Single, Janus, and Cerberus emulsions from the vibrational emulsification of oils with significant mutual solubility.

Single, Janus, and Cerberus emulsions are prepared in one system consisting of three oils: silicone (SO), fluorocarbon (FO) and ethoxylated trimethylolpropane triacrylate (ETPTA) with mutual solubility. An aqueous solution of Pluronic F127, which is an poly(ethylene oxide)/poly(propylene oxide) co-polymer of average composition EO97PO68EO97, was employed as the continuous phase. The three-dimensional phase diagram of the oils was determined, and different oil compositions within the various regions of the phase diagram were emulsified by one-step vortex mixing with an F127 aqueous solution. The result showed single, Janus, and Cerberus emulsions within the different regions of the phase diagram; i.e. the emulsions reflected the equilibrium system. The topology of the Cerberus droplets is to an overwhelming extent linear-singlet and exclusively lobe order of EF/FO/SF. Since the results indicate a significant effect of the equilibrium interfacial tensions on the drop topology, thermodynamic calculations were made using the experimentally determined interfacial tensions. The results, as expected, show that the Cerberus emulsions are thermodynamically preferred over separate drops of the individual oils. In addition, the calculations demonstrate that the order of lobes within a drop is thermodynamically favored.

Janus emulsion mediated porous scaffold bio-fabrication.

A three dimensional biopolymer network structure with incorporated nano-porous calcium phosphate (CaP) balls was fabricated by using gelatin-chitosan (GC) polymer blend and GC stabilized olive/silicone oil Janus emulsions, respectively. The emulsions were freeze-dried, and the oil droplets were washed out in order to prepare porous scaffolds with larger surface area. The morphology, pore size, chemical composition, thermal and swelling behavior was studied by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and micro-Differential Scanning Calorimetry (micro-DSC). Microscopic analysis confirmed that the pore size of the GC based sponges after freeze-drying may be drastically reduced by using Janus emulsions. Besides, the incorporation of nanoporous calcium phosphate balls is also lowering the pore size and enhancing thermal stability.

Topical application of retinyl palmitate-loaded nanotechnology-based drug delivery systems for the treatment of skin aging.

The objective of this study was to perform a structural characterization and evaluate the in vitro safety profile and in vitro antioxidant activity of liquid crystalline systems (LCS) with and without retinyl palmitate (RP). LCS containing polyether functional siloxane (PFS) as a surfactant, silicon glycol copolymer (SGC) as oil phase, and water in the ratios 30 : 25 : 45 and 40 : 50 : 10 with (OLS(v) = RP-loaded opaque liquid system and TLS(v) = RP-loaded transparent liquid system, respectively) and without (OLS and TLS, respectively) RP were studied. Samples were characterized using polarized light microscopy (PLM) and rheology analysis. In vitro safety profile was evaluated using red cell hemolysis and in vitro cytotoxicity assays. In vitro antioxidant activity was performed by the DPPH method. PLM analysis showed the presence of lamellar LCS just to TLS. Regardless of the presence of RP, the rheological studies showed the pseudoplastic behavior of the formulations. The results showed that the incorporation of RP in LCS improved the safety profile of the drug. In vitro antioxidant activity suggests that LCS presented a higher capacity to maintain the antioxidant activity of RP. PFS-based systems may be a promising platform for RP topical application for the treatment of skin aging.

Equilibrium topology and partial inversion of Janus drops: a numerical analysis.

The equilibrium topology of an aqueous Janus emulsion of two oils, O1 and O2, with water, W, [(O1+O2)/W], is numerically evaluated with the following realistic interfacial tensions (γ): γO2/W =5 mN m(-1) , γO1/O2 =1 mN m(-1) , and γO1/W varies within the range 4-5 mN m(-1) , which is the limiting range for stable Janus drop topology. The relative significance of the two independently pivotal factors for the topology is evaluated, that is, the local equilibrium at the line of contact between the three liquids and the volume fraction of the two dispersed liquids within the drop. The results reveal a dominant effect of the local equilibrium on the fraction of the O2 drop surface that is covered by O1. In contrast, for a constant volume of O2, the impact of the interfacial tension balance on the limit of the coverage is modest for an infinite volume of O1. Interestingly, when the O1 volume exceeds this value, an emulsion inversion occurs, and the O1 portion of the (O1+O2)/W topology becomes a continuous phase, generating a (W+O2)/O1 Janus configuration.

