Emulsion preparation using beta-cyclodextrin and its derivatives acting as an emulsifier

The preparation and formation mechanism of n-hexadecane/water emulsions using natural beta-cyclodextrin (beta-CD) and chemically modified beta-CDs (triacylated beta-cyclodextrins) as an emulsifier were investigated. The stable water/oil (W/O) emulsion was formed using tripropanoyl-beta-CD (TP-beta-CD). From observation using the contact angle (theta(ow)) of precipitates derived from CD, it was clarified that oil/water (O/W) emulsion at theta(ow)<90 degrees and (W/O) emulsion at theta(ow)>90 degrees are formed when the composition of each oil and water was mixed with natural beta-CD or triacylated beta-CDs.     

A one-step process for oil-in-water-in-oil double emulsion formation using a single surfactant

A one-step double emulsification protocol using one surfactant was developed for oil-in-water-in-oil (O(1)/W/O(2)) double emulsions. Two n-alkane oils and three different surfactants were studied, with focus placed on a formulation containing mineral oil, glycerol monoleate (GMO) and deionized water. Phenomenologically, double emulsion formation and stability originate from the combined actions of phase inversion and interfacial charging of the oil/water interface during high shear homogenization. Based on the extent of double emulsion formation and stability, a critical emulsification zone dependent on the weight ratios of GMO to water was identified. Within this critical zone, enhanced O(1)/W/O(2) emulsion formation occurred at higher pH and lower salt concentrations, demonstrating the key role of interfacial charging on double emulsification. Overall, this novel approach provides a novel platform for the development of double emulsions with simple compositions and processing requirements.     

Magnetic Pickering emulsions stabilized by Fe3O4 nanoparticles

Superparamagnetic Fe(3)O(4) nanoparticles prepared by a classical coprecipitation method were used as the stabilizer to prepare magnetic Pickering emulsions, and the effects of particle concentration, oil/water volume ratio, and oil polarity on the type, stability, composition, and morphology of these functional emulsions were investigated. The three-phase contact angle (θ(ow)) of the Fe(3)O(4) nanoparticles at the oil-water interface was evaluated using the Washburn method, and the results showed that for nonpolar and weakly polar oils of dodecane and silicone, θ(ow) is close to 90°, whereas for strongly polar oils of butyl butyrate and 1-decanol, θ(ow) is far below 90°. Inherently hydrophilic Fe(3)O(4) nanoparticles can be used to prepare stable dodecane-water and silicone-water emulsions, but they cannot stabilize butyl butyrate-water and decanol-water mixtures with macroscopic phase separation occurring, which is in good agreement with the contact angle data. Emulsions are of the oil-in-water type for both dodecane and silicone oil, and the average droplet size increases with an increase in the oil volume fraction. For stable emulsions, not all of the particles are adsorbed to drop interfaces; the fraction adsorbed decreases with an increase in the initial oil volume fraction. Changes in the particle concentration have no obvious influence on the stability of these emulsions, even though the droplet size decreases with concentration.     

Screening of the effect of surface energy of microchannels on microfluidic emulsification

We report the results of a systematic study of the effect of the surface energy of the walls of microchannels on emulsification in parallel flow-focusing microfluidic devices. We investigated the formation of water-in-oil (W/O) and oil-in-water (O/W) emulsions and found that the stability of microfluidic emulsification depends critically on the preferential wetting of the walls of the microfluidic device by the continuous phase. The condition for stable operation of the device is, however, different than that of complete wetting of the walls by the continuous phase at equilibrium. We found that W/O emulsions form when the advancing contact angle of water on the channel wall exceeds theta approximately 92 degrees. This result is unexpected because at equilibrium even for theta < 92 degrees the microchannels would be completely wet by the organic phase. The criterion for the formation of W/O emulsions (theta > 92 degrees) is thus more stringent than the equilibrium conditions. Conversely, we observed the stable formation of O/W emulsions for theta < 92 degrees, that is, when the nonequilibrium transition to complete wetting by oil takes place. These results underlie the importance of pinning and the kinetic wetting effects in microfluidic emulsification. The results suggest that the use of parallel devices can facilitate fast screening of physicochemical conditions for emulsification.     

