of this study was to establish the optimum conditions for preparing stable oil-in-water emulsions containing droplets surrounded by surfactant-chitosan layers. A primary emulsion containing small droplets (d32 approximately = 0.3 microm) was prepared by homogenizing 20 wt% corn oil with 80 wt% emulsifier solution (20 mM SDS, 100 mM acetate buffer, pH 3) using a high-pressure valve homogenizer. The primary emulsion was diluted with chitosan solutions to produce secondary emulsions with a range of oil and chitosan concentrations (0.5-10 wt% corn oil, 0-1 wt% chitosan, pH 3). The secondary emulsions were sonicated to help disrupt any droplet aggregates formed during the mixing process. The electrical charge, particle size, and amount of free chitosan in the emulsions were then measured. The droplet charge changed from negative to positive as the amount of chitosan in the emulsions was increased, reaching a relatively constant value (approximately +50 mV) above a critical chitosan concentration (C(Sat)), which indicated that saturation of the droplet surfaces with chitosan occurred. Extremely large droplet aggregates were formed at chitosan concentrations below C(Sat), but stable emulsions could be formed above C(Sat) provided the droplet concentration was not high enough for depletion flocculation to occur. Interestingly, we found that stable multilayer emulsions could also be formed by mixing chitosan with an emulsion stabilized by a nonionic surfactant (Tween 20) due to the fact the initial droplets had some negative charge. The information obtained from this study is useful for preparing emulsions stabilized by multilayer interfacial layers.     

Optimization of Phytosterols Dispersion in an Oil/Water Emulsion Using Mixture Design Approach

Major problems related to enrichment of products with phytosterols are high melting temperature, chalky taste and low solubility in water phase. Dispersion of phytosterols in an emulsion was optimized using a mixture design with four components (phytosterols, emulsifier, soy oil, and water). It was found that the particle size of the dispersed phase decreased with the increase in emulsifier concentration. The appearance viscosity was increased with decreasing particle size. The stability of these emulsions could be correlated with the decrease in surface tension and particle size by using oil and emulsifier as components of oil phase.     

Encapsulation and Prolonged Release Behaviour of W/O/W Type Multiple Emulsions

W/O/W type multiple emulsions were prepared by two step emulsification procedures using an oily lymphographic agent, lipiodol, as an inner oil phase and Pluronic F-68 as a hydrophilic emulsifier contained in the outer aqueous phase. Span 80, Pluronic L-64 and HCO-60 were used as emulsifiers incorporating them into the inner oil phase. The phase volume of the inner and outer aqueous phases and the yield of the w/o/w type multiple emulsions were studied. The dissolution behaviour of the w/o/w type multiple emulsions were determined by a dialysis method employing cellulose tubing. The effect of emulsifier type and the amount of HCO-60 on the stability and prolonged release behavior of the w/o/w type multiple emulsions with or without lecithin, was also examined. The results indicate the HCO-60 is a better emulsifier than Span 80 or Pluronic L-64. Its use improves the stability and the prolonged release behavior of w/o/w type multiple emulsions.     

Multilayer emulsions stabilized by vegetable proteins and polysaccharides

There is great interest in the food, cosmetic and pharmaceutical industry in the use of proteins and polysaccharides as natural hydrocolloids to create novel emulsion systems with improved stability and functionality. For example, the electrostatic interaction between proteins and polysaccharides may be used to form oil-in-water (O/W) emulsions with multilayered interfacial membranes around oil droplets or multilayer emulsions. This type of emulsions have been developed using the layer-by-layer (LbL) technique, which consists of direct adsorption of an oppositely charged polyelectrolyte layer (e.g. polysaccharides) on a primary layer of ionic emulsifiers (e.g. proteins). The polymeric structure and electrical charge of proteins make them a special class of compounds very suitable for its utilization in the LbL technique. In recent years, the utilization of proteins as emulsifiers in food and pharmaceutical industry has been turning towards plants as a preferred alternative to animal-based sources. This article reviews the current understanding of the utilization of different vegetable proteins as emulsifier in order to stabilize O/W multilayer emulsion systems. Additionally, it highlights some potential applications of the multilayer emulsion technology in the industry, for improving the stability of emulsions to environmental stresses and for developing controlled or triggered release systems.     