Spontaneous emulsification between incompatible aqueous solutions in the water/ethanol/benzene system.

Two aqueous solutions on the de-mixing line in the water/benzene/ethanol system formed an O/W emulsion, when mixed. Contacting the solutions without mixing gave a slow spontaneous emulsification over several hours. The emulsion in question was found exclusively in the solution of greater water fraction and the dimension of the emulsion layer expanded as the square root of time. The reduction in the volume fraction the solution with less water was divided by the volume fraction of the emulsion, giving an - albeit exaggerated - measure of the volume fraction of the dispersed phase in the emulsion. It reached 0.6 after 1h, after which it remained constant for 3h. The composition change from the initial stage to the final equilibrium was calculated using a combination of the phase diagram features and earlier diffusion flux calculations in a similar system to estimate the fraction of the compounds transferred between the layers. These transfers were unexpectedly clear-cut, 95 wt% of the water in the less water solution was transferred into the water rich solution as was 80% of the ethanol. In the same manner 95% of the benzene in the water rich solution was relocated into the water poor solution.

Destabilization mechanisms in a triple emulsion with Janus drops.

The destabilization mechanism was investigated of a triple Janus emulsion. The inner part of the emulsion consisted of Janus drops of a vegetable oil (VO) and a silicone oil (SO) in an aqueous (W) drop, (VO+SO)/W. This drop, in turn was dispersed in a VO drop forming a double emulsion (VO+SO)/W/VO. Finally, these complex drops generated a complex Janus (SO+VO)/W/VO/SO triple emulsion by being dispersed in a continuous SO phase. The observations were limited to the time dependence of the over-all creaming/sedimentation processes, to the separation of layers of the compounds and to optical microscopy of the drop configuration with time. In the destabilization process the rise of the complex drops, (SO+VO)/W/VO, caused crowding in the upper part of the emulsion, which in turn led to enhanced coalescence, inversion and separation of a dilute vegetable oil emulsion. As a consequence of the separation of VO in the process, the remaining drops contained a greater W fraction and greater density. This change, in turn, resulted in sedimentation of the complex drops to form several high internal ratio morphologies in an SO continuous emulsion in the lower part of the test tube, among them a W/VO/SO emulsion. Finally, an inversion took place into an SO/VO/W double emulsion forming a separate bottom layer.

One-step inversion process to a Janus emulsion with two mutually insoluble oils.

High internal phase ratio (HIPR) aqueous Janus emulsions of two immiscible oils, silicone oil (SO) and a vegetable oil (VO), were prepared using a vibration mixer. The simple HIPR Janus emulsions, (VO + SO)/W, were found at weight fractions of the aqueous phase in excess of 0.3, while at a corresponding fraction of 0.1, a triple emulsion was obtained with the Janus emulsion forming a drop inside the vegetable oil to give a double Janus emulsion, (VO + SO)/W/VO, which in turn formed drops in the silicone oil resulting in a triple Janus emulsion (VO + SO)/W/VO/SO. Increasing the aqueous-phase fraction from 0.1 to 0.3 consequently meant an inversion, of which one intermediate stage was observed: a more complex configuration, e.g., one in which large SO drops with highly distorted VO drops attached were dispersed in a regular aqueous emulsion with spherical Janus (VO + SO) drops. A preliminary investigation was made into the destabilization process of the triple emulsions.

A one-step process to a Janus emulsion.

Aqueous high internal phase volume ratio (O/W 90/10) Janus emulsions of a vegetable oil and a silicone fluid were prepared in a single step emulsification by the common vibrator equipment. The basis for the unique structure is discussed in relation to pair-wise interactions between the components with especial emphasis on the surfactant concentration in the aqueous phase.

Perspectives of phase changes and reversibility on a case of emulsion inversion.

The conventional treatment of catastrophic inversion is based on a two-phase model of oil-in-water (O/W) or water-in-oil (W/O). The present investigation takes a closer look at the process of inversion with focus on its relation to the detailed phase changes in the system. It is found that phase behavior inserts a decisive call for when the inversion starts and completes, even for an inversion seemingly brought by a simple change of water-to-oil ratio. The phases involved also play a critical role in the fine details of the emulsion structure, during both emulsification and evaporation. The presence of liquid crystal is instrumental in the inversion process as substantiated by the observation that its presence coincides with the presence of the intermediate multiple emulsions during emulsification. Multiple emulsions also appear during evaporation, though the mechanism of their formation is different from that during emulsification. The temporary stability of the multiple emulsions during both emulsification and evaporation is affected by the presence of the liquid crystal. It had been well established that the phase behavior plays a decisive role in transitional inversions and that the transformation to the inverse state is a gradual one. This is apparently also the case with the catastrophic inversion investigated here.

Role of liquid crystal in the emulsification of a gel emulsion with high internal phase fraction.

A gel emulsion with high internal oil phase volume fraction was formed via an inversion process induced by a water-oil ratio change. The process involved the formation of intermediate multiple emulsions prior to inversion. The multiple emulsions contain a liquid crystal formed by the surfactant with water; this was both predicted by the equilibrium phase diagram as well as observed using polarization microscopy. These multiple emulsions were more stable compared to alternative multiple emulsions prepared in the same way with a surfactant that does not form liquid crystals. While the formation of a stable intermediate multiple emulsion may not be a necessary condition for the inversion to occur, the transitional presence of a liquid crystal proved to be a significant factor in the stabilization of the intermediate multiple emulsions. The resulting gel emulsion contained a small fraction of the liquid crystal according to the phase diagram, and it exhibited excellent stability.

Phase diagram approach to evaporation from emulsions with n oil compounds.

The initial evaporation path was calculated for an emulsion of water and a multicomponent oil phase under the following conditions. The computations were based on the phase diagram of the emulsion system combined with an algebraic system to extract information from phase diagrams to facilitate the mathematical treatment. An inherent consequence of the use of the phase diagram as a basis to calculate an evaporation path is the condition of equilibrium between the phases in the emulsion as well as between the vapor and the condensed phases. In addition to this fundamental limitation, the features of the phase diagram of the actual emulsion were restricted as follows. There is no solubility of significance in the water of either the oil or of the surfactant. The nonaqueous compounds display extensive mutual solubility with the solutions being close to ideal. This solution of the nonaqueous compounds does not dissolve nor solubilize water to a degree to affect the calculations in the stage of evaporation treated; an emulsion in the two-phase region of lowest surfactant content.

Effect of relative humidity on the evaporation path from a phenethyl alcohol emulsion.

The evaporation path for emulsions of phenethyl alcohol stabilized by a non-ionic surfactant, Laureth 4, a commercial ethoxy adduct, approximately C(12)(EO)(4), was estimated by calculations using the phase diagram. The results for emulsions with an O/W ratio equal to or greater than 1/3 showed the relative humidity only in excess of 90% to have a significant effect on the evaporation path. In fact the path was not significantly modified for relative humidities from 0% to 90%, but in the range 90-100% the modification of the evaporation path was most pronounced; not only altering the path, but causing entirely different phases to appear in the emulsion. On the other hand, for emulsions with lower O/W ratios these effects were substantial for relative humidities down to the level of 40%.

Geranyl acetate emulsions: surfactant association structures and emulsion inversion.

Three emulsions of geranyl acetate (GA)-in-water (W) with identical GA/W ratios and varying surfactant (S), Laureth 4, a commercial C(12)EO (4) compound, fractions were investigated for nature and stability. The emulsions with up to 6% surfactant were W/O, as expected with respect to the solubility of the surfactant in the oil. At 10% surfactant, the aqueous phase became the continuous one and the apparent stability of the emulsion was significantly enhanced. Analysis of the phase diagram and experimental evidence showed the high water content emulsion to be a liquid crystal-in-water emulsion; a kind that did not change even at extreme O/W and LC/W ratios.

Constant vapor pressure emulsions evaporation: Linalool/water stabilized by Laureth 4.

