Emulsion stability in sucrose monoalkanoate system with addition of cosurfactants

The hydrophile-lipophile property of the sucrose monododecanoate changes from hydrophilic to lipophilic by adding an alcohol as a cosurfactant. With the addition of a short-alkyl-chain alcohol (pentanol, hexanol), the surfactant forms the middle-phase microemulsion whereas a lamellar liquid crystal (L_!) appears with a medium- or long-chain alcohol (heptanol, octanol, decanol) at the balanced state in water/ SE/ cosurfactant/ decane system. The effect of changing oil was also studied in the presence of a middle-chain cosurfactant (heptanol). A short-chain aromatic oil (m-xylene) forms middle-phase microemulsion whereas a longer aliphatic one (hexadecane) forms lamellar liquid crystalline phase in a dilute region when the HLB of surfactant is balanced in a given system. O/W emulsions become stable on the hydrophilic-surfactant-rich side whereas W/O emulsions are stable on the cosurfactant-rich side. Emulsions are very unstable in the three-phase regions. However, when the lamellar phase is produced, emulsions become stable at the balanced state because water and oil are incorporated in L_! phase in the longer cosurfactant systems such as water/ SE/ octanol/ decane and water/ SE/ decanol/ decane.     

Effect of ionic surfactants on the phase behavior and structure of sucrose ester/water/oil systems

The phase behavior and structure of sucrose ester/water/oil systems in the presence of long-chain cosurfactant (monolaurin) and small amounts of ionic surfactants was investigated by phase study and small angle X-ray scattering. In a water/sucrose ester/monolaurin/decane system at 27 degrees C, instead of a three-phase microemulsion, lamellar liquid crystals are formed in the dilute region. Unlike other systems in the presence of alcohol as cosurfactant, the HLB composition does not change with dilution, since monolaurin adsorbs almost completely in the interface. The addition of small amounts of ionic surfactant, regardless of the counterion, increases the solubilization of water in W/O microemulsions. The solubilization on oil in O/W microemulsions is not much affected, but structuring is induced and a viscous isotropic phase is formed. At high ionic surfactant concentrations, the single-phase microemulsion disappears and liquid crystals are favored.     

Formation of Microemulsions in Aqueous NaCl/Sodium (3-Dodecanoyloxy-2-Hydroxy-Propyl) Succinate/Glycerol Mono(2-Ethylhexyl) Ether/Oil Systems

Sodium (3-dodecanoyloxy-2-hydroxy-propyl) succinate (SLGMS) forms microemulsions by mixing with cosurfactants such as glycerol mono(2-ethylhexyl) ether (MEH), although the combination with ordinary cosurfactant such as hexanol does not form a microemulsion of large solubilization. The middle-phase microemulsion coexists with excess water and oil (octane) phases at an optimum-mixing fraction of SLGMS and MEH in the presence of salt. The monomeric solubility of MEH in oil is low and MEH is mainly combined with SLGMS at an oil—water interface inside microemulsions. With decreasing salinity, the three-phase body shrinks and eventually disappears. The three-phase body may be terminated at a tricritical point, at which three phases simultaneously coexist. The effect of type of oil on the solubilization capacity of the microemulsions is also discussed.     

Water Solubilization in Mixed Nonionic Surfactants Microemulsions

The systems investigated were water/sucrose laurate/ethoxylated mono-di-glyceride/oleic phase. The oleic phase used first was the pure oils R (+)-limonene, isopropylmyristate, and caprylic-capric triglyceride; these oils were then mixed with ethanol at different mixing ratios (w/w). The total area of the one phase microemulsion region is dependent on the mixing ratios (w/w) of the mixed surfactants and that of the ethanol/oil. The largest microemulsion phase area formed with a surfactants mixing ratio (w/w) equals unity. For the systems where the oleic phase was a mixture of oil and ethanol, the total area of the monophasic microemulsion increases with the increase in the ethanol/oil mixing ratio (w/w). The Gibbs free energy of solubilization was estimated. It increases as the mixing ratio (w/w) of ethoxylated mono-di-glyceride/sucrose laurate increases and with the increase in the ethanol/oil mixing ratio (w/w). The Gibbs free energy of solubilization decreases with the increase in the water content in the water-in-oil microemulsions. The values of the Gibbs free energy of solubilization are higher for oil-in-water microemulsions compared to those of the water-in-oil microemulsions.     