Effect of dispersion pH on the formation and stability of Pickering emulsions stabilized by layered double hydroxides particles

Using positively charged plate-like layered double hydroxides (LDHs) particles as emulsifier, liquid paraffin-in-water emulsions stabilized solely by such particles are successfully prepared. The effects of the pH of LDHs aqueous dispersions on the formation and stability of the emulsions are investigated here. The properties of the LDHs dispersions at different pHs are described, including particle zeta potential, particle aggregation, particle contact angle, flow behavior of the dispersions and particle adsorption at a planar oil/water interface. The zeta potential decreases with increasing pH, leading to the aggregation of LDHs particles into large flocs. The structural strength of LDHs dispersions is enhanced by increasing pH and particle concentration. The three-phase contact angle of LDHs also increases with increasing pH, but the variation is very small. Visual observation and SEM images of the interfacial particle layers show that the adsorption behavior of LDHs particles at the planar oil/water interface is controlled by dispersion pH. We consider that the particle-particle (at the interface) and particle-interface electrostatic interactions are well controlled by adjusting the dispersion pH, leading to pH-tailored colloid adsorption. The formation of an adsorbed particle layer around the oil drops is crucial for the formation and stability of the emulsions. Emulsion stability improves with increasing pH and particle concentration because more particles are available to be adsorbed at the oil/water interface. The structural strength of LDHs dispersions and the gel-like structure of emulsions also influence the stability of the emulsions, but they are not necessary for the formation of emulsions. The emulsions cannot be demulsified by adjusting emulsion pH due to the irreversible adsorption of LDHs particles at the oil/water interface. TEM images of the emulsion drops show that a thick particle layer forms around the oil drops, confirming that Pickering emulsions are stabilized by the adsorbed particle layers. The thick adsorbed particle layer may be composed of a stable inner particle layer which is in direct contact with the oil phase and a relatively unstable outer particle layer surrounding the inner layer.     

Formula Optimization of Emulsifiers for Preparation of Multiple Emulsions Based on Artificial Neural Networks

Formulation optimization of emulsifiers for preparing multiple emulsions was performed in respect of stability by using artificial neural network (ANN) technique. Stability of multiple emulsions was expressed by the percentage of reserved emulsion volume of freshly prepared sample after centrifugation. Individual properties of multiple emulsions such as droplet size, δ, viscosity of the primary and the multiple emulsions were also considered. A back‐propagation (BP) network was well trained with experimental data pairs and then used as an interpolating function to estimate the stability of emulsions of different formulations. It is found that using mixtures of Span 80 and Tween 80 with different mass ratio as both lipophilic and hydrophilic emulsifiers, multiple W/O/W emulsions can be prepared and the stability is sensitive to the mixed HLB numbers and concentration of the emulsifiers. By feeding ANN with 39 pairs of experimental data, the ANN is well trained and can predict the influences of several formulation variables to the immediate emulsions stability. The validation examination indicated that the immediate stability of the emulsions predicted by the ANN is in good agreement with measured values. ANN therefore could be a powerful tool for rapid screening emulsifier formulation. However, the long‐term stability of the emulsions is not good, possibly due to the variation of the HLB number of the mixed monolayers by diffusion of emulsifier molecules, but can be greatly improved by using a polymer surfactant Arlacel P135 to replace the lipophilic emulsifier.     

Phase transitions and microstructure of emulsion systems prepared with acylglycerols/zinc stearate emulsifier

The emulsification processes, during which acylglycerols/zinc stearate emulsifier, water, and oil phase formed ternary systems, such as water-in-oil (W/O) emulsions, oil-in-water (O/W) dispersions, and unstable oil-water mixtures, were investigated in order to characterize the progressive transformations of the dispersed systems. The type, structure, and phase transitions of the systems were found to be determined by temperature and water phase content. Crystallization of the emulsifier caused the destabilization and subsequent phase inversion of the emulsions studied, at a temperature of 60-61 degrees C. The observed destabilization was temporary and led, at lower temperature, to W/O emulsions, "O/W + O" systems, or O/W dispersions, depending on the water content. Simultaneous emulsification and cooling of 20-50 wt % water systems resulted in the formation of stable W/O emulsions that contained a number of large water droplets with dispersed oil globules inside them ("W/O + O/W/O"). In water-rich systems (60-80 wt % of water), crystallization of the emulsifier was found to influence the formation of crystalline vesicle structures that coexisted, in the external water phase, with globules of crystallized oil phase. Results of calorimetric, rheological, and light scattering experiments, for the O/W dispersions obtained, indicate the possible transition of a monostearoylglycerol-based alpha-crystalline gel phase to a coagel state, in these multicomponent systems.