Effect of Nanoparticle Hydrophobicity on Stability of Highly Concentrated Emulsions

The effect of hydrophobicity index (HI) of fumed nanosilica specimens on stability of water-in-oil (W/O) highly concentrated emulsions (HCE with ? = 90 vol%) with an overcooled dispersed phase was studied. A series of five silica with HI in the 0.60–1.34 range and HI > 3 were used separately and in combination with a low molecular weight traditional surfactant, Sorbitan MonoOleate (SMO). First, it was shown that SMO alone can stabilize W/O HCE whereas only silica nanoparticles with intermediate HI in the range 0.97 ≤ HI ≤ 1.34 could form W/O emulsions only up to 77–79 vol%. Then, on the contrary to SMO-based emulsions, Pickering emulsions are unstable under shearing. When mixed (silica plus SMO) emulsifier systems were used, firstly a thermodynamic consideration revealed that only SMO is likely to adsorb at the W/O interface and controls the emulsifying process by the decrease in the interfacial tension. Then, interestingly, all different kinds of emulsion stability investigated in this study demonstrate a breaking point (BP) at HI = 0.97. Below the BP the emulsions were found to be very unstable on shelf as well as under shear. Above the BP, a clear synergy between colloidal silica and SMO surfactant has been found.      

Water-in-oil emulsions stabilized by water-dispersible poly(N-isopropylacrylamide) microgels: understanding anti-Finkle behavior

Emulsions were prepared using poly(N-isopropylacrylamide) microgels as thermoresponsive stabilizers. The latter are well-known for their sensitivity to temperature: they are swollen by water below the so-called volume phase transition temperature (VPTT = 33 °C) and shrink when heated above it. Most of the studies reported in the literature reveal that the corresponding emulsions are of the oil-in-water type (O/W) and undergo fast destabilization upon warming above the VPTT. In the present study, whereas O/W emulsions were obtained with a wide panel of oils of variable polarity and were all thermoresponsive, water-in-oil (W/O) emulsions were found only in the presence of fatty alcohols and did not exhibit any thermal sensitivity. To understand the peculiar behavior of emulsions based on fatty alcohols, we investigated the organization of microgels at the oil-water interface and we studied the interactions of pNIPAM microgels with octanol. By combining several microscopy methods and by exploiting the limited coalescence process, we provided evidence that W/O emulsions are stabilized by multilayers of nondeformed microgels located inside the aqueous drops. Such behavior is in contradiction with the empirical Finkle rule stating that the continuous phase of the preferred emulsion is the one in which the stabilizer is preferentially dispersed. The study of microgels in nonemulsified binary water/octanol systems revealed that octanol diffused through the aqueous phase and was incorporated in the microgels. Thus, W/O emulsions were stabilized by microgels whose properties were substantially different from the native ones. In particular, after octanol uptake, they were no longer thermoresponsive, which explained the loss of responsiveness of the corresponding W/O emulsions. Finally, we showed that the incorporation of octanol modified the interfacial properties of the microgels: the higher the octanol uptake before emulsification, the lower the amount of particles in direct contact with the interface. The multilayer arrangement was thus necessary to ensure efficient stabilization against coalescence, as it increased interface cohesiveness. We discussed the origin of this counterexample of the Finkle's rule.     

W/O/W多重乳液中水传递的控制

建立了简化的W/O/W(水/油/水)多重乳液乳珠模型——统计平均半径模型, 预测出当W/O/W多重乳液内水相水滴之间以及内外水相之间均达到水传递平衡时的内外水相中盐的浓度, 从而实现对水传递的控制, 以维持W/O/W多重乳液的稳定. 按理论预测制备出了不同稳定态的W/O/W多重乳液, 利用差分扫描量热仪(DSC)检测了多重乳液中水的传递过程, 确定体系在实验状态下的稳定程度, 实验结果与理论预测基本吻合.     