Formulation and characterization of a biocompatible microemulsion composed of mixed surfactants: lecithin and Triton X-100

We report on the formation and characterization of a biocompatible microemulsion (ME) system composed of lecithin (L), Triton X-100 (T) as the surfactant(s), butyl lactate (BL) as the cosurfactant, and isopropyl myristate (IPM) as the oil phase and water. Detailed phase construction reveals that mixing of surfactants (L and T) produces larger single-phase ME region compared to L. In the mixed surfactant systems, a three-phase body appears which is otherwise not obtained in the single surfactant counterparts signifying the synergistic solubilization behaviour upon mixing. The maximum solubilization capacity decreases as the content of T increases in the mixture. Viscosity, conductance and adiabatic compressibility measurements of the single-phase ME systems at a constant amphiphile concentration (80 % w/w) show a linear trend with increasing water content revealing a droplet-type structure of all the studied formulations. FTIR studies in the water-in-oil (w/o) region identify the presence of three distinct types of water molecules in these systems and their relative content changes with the interfacial composition as well as the total water content in the system. Our study offers a biocompatible mixed ME system in which the physical properties do not differ much from those of the lecithin-based systems with the additional advantage of having higher solubilization capacity, low pH dependency and low viscosity, which renders its potential to be used for specific pharmaceutical applications.     

Sucrose ester-based biocompatible microemulsions as vehicles for aceclofenac as a model drug: formulation approach using D-optimal mixture design

We assessed the functionality of sucrose esters (sucrose laurate, myristate, palmitate, and stearate), relatively innocuous nonionic surfactants, in formulation of biocompatible microemulsions. The putative influence of surfactant structure on the extension of microemulsion region was explored through the construction of the pseudo-ternary phase diagrams for the isopropyl myristate/sucrose ester-isopropyl alcohol/water system, using the titration method and mixture experimental approach. Minor changes in surfactant tail length strongly affected the microemulsion area boundaries. D-optimal mixture design proved to be highly applicable in detecting the microemulsion regions. Examination of conductivity, rheology, and thermal behavior of the selected sucrose laurate and sucrose myristate-based microemulsions, upon dilution with water, indicated existence of percolation threshold and suggested the phase inversion from water-in-oil to oil-in-water via a bicontinuous structure. Atomic force micrographs confirmed the suggested type of microemulsions and were valuable in further exploring their inner structure. The solubilization capacity of aceclofenac as a model drug has decreased as the water volume fraction in microemulsion increased. High surfactant concentration and the measured solubility of aceclofenac in microemulsion components suggested that the interfacial film may mostly contribute to aceclofenac solubilization.     

Catanionic surfactants: microemulsion formation and solubilization

We review and summarize the three-phase behavior and solubilization of microemulsions with catanionic surfactants. Particular emphasis is placed to the three-phase behavior of mixtures of oil, water and alcohol with mixed surfactants containing one anionic and one cationic surfactant. The effect of salt and catanionic surfactant on the HLB composition and solubilizing capacity of surfactants to form microemulsions is discussed.     

Three-phase behavior in a mixed nonionic surfactant system

The effect of monodisperse solubilities of each surfactant in an excess oil phase on the three-phase behavior was investigated in a water/octaethyleneglycol dodecyl ether (R₁₂EO₈)/tetraethyleneglycol dodecyl ether (R₁₂EO₄)/heptane system. The mid temperature of the three-phase region is defined as the HLB temperature. The HLB temperature is largely skewed to higher temperature in a dilute region due to the difference in the distribution of each surfactant between excess oil and microemulsion (surfactant) phases forming the three-phase body. Taking account of the monodisperse solubilities, the equation for the HLB temperature was obtained on the basis of geometrical calculation of a particular three-phase triangle. The equation well describes the three-phase behavior for a mixed surfactant system in a space of compositions and temperature.In the mixed surfactant system, the monodisperse solubility of R₁₂EO₈ in oil phase forming a three-phase body is monotonously increased with the rise in temperature, whereas that of R₁₂EO₄ is first increased and then is decreased. Consequently, the sum of both solubilities does not change greatly in a wide range of temperature.     