Evaporation paths were calculated in the title system using the relevant part of its published phase diagram and the assumption of equilibrium between vapor and liquids. The vapor pressure of linalool was reduced while the emulsion resided in the two-phase region but remained constant within the three-phase range. The duration of the time for constant vapor pressure depended on the relative humidity (RH) to a surprising degree.

A simple analysis of the changes during evaporation of a commercial emulsion of unknown composition.

Optical microscopy and centrifugation were used to observe the structural changes during evaporation of a commercial skin lotion of unknown composition. The degree of evaporation was determined from the changed weight of a microscope slide with the emulsion on a defined area and thickness, the evaporation loss versus time being measured by a balance under an infrared lamp. The results revealed not only which parts of the emulsion were most prone to evaporation without chemical analysis, but also gave surprising information as to which kind of structures would appear after extensive evaporation. The importance of these changes for the action of a skin lotion is briefly discussed.

Evaporation from an ionic liquid emulsion.

The conditions during evaporation in a liquid crystal-in-ionic liquid microemulsion (LC/microEm) were estimated using the phase diagram of the system. The equations for selected tie lines were established and the coordinates calculated for the sites, at which the evaporation lines crossed the tie lines. These values combined with the coordinates for the phases connecting the tie lines were used to calculate the amounts and the composition of the fractions of the two phases present in the emulsion during the evaporation. One of the emulsion phases was a lamellar liquid crystal and high energy emulsification would lead to the liquid crystal being disrupted to form vesicles. Such a system tenders a unique opportunity to study the interaction between vesicles and normal micelles, which gradually change to inverse micelles over bi-continuous structures. The amount of vesicles in the liquid phase versus the fraction liquid crystal was calculated for two extreme cases of vesicle core size and shell thickness. The limit of evaporation while retaining the vesicle structure was calculated for emulsions of different original compositions assuming the minimum continuous liquid phase to be 50% of the emulsion.

Some non-equilibrium phenomena in the malic acid/water/Polysorbate 81 system.

Topical formulations undergo radical structural changes after application and the action on the skin is not directly related to the original structure of the formulation. This fact has been well established in the scientific literature. However, and more essential, is the fact that these changes in the formulation structure are not equilibrium ones. Especially so, with the hydroxy acids, which are widely used in cosmetic and dermatological treatment of skin. The article reports the first investigation into the non-equilibrium conditions in a hydroxy acid system. Different phases in the title system, which were not in mutual equilibrium, were brought in contact while avoiding convection. The transfer of substance between them was estimated from the changes in volume of each phase. The results showed, unexpectedly, that the systems were far from equilibrium even after prolonged times in contact. The kinetics of the changes varied to significant degree, from extremely slow, when solid phases were involved to fast for liquid phases. In one case was observed a separated layer, which was not found in the phase diagram under equilibrium conditions.

Some pertinent factors in skin care emulsion.

Emulsion structures are reviewed with special consideration given to the conditions in emulsions for topical applications with more phases than the traditional two liquids. The fundamentals of emulsions containing liquid crystals and vesicles are described, focussing on the dependence of the volume ratios of liquid crystals and vesicles on the surfactant content.

Phase behavior of beta hydroxy-acids with laureth 4.

The colloidal structures of beta carboxylic acid topical vesicle formulations were determined and the changes during evaporation after applications were estimated from phase diagrams. The results showed significant difference during evaporation between salicylic acid on one hand and three water soluble acids; malic, tartaric, and citric acid, on the other. The water soluble acids showed an increase in the acid concentration in the aqueous solution to levels that must be considered harmful, while salicylic acid showed no increase in concentration in the individual phases even after 99% evaporation of water.

Analytical expressions to calculate relative amounts of phases in a three-component phase diagram.

The relative amounts of different phases in multiphase regions in the common three-component phase diagrams are usually estimated graphically using geometrical features of the diagram. The present contribution introduces algebraic expressions for the lines in the diagram, which allow these numbers to be calculated directly from the experimental results. The method is an extension of the classical methods, which were translated into convenient computer programs [Laughlin, R. G. The Aqueous Phase Behavior of Surfactants; Academic Press: New York, 1994] to calculate the amount of different phases for individual compositions. The introduction of analytical geometry allows simplified expressions to be used for the calculations and the amounts to be presented as continuous functions of the total composition.