Ethanol-in-oil emulsion (E/O) stabilized by polyglycerol polyricinoleate: A potential delivery system for ethanolic extract

This study evaluated how variations in polyglycerol polyricinoleate (PGPR) concentration and ethanol dispersed phase content affect the stability of ethanol-in-oil (E/O) emulsions. Results indicate that the stable 10?wt% E/O emulsions can be produced using 2?wt% PGPR. Increasing the ethanol dispersed phased content at constant PGPR concentration caused instability in emulsion. These emulsions remained stable to droplet flocculation and coalescence in the presence of Centella asiatica ethanol extract. PGPR does not greatly decrease the interfacial tension of the ethanol–oil interface. However, it adsorbed at the interface and stabilized the ethanol droplets in the emulsion via steric mechanism.     

Stability of W/O Emulsions Encapsulating Polysaccharides

In the frame of formulation of W/O emulsions entrapping polysaccharides devoted to agricultural applications, the aim of this work was to study the stability over time of these emulsions, stabilized with either soybean lecithin or polyglycerol polyricinoleate (PGPR) as emulsifiers. Emulsifiers were dissolved in oil phase, and polysaccharides (carboxymethycellulose (CMC), guar, xanthan) in ultrapure water. Emulsions stability was studied through natural aging tests and accelerated aging tests, using bottle tests, microscopy and calorimetry. Experiments showed that PGPR was more efficient than lecithin to stabilize emulsions containing the polysaccharides studied, and that emulsions prepared with CMC showed the best stability.     

Stabilization of Water‐Soluble Antioxidant in Water‐in‐Oil‐in‐Water Double Emulsions

Abstract

In this study, we are introducing a method that can effectively stabilize antioxidants in water‐in‐oil‐in‐water (W/O/W) double emulsions. Preliminarily, stable W/O/W double emulsions were produced by manipulating the characteristics of internal aqueous phase via two‐stage emulsification, resulting consequently in the formation of fine internal water droplets in the dispersed oil droplets. From conductivity measurements that can determine the elution amount of internal aqueous phase, it was confirmed that the double emulsion stability could be improved by treating the internal aqueous phase with a hydroxypropyl‐beta‐cyclodextrin. In this study, kojic acid, 5‐hydroxy‐2‐(hydroxymethyl)‐4‐pyrone was selected as a model antioxidant. The stabilization of kojic acid was attempted by locating it in the internal water droplets of the stable W/O/W double emulsions. The stability of kojic acid in the double emulsion system could be maintained at 90% for 10 weeks at high temperature. We believe that these stable W/O/W double emulsions could be used meaningfully as a carrier for many unstable antioxidants.     

Stabilization and destabilization of water-in-crude oil emulsions from the norwegian continental shelf. Correlation with model systems

A summary of properties of water-in-crude oil emulsions from the Norwegian Continental Shelf or model water-in-oil emulsions is given. A separation method for the indigenous surface active crude oil components based on adsorption/extraction was developed. These components and their films were characterized by M_w determinations, FT-IR, Langmuir-Blodgett, surface/interfacial tension, dielectric spectroscopy and interactions with chemical destabilizers. The stability/instability properties of authentic water-in-crude oil emulsions can be reproduced by model W/O emulsions stabilized by the interfacially active crude oil fraction. Processes inside the water droplets and at the W/O interface taking place upon destabilization were followed by means of dielectric spectroscopy.     

Thickening properties and emulsification mechanisms of new derivatives of polysaccharides in aqueous solution

The thickening properties of aqueous solutions of HHM-HEC (hydrophobically-hydrophilically modified hydroxyethylcellulose) and the emulsification mechanisms of HHM-HEC/water/oil systems were investigated. A dramatic increase in viscosity was observed with increased HHM-HEC concentration in water, caused by aggregation of hydrophobic alkyl chains. At higher concentrations of HHM-HEC (above 0.6 wt%) in water, it forms an elastic gel, which has good thixotropic properties and a high yield value. O/W (oil-in-water) type emulsions were obtained using HHM-HEC, which can emulsify various kinds of oil, including hydrocarbon, silicone, and perfluoropolymethylisopropyl ether. The viscosity of these emulsions depends only upon the oil volume fraction, not on the kind of oil. In addition, the oil particle size in the emulsions remained constant after a certain period because HHM-HEC formed a strong gel network structure and a protective layer, which prevented the emulsion from coalescing. Measurements of interfacial tension revealed that the alkyl chains in HHM-HEC did not significantly lower the interfacial tension at the water/oil interface when 0.5 wt% of HHM-HEC was added to water. Steady flow and oscillatory experimental results show that the rheological behavior of HHM-HEC/water/oil emulsions was similar to that of aqueous solutions of HHM-HEC. In the HHM-HEC/water/oil emulsion system, oil droplets were dispersed and kept stable in the strong gel structure of HHM-HEC. The aqueous solution of HHM-HEC showed salt resistance. It is thought to be due to sulfonic acid groups in HHM-HEC. The stability of the emulsion using HHM-HEC is based on both protective colloidal effects and associative thickening caused by alkyl chains in HHM-HEC.     

Effects of compositions on the stability of polyols-in-oil-in-water (P/O/W) multiple emulsions

Polyols-in-oil-in-water (P/O/W) multiple emulsions were successfully prepared by using polyols as inner aqueous phase to avoid instabilities caused by water. The influence of polyols, oils and emulsifiers on the morphology and stability of P/O/W multiple emulsions were studied and the stability mechanisms of this new kind of multiple emulsions were also explored. Glycerol that has the worst solubility in oil phase contributed to the formation of stable inner droplets which agree with the Ostwald Ripening theory. Mineral oil worked well with the system proving that oils possessing similar solubility parameters with the hydrophobic group of emulsifiers benefited for system stability. Several typical surfactants had been investigated in this article, and it turned out that emulsifiers Cetyl PEG/PPG-10/1 Dimethicone and the block copolymer Poloxamer 407 were suitable for the P/O/W system. The stability of the system affected by different compositions was evaluated based on microscopic observation and rheological measurements. The novel multiple emulsions will provide enlightening recommendations for future investigations and applications in cosmetic, food and pharmaceuticals, including drug delivery and the encapsulation of hydrophilic actives and actives that are soluble in polyols.     

Emulsifying Ability of β-Cyclodextrins for Common Oils

Emulsification of various common oils was investigated using natural β-cyclodextrin (β-CD) and its derivatives as emulsifiers. An oil/water (O/W) emulsion was formed using β-CD, whereas a water/oil (W/O) emulsion was formed using tripropanoyl-β-CD and tributanoyl-β-CD derivatives. Triacetyl-β-CD gave rise to both O/W and W/O emulsions. The type of emulsion was governed by the contact angle (θ_ow), which the precipitate of CD origin make with the oil-water interface.     

细菌纤维素纳米纤维稳定乳液的性能

采用超声和高压均质两种方式分散的细菌纤维素(BC)悬浮液制备了BC纳米纤维稳定的水包油型Pickering乳液, 并考察了纤维用量、 pH值和机械分散方式对乳液稳定性的影响. 结果表明, 乳液的稳定性随纳米纤维用量的增加而增加; 碱性条件比酸性条件制备的乳液稳定性高, 且在pH=12时达到最高. 用高压均质方式分散的BC稳定乳液的效果优于采用超声方式分散的BC的效果, 这是由于高压均质后的纤维较短, 可以提供更多的纳米纤维稳定乳液. 计算结果表明, BC纳米纤维在液体石蜡/水界面上的三相接触角为72.5°, 说明BC适合稳定水包油型乳液.     

Emulsifying potency of new amino acid-type surfactant (II): stable water-in-oil (W/O) emulsions containing 85 wt% inner water phase

The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.     

Effect of lateral heterogeneity in mixed surfactant-stabilized interfaces on the oxidation of unsaturated lipids in oil-in-water emulsions

The development of lipid oxidation in oil-in-water (O/W) emulsions is widely influenced by the properties of the interfacial layer, which separates the oil and water phases. In this work, the effect of the structure of the interface on the oxidative stability of surfactant stabilized O/W emulsions was investigated. Emulsions were prepared with either single Tween 20 or Tween 20/co-surfactant mixtures in limiting amounts. The co-surfactants, Span 20 and monolauroyl glycerol have the same hydrophobic tail as Tween 20 but differ by the size and composition of their polar headgroup. Metal-initiated lipid oxidation, monitored through the measurement of oxygen uptake, formation of conjugated dienes and volatile compounds, developed more rapidly in the emulsions stabilized by the surfactant mixture than in the single Tween 20-stabilized emulsion. The reconstitution of Tween 20/co-surfactant films at the air-water interface and their surface-pressure isotherms highlighted that, contrary to single Tween 20 molecules, Tween 20/co-surfactant mixtures exhibited an heterogeneous distribution within the interfacial layer, offering probably easier access of water-soluble pro-oxidants to the oil phase. These observations provide direct information about the link between the homogeneity of the interface layer and the oxidative stability of emulsions.     

Microscope measurements for the transient formation of W/O emulsions of sodium bis(2-ethylhexyl) sulfosuccinate in the dodecane/water interfacial region

The present study investigated the transient formation of water-in-oil (W/O) emulsions of sodium bis(2-ethylhexyl) sulfosuccinate (aerosol OT, AOT) in a dodecane/water interfacial region and the anomalous uptake of water in the dodecane phase by in situ bright-field optical microscopy and water concentration measurements in detail. The hydrodynamic radius of the individual W/O emulsions in the dodecane phase was determined to be 0.1-1.2 μm from the analysis of their diffusion behavior; they are much larger than common W/O microemulsions (a few nanometers in radius). At first, they were formed spontaneously in the dodecane/water interfacial region without shaking, and they diffused away into the dodecane phase. Then, almost all of them vanished at the interface by fusion. Their number and the water concentration in the dodecane phase increased first and then decreased gradually. The formation mechanism was discussed with estimated concentration profiles of AOT and water molecules, which suggests that larger W/O emulsions of 0.01-0.44 μm in radius can be formed in the dodecane phase near the interface (within 2 μm) because the concentration of AOT becomes lower than that of water there.     

Behavior and Stability of Naphthenic Acid/Naphthenate Stabilized Emulsions. Mixed C80-Tetraacid and Stearic Acid Stabilization

Previous studies have focused on monomeric naphthenic acids and their ability to stabilize emulsions, but little has been reported on C80-tetraacids and their ability to function as an emulsifier. In this article, we report on the chemistry of the C80-tetraacids as an emulsion stabilizer and also on the role this acid has in mixed monoacid-tetraacid systems. The study focuses on the type of emulsion formed and the stability of these emulsions with respect to water cut, pH, salinity of the water phase, and type of counterion. Interfacial behavior and the electrostatic properties of the emulsion were studied in order to determine which of the acids were present at the interface and which of the acids gave the largest contribution to the emulsion stability. It was found that C80-tetraacids form only O/W emulsion under the conditions studied. Addition of monoacid to the system did not change the type of emulsion formed. Highest stability was seen for emulsions containing both monoacid and tetraacids. When adding NaCl a phase inversion from O/W to W/O emulsion appeared around a concentration of 2 wt% of NaCl.     

Water mass transfer in W/O emulsions

Water transportation through the oil phase in W/O emulsions and in W1/O/W2 systems (W/O emulsion in contact with water) was examined. Substance diffusion through interfaces led to interface instability and spontaneous emulsification which caused nanodispersion formation. The photomicrographs of Pt/C replicas of emulsions showed the presence in the continuous oil phase a lot of nanodispersion droplets with a diameter in the range 17-25 nm. Diffusion coefficient (D) of water calculated on the base of Lifshiz-Slezov-Wagner (LSW) equation was about 15 times lower than the coefficients of molecular diffusion. Since such emulsions were extremely unstable toward coalescence, the growth of water droplets took place through as Ostwald ripening as coalescence. In three-phase W1/O/W2 systems diffusion of water, Rhodamine C, and ethanol was studied. D calculated on the base of the equation of nonstationary diffusion were approximately 1000 times lower than molecular ones. It was assumed, that nanodispersion droplets were more likely water carriers in investigated W/O emulsions stabilized by sorbitan monooleate.