Formation of Cubic-Phase Microemulsions with Anionic and Cationic Surfactants at Equal Amounts of Oil and Water

The formation and microstructure of cubic phases were investigated in anionic and cationic surfactant-containing systems at 25 degrees C. In the system sodium dodecyl sulfate(SDS)-dodecyltrimethylammonium bromide(DTAB)-water, mixing of two surfactants shows the phase transition hexagonal phase (H(1))-->surfactant precipitate, accompanied by an obvious decrease in the cross-sectional area per surfactant in the rod micelles of the hexagonal liquid crystal. In the mixed systems brine(A)-dodecane(B)-SDS(C)-DTAB(D)-hexanol(E), the isotropic discontinuous cubic phase is formed from the H(1) phase at a low cationic surfactant weight fraction, Y=D/(C+D), and from the lamellar phase at high Y upon dilution with equal amounts of oil and brine, respectively. The minimum surfactant concentration to form the cubic phase decreases with increases both in cationic surfactant weight fraction Y from 0 to 0.30 and in hexanol weight fraction, W(1)=E/(C+D+E), accordingly. The maximum solubilization for oil of the cubic phase reaches 43 wt% at 14 wt% of mixed surfactants and alcohol. Copyright 2000 Academic Press.     

Phase behavior at low oil contents in systems containing anionic surfactants

The transition from liquid crystalline to microemulsion phases has been investigated by adding oil to surfactant—alcohol—brine mixtures in two systems containing anionic surfactants. At high salinities where the surfactant is preferentially soluble in oil, addition of oil first causes transition from a lamellar liquid crystal to a water-continuous isotropic phase which exhibits streaming birefringence and probably contains large, anisotropic micelles. This isotropic phase inverts to an oil-continuous microemulsion as oil content further increases. At somewhat lower salinities just below the “optimum” where the surfactant has equal solubilization capacities for oil and brine, the system passes through three three-phase regions as oil is added. In order of increasing oil content, these consist of two microemulsions in equilibrium with a lamellar liquid crystalline phase, the same two microemulsions in equilibrium with excess brine, and a microemulsion in equilibrium with excess oil and excess brine.     

Modeling solubilization of oil mixtures in anionic microemulsions II. Mixtures of polar and non-polar oils

Polar/amphiphilic oils, called lipophilic linkers, are sometimes added to oil-water-ionic surfactant microemulsions in order to increase the solubilization of hydrophobic oils. The solubilization increase has been well documented for a number of systems. However, mathematical models to calculate the solubilization increase have been proposed only for optimum microemulsions (i.e., middle phase microemulsions solubilizing equal volumes of oil and water). In this paper we propose a model, which predicts solubilization enhancement for non-optimum microemulsion systems as well. The model is an extension of the net-average curvature model of microemulsion. The net-average curvature model is combined with a surface activity model to account for the increased palisade layer solubilization due to the presence of the polar/amphiphilic oil component. New non-linear mixing rules are also incorporated to account for the optimum salinity and the characteristic length variation of the anionic surfactant microemulsion as a function of the lipophilic linker concentration. The model predicts the effect of the lipophilic linker and the electrolyte concentration on the oil solubilization in accordance with the experimental results.     

The Effect of Fatty Alcohols and Valeric Acid on the Regions of Existence of a Three-Phase System Containing Water, Oil, and Surfactant

For different water–oil–surfactant systems with added aliphatic alcohols and valeric acid, conditions for the formation of the microemulsion (third) phase containing approximately equal amounts of oil and water were determined. It was established that the microemulsion phases are formed in the initial two-phase system (oil-in-water microemulsion–oil) on adding alcohols or the acid, which can be more hydrophilic or more hydrophobic than micelle-forming surfactants. Concentrations of alcohols necessary for the transformation of the three-phase system into the two-phase one were determined. The influence of energy parameters of surfactants and structural characteristics of the alcohol and basic micelle-forming surfactant on the stability of the three-phase system is discussed.     

Effect of temperature and salt on the phase behavior of nonionic and mixed nonionic-ionic microemulsions with fish-tail diagrams

The phase behavior of Brij-56/1-butanol/n-heptane/water is investigated at 30 degrees C with alpha [weight fraction of oil in (oil+water)]=0.5, wherein a 2-->3-->2 phase transition occurs with increasing W1 (weight fraction of 1-butanol in total amphiphile) at low X (weight fraction of both the amphiphiles in the mixture) and a 2-->1-->2 phase transition occurs at higher X. Addition of an ionic surfactant, sodium dodecylbenzene sulfonate, destroys the three-phase body and decreases the solubilization capacity of the system at different delta (weight fraction of ionic surfactant in total surfactant). A three-phase body appears at alpha=0.25, but not at alpha=0.75 for the single system. No three-phase body appears with the mixed system at either alpha value. Increased temperature increases the solubilization capacity of the Brij-56 system; on the other hand, a negligible effect of temperature on the Brij-56/SDBS mixed system has been observed. Addition of salt (NaCl) produces a three-phase body for both single and mixed systems and increases their solubilization capacities. The monomeric solubility of 1-butanol in oil (S1) and at the interface (S1s) has been calculated using the equation hydrophile-lipophile balance plane for both singles- and mixed-surfactant systems. These parameters have been utilized to explain the increase in solubilization capacity of these systems in the presence of NaCl.     

Effect of Adding an Amphiphilic Solubilization Improver, Sucrose Distearate, on the Solubilization Capacity of Nonionic Microemulsions

We have studied the effect of adding sucrose distearate (2C(18)SE) on the solubilization capacity of microemulsions formed in the water/C(12)EO(6)/n-decane system. Upon addition of 2C(18)SE to the binary water/C(12)EO(6) system, a lamellar liquid crystal region developed. This suggests that the rigidity of the surfactant layer is strengthened. The solubilization of water and n-decane in the bicontinuous microemulsions increases about three times upon replacing 10% C(12)EO(6) with 2C(18)SE; besides, the HLB temperature is not greatly affected by 2C(18)SE. On the other hand, sucrose monostearate (C(18)SE) does not have such a function. The effect of added 2C(18)SE on the solubilization capacity of the discrete droplet-type o/w or w/o microemulsions was also studied. The efficiency of the solubilization-improving effect is reduced when the system is far from the HLB temperature. Copyright 2001 Academic Press.     

MINIMIZING COSOLVENT REQUIREMENTS FOR MICROEMULSION FORMED WITH BINARY SURFACTANT MIXTURES

The role of alcohols in microemulsion formation is primarily two-fold. They function as cosolvents by modifying surfactant partitioning between the aqueous and oleic phases and they function as cosurfactants stabilizing microemulsion to the exclusion of unbounaed structures such as liquid crystals, gels or precipitates. Given the freedom of choice among surfactants and their mixtures, the former role of the alcohol can easily be obviated. However, the latter requirement is more fundamental and not so easily removed. This study provides guidance in the purposeful construction of mixtures of synthetic surfactants which can minimize or eliminate alcohol requirements, depending on temperature and salinity. The approach Involves mixing straight tailed (high solubilization parameter) species with mid-chain branched (low cosolvent requirement) species in a spectrum of mole ratios and identifying the minimum alcohol concentration for stable microemulsion. A number of acceptable systems were found.     

Solubilization by different-sized surfactant mixtures

The solubilization phenomenon was investigated in mixed surfactant systems. The solubilization power of a mixed surfactant reaches its maximum at a particular temperature at each mixing ratio of surfactants. When the mole fraction of C4E1 in the total surfactant (w1 value) was varied in a water/C12E5/C4E1/decane system, the minimum mole fraction of total surfactant in the system necessary to obtain a single microemulsion phase (xi value) was almost unchanged for w1<0.3, whereas it increased remarkably for w1>0.8. The molar solubilization capacity (Cs=(1-xi)/xi) of the mixed surfactant decreased remarkably for w1<0.3, whereas it decreased gradually for w1>0.8. The result [Formula: see text] is due largely to the characteristic of the function xi(Cs)=1/(1+Cs), specifically, [Formula: see text] , where dxi/dw1=(dxi/dCs)(dCs/dw1). The partial molar solubilization capacity (Cs) of C4E1 was negative at almost all w1, but the Cs value of C12E5 went through a maximum on the addition of C4E1. Propanol (a cosurfactant) has the same effect on the solubilization phenomenon in the water/C12E6/propanol/heptane system. In the water/C12E5/C12E7/decane system, the Cs value of each surfactant did not vary greatly as the mixing ratio of surfactants was varied. The Cs and xi values were close to molar additivity for each mixing ratio.     

阴/阳离子表面活性剂复配体系的中相微乳液研究

阴离子表面活性剂双-2-乙基己基磺化琥珀酸钠(简称AOT), 和阳离子表面活性剂十六烷基三甲基溴代铵(简称CTAB), 在有醇、正辛烷、盐水存在的情况下,能形成多相微乳液。本文系统地研究了阴/阳离子表面活性剂配比、醇的种类、醇的浓度对该体系的中相微乳液的形成及特性的影响, 得到了中相微乳液的特性参数(最佳含盐量S^*, 最佳中相微乳液体积V^*, 界面张力r~E、盐宽△S等)。这些性质对与阴/阳离子表面活性剂复配体系, 三次采油及日用化工上的应用开发具有重要意义。最后还开展单独阴离子表面活性剂体系和阴/阳离子表面活性剂复配体系进行了比较, 得到一些有价值规律, 并从理论上进行了探讨。     

Phase behavior of sucrose monoalkanoate in a water-long-chain alcohol system

Phase diagram of a water/sucrose monododecanoate (SE)/hexanol system was determined at 30°C. Aqueous micellar, reverse micellar, normal hexagonal liquid crystalline, and lamellar liquid crystalline phases appear in the phase diagram. The change in interlayer spacing and interfacial section area of surfactant in the liquid crystalline phases was investigated by small-angle x-ray scattering. Upon addition of water, the section area and the radius of cylindrical aggregates are almost constant in a hexagonal liquid crystal, whereas the distance between each cylinder is separated on the water-SE axis. The interlayer spacing slightly decreases or is almost unchanged on the surfactant-hexanol axis, because alcohol molecules penetrate into the palisade of bilayers. Although the average section area decreases with increasing alcohol content, each section area of SE and alcohol molecules are kept constant. Since the interfacial section area of alcohol is less than the section area of hydrocarbon chain, the phase transition from lamellar liquid crystal to reverse micelle occurs in an alcohol-rich region.     

Diclofenac Solubilization in Microemulsions Based on Mixed Nonionic Surfactants and R (+)-limonene

Diclofenac is a nonsteroidal anti-inflammatory drug that reduces inflammation and pain hormones in the body. Dispersing the drug in water is impossible and its solubility in oils is very limited. In this study, we solubilized sodium diclofenac in nanostructures of the constructed U-type water/sucrose laurate/ethoxylated mono-di-glyceride/oleic phase microemulsions. The mixing ratio (w/w) of sucrose laurate/ethoxylated mono-di-glyceride equals unity. The oleic phase was the pure R (+)-limonene or R (+)-limonene mixed with ethanol at a weight ratio equals unity. The solubilization capacity of the drug in these systems is many times higher than in either oil or water systems. The sodium diclofenac solubilized microemulsions are fully diluted with water without phase separation. The solubilization capacity decreases as the water content increases. The system free of alcohol solubilizes less amounts of drug over all the range of water contents compared to the system containing alcohol. Small angle x-ray scattering was used to evaluate the effect of solubilized sodium diclofenac on the microstructure and diffusion properties of the loaded microemulsions. From the periodicity and correlation length measured by small angle x-ray scattering, we learned that the drug affects the structure of loaded microemulsion droplets probably less spherical than the empty systems. The transition from water-in-oil to a bicontinuous phase occurs at the different water contents compared to the empty (i.e., without drug) microemulsions. The drug remains solubilized at the interface upon further dilution with water and is oriented with its hydrophilic part facing the water, and strongly affects the inversion to oil-in-water droplets.     

Effect of Amino‐Acid‐Based Polar Oils on the Krafft Temperature and Solubilization in Ionic and Nonionic Surfactant Solutions

Abstract

The Krafft temperature and solubilization power of ionic and nonionic surfactants in aqueous solutions are strongly affected by added polar oils such as amino‐acid‐based oils (e.g., N‐acylamino acid esters, AAE), because they tend to be solubilized in the surfactant palisade layer. The Krafft temperatures of 5 wt.% sodium dodecyl sulfate (SDS)‐water and octaoxyethylene octadecyl ether (C₁₈EO₈)‐water systems largely decreases upon addition of AAE and 1‐hexanol, whereas it decreases very slightly in isopropyl myristate (IPM) and n‐dodecane. The lowering of the Krafft temperature can be explained by the same mechanism as the melting‐temperature reduction of mixing two ordinary substances. Namely, the polar oils are solubilized in the surfactant palisade layer of micelles and reduce the melting temperature of hydrated solid‐surfactant (Krafft temperature). On the other hand, non‐polar oil such as dodecane is solubilized deep inside micelles and makes an oil pool. The solubilization of non‐polar oil is enhanced by mixing surfactant with AAE due to an increase in micellar size.