Formation of intermediate micellar phase between hexagonal and discontinuous cubic liquid crystals in brine/N-acylamino acid surfactant/N-acylamino acid oil system

The phase behavior in the brine/sodium N-dodecanoyl sarcosinate (Sar)/isopropyl N-dodecanoyl sarcosinate (SLIP) system has been investigated by means of phase study, static light scattering, and small-angle X-ray scattering. The liquid crystal phases, hexagonal (H(1)) and discontinuous cubic (I(1)), melt upon the addition of NaCl, which shows the similar effect to the increasing of temperature. The addition of SLIP to the brine/Sar solution at high Sar concentration induces the phase transition from H(1) to I(1) via the isotropic micellar solution (W(m2)). The micellar structure in the W(m2) phase also changes from the wormlike to the globular micelle with SLIP concentration. Adding NaCl reduces the repulsive force between the Sar head groups and simultaneously the space of the solubilized SLIP in the palisade layer, leading SLIP to shift their location further into the micelle core. As a consequence, the hexagonal symmetry breaks into the micelle solution and the liquid crystal order is destabilized entropically.     

Solubilization of triglycerides in liquid crystals of nonionic surfactant

The solubilization of triglycerides [1,2,3-tributanoylglycerol (TBG) and 1,2,3-trihexanoylglycerol (THG)] in water/octa(oxyethylene) dodecyl ether (C(12)EO(8)) systems has been investigated. Oil-induced changes in the structure of liquid crystals in water/C(12)EO(8) system have been studied by optical observation and small-angle X-ray scattering (SAXS) measurements. In the water/C(12)EO(8)/oil systems, solubilization of THG and TBG induces a transition between H(1) (hexagonal) and L(alpha) (lamellar) liquid crystals at high C(12)EO(8) concentrations, whereas at low surfactant concentrations a H(1)-I(1) (discontinuous micellar cubic phase) transition occurs. This anomalous behavior is attributed to the partitioning of solubilized oil in the micelles. At low surfactant concentrations THG is mainly solubilized into the hydrophobic cores of the surfactant micelles, indicating high swelling or low penetration tendency, resulting in a steep increase in the radius of the aggregates (r(H)), thereby inducing a rod-sphere transition. At high surfactant concentrations, THG is not mainly solubilized into the core but distributed between the palisade layer and the core of the aggregates. The TBG is considerably solubilized into the surfactant palisade layer, indicating a high penetration tendency, resulting in an increase in the effective cross-sectional area per surfactant molecule, a(s). The thermal stability of the I(1) phase increases with the solubilization of THG into the aggregate cores. The percentage deviation of the experimental interlayer spacings (P(d)) from complete swelling was also evaluated for different triglycerides in the H(1) and L(alpha) phases or different surfactant concentrations. It is found that the penetration tendency of triglycerides could be used as a tuning parameter for I(1) phase formation depending on the surfactant concentration and the molecular weight of the oil.     

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.     

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.     

Aqueous microemulsions of a fluorinated surfactant and oil studied by PFG-NMR: transformation from threadlike to spherical micelles

The aqueous microemulsion system consisting of the fluorinated surfactant tetraethylammonium perfluorooctylsulfonate (TEAFOS) and the fluorinated oil 1H-perfluorohexane (PFH) has been investigated using the pulsed field gradient NMR self-diffusion method on both 1H and 19F. Neat TEAFOS(aq) builds threadlike micelles from rather low surfactant concentrations up to ca. 80 mmol kg(-1). The addition of PFH to TEAFOS(aq) solutions induces a transition from threadlike micelles to spherical micelles solubilizing the oil. In this paper, information from the self-diffusion coefficients of oil (PFH), surfactant counterion (TEA+), surfactant ion (FOS-), and water (HDO) during the transition is presented.     

Model calculations of the spontaneous curvature, mean and Gaussian bending constants for a thermodynamically open surfactant film

The spontaneous curvature (H(0)), mean and Gaussian bending constants (k(c) and k (c)), as defined in the well-known Helfrich expression, have been calculated from a detailed model for a thermodynamically open surfactant layer. The effect of head group cross-section area, surfactant tail length and electrolyte concentration for monovalent ionic surfactants have been investigated. Geometrical packing constraints subjected to the aggregated hydrocarbon tails and electrostatics are found to be the dominant contributions to H(0), k(c) and k (c). In addition, the transition from spherocylindrical micelles to vesicles were investigated in terms of the three parameters and the following simple expressions were derived as criteria for coexistence between micelles and vesicles H(0)=1/4 xi and N(ves)/N(mic)=exp[4 pi(k(c)+k (c))/kT], where xi is the thickness of the hydrocarbon part of the film and N(mic) and N(ves) the average aggregation numbers of micelles and vesicles, respectively. However, it is found that the ratio N(ves)/N(mic) is order of magnitudes too large for vesicles to form at all in charged single-surfactant systems where the surfactant head is of moderate size.     

Emulsification through surfactant hydration: the PIC process revisited

We have performed sudden composition changes on a (surfactant + oil + water) system by adding water to a (surfactant + oil) solution. This composition change quenches the system into a metastable oil-in-water emulsion with a population in the 100 nm range. The conditions for a successful quench are as follows: the initial water content should be below a boundary called the "clearing boundary" (CB), the final water content should be sufficiently beyond CB, and the quench should be fast. We have used high purity components to avoid the complex phase separation patterns that occur with low purity ingredients: the surfactant is octaethylenehexadecyl ether (C(16)E(8)) and the oil is hexadecane (C(16)). Under these conditions, we show that the pathway for this type of quench proceeds through the swelling of the reverse micellar phase by the added water and the formation of a sponge phase. Then, further water addition causes the nucleation of oil droplets in this sponge phase, with a size that matches the spontaneous curvature of the sponge phase. Part of the surfactant remains adsorbed on these droplets, and the rest is expelled as micelles that coexist with the droplets. It is concluded that a PIC emulsification will always lead to a bimodal size distribution with surfactant "wasted" in small micelles. This is in contrast with the more efficient PIT emulsification.     

Phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer and poly(oxyethylene) surfactant in water

The phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer (PI-PEO or C250EO70) and poly(oxyethylene) surfactant (C12EO3, C12EO5, C12EO6, C12EO7, and C12EO9) in water was investigated by phase study, small-angle X-ray scattering, and dynamic light scattering (DLS). The copolymer is not soluble in surfactant micellar cubic (I1), hexagonal (H1), and lamellar (Lalpha) liquid crystals, whereas an isotropic copolymer fluid phase coexists with these liquid crystals. Although the PI-PEO is relatively lipophilic, it increases the cloud temperatures of C12EO3-9 aqueous solutions at a relatively high PI-PEO content in the mixture. Most probably, in the copolymer-rich region, PI-PEO and C12EOn form a spherical composite micelle in which surfactant molecules are located at the interface and the PI chains form an oil pool inside. In the C12EO5/ and C12EO6/PI-PEO systems, one kind of micelles is produced in the wide range of mixing fraction, although macroscopic phase separation was observed within a few days after the sample preparation. On the other hand, small surfactant micelles coexist with copolymer giant micelles in C12EO7/ and C12EO9/PI-PEO aqueous solutions in the surfactant-rich region. The micellar shape and size are calculated using simple geometrical relations and compared with DLS data. Consequently, a large PI-PEO molecule is not soluble in surfactant bilayers (Lalpha phase), infinitely long rod micelles (H1 phase), and spherical micelles (I1 phase or hydrophilic spherical micelles) as a result of the packing constraint of the large PI chain. However, the copolymer is soluble in surfactant rod micelles (C12EO5 and C12EO6) because a rod-sphere transition of the surfactant micelles takes place and the long PI chains are incorporated inside the large spherical micelles.     

Morphological transitions in model membrane systems by the addition of anesthetics

The mechanism of anesthetic action on membranes is still an open question, regardless of their extensive use in medical practice. It has been proposed that anesthetics may have the effect of promoting pore formation across membranes or at least switching transmembrane channels. In both cases this may be the result of changes in the interfacial curvature of the membrane due to the presence of anesthetic molecules. Aqueous solutions of surfactants display phases that mimic, in a simplified manner, real biological membranes. Therefore, in this study, two nonionic surfactant systems C16E6/H2O in concentrated solution and C10E3/H2O in dilute solution have been used as model membranes for the investigation of the effects of six common anesthetics (halothane, sodium thiopental, lidocaine base form and hydrochloride, prilocaine hydrochloride, and ketamine hydrochloride). Both binary surfactant-water systems exhibit phase transitions from the lamellar phase, Lalpha, that has zero spontaneous curvature and zero monolayer curvature to phases with more local interfacial curvature. These are the random mesh phase, Mh1(0), which consists of lamellae pierced by water-filled pores with local areas of positive interfacial curvature and the sponge phase, L3, that consists of the lamellar phase with interlamellae attachments, often referred to as a "melted" cubic phase, possessing negative monolayer curvature. Small-angle X-ray scattering and 2H NMR experiments upon the C16E6/2H2O system and optical observations of the C10E3/H2O system showed that all anesthetics employed in this study cause a shift in the Mh1(0) to Lalpha phase transition temperature and in the Lalpha to L3 transition temperature, respectively. All of the anesthetics studied bind to the interfacial region of the surfactant systems. Two types of behavior were observed on anesthetic addition: type I anesthetics, which decreased interfacial curvature, and type II, which increased it. However, at physiological pH both types of anesthetics decreased interfacial curvature.     

BEHAVIOUR OF OIL/WATER MICROEMULSIONS UPON DILUTION WITH WATER

The dilution of series of oil-in-water microemulsions, formulated with Aerosol-OT as surfactant, water, isopropyl myristate as oil and varying amounts of butanol as cosurfactant, was studied. An infinite dilution could be obtained only adding water containing surfactant; the minimum amount of Aerosol-OT required was determined. The behaviour of the microemulsions upon dilution was related to the presence of nixed micelles in the aqueous phase.     

Phase behavior and preparation of mesoporous silica in aqueous mixtures of fluorinated surfactant and hydrophobic fluorinated polymer

The phase behavior and formation of self-assemblies in the ternary water/fluorinated surfactant (C(8)F(17)EO(10))/hydrophobic fluorinated polymer (C(3)F(6)O)(n)COOH system and the application of those assemblies in the preparation of mesostructured silica have been investigated by means of phase study, small angle X-ray scattering, and rheology. Hexagonal (H(1)), bicontinuous cubic (V(1)) with Ia3d symmetry, and polymer rich lamellar (L(alpha)(')) are observed in the ternary diagram. C(8)F(17)EO(10) molecules are dissolved in polymer rich aggregates, whereas (C(3)F(6)O)(n)COOH molecules are practically insoluble in the surfactant lamellar phase due to packing restrictions. Hence, two types of lamellar phases exist: one with surfactant rich (L(alpha)) and the other with polymer rich (L(alpha)(')) in the water/C(8)F(17)EO(10)/(C(3)F(6)O)(n)COOH system. As suggested by rheological measurements, worm-like micelles are present in C(8)F(17)EO(10) aqueous solutions but a rod-sphere transition takes place by solubilization of (C(3)F(6)O)(n)COOH. C(8)F(17)EO(10) acts as a structure directing agent for the preparation of hexagonal mesoporous silica by the precipitation method. The addition of (C(3)F(6)O)(n)COOH induces the formation of larger but disordered pores.     

Morphological transitions during the formation of templated mesoporous materials: theoretical modeling

We put forward a theoretical model for the morphological transitions of templated mesoporous materials. These materials consist of a mixture of surfactant molecules and inorganic compounds which evolve dynamically upon mixing to form different morphologies depending on the composition and conditions at which mixing occurs. Our theoretical analysis is based on the assumption that adsorption of the inorganic compounds onto mesoscopic assemblies of surfactant molecules changes the effective interactions between the surfactant molecules, consequently lowering the spontaneous curvature of the surfactant layer and inducing morphological changes in the system. On the basis of a mean field phase diagram, we are able to follow the trajectories of the system starting with different initial conditions, and predict the final morphology of the product. In a typical scenario, the reduction in the spontaneous curvature leads first to a smooth transition from compact spherical micelles to elongated worm-like micelles. In the second stage, the layer of inorganic material coating the micelles gives rise to attractive inter-micellar interactions that eventually induce a collapse of the system into a closely packed hexagonal array of coated cylinders. Other pathways may lead to different structures including disordered bicontinuous and ordered cubic phases. The model is in good qualitative agreement with experimental observations.     

Phase polymorphism by mixing of poly(oxyethylene)-poly(dimethylsiloxane) copolymer and nonionic surfactant in water

The phase behavior of the water/poly(oxyethylene)-poly(dimethylsiloxane) copolymer (Si25C3EO51.6)/pentaoxyethylene dodecyl ether (C12EO5) ternary system has been studied. Both the silicone copolymer and the surfactant have equal volumes of hydrophilic and lipophilic parts; i.e., these are balanced amphiphiles. Although only a lamellar phase is observed in water-Si25C3EO51.6 and water-C12EO5 binary systems, a variety of liquid crystalline phases, including normal micellar cubic (I1), hexagonal (H1), bicontinuous cubic (V1), lamellar (L(alpha)), reverse bicontinuous cubic (V2), and reverse hexagonal (H2), are observed in the copolymer-rich region of the ternary phase diagram. The small C12EO5 molecules dissolve at the hydrophobic interface in the thick bilayer of the Si25C3EO51.6 L(alpha) phase occupying a large area of the total interface of the aggregates and modulate the curvature of the aggregates. Hence a variety of self-assembled structures are observed. In contrast, Si25C3EO51.6 is not dissolved in the thin bilayer of the C12EO5 lamellar phase (L'(alpha)). Hence, the C12EO5 L'(alpha) phase coexists with copolymer-rich L(alpha) and H2 phases. Consequently, small surfactant molecules are dissolved in a large silicone copolymer aggregate to induce a change in layer curvature, but a large copolymer molecule is hard to incorporate with surfactant aggregates.     

Small-angle X-ray scattering (SAXS) study on nonionic fluorinated micelles in aqueous system

We have investigated the self-organization structures of perfluoroalkyl sulfonamide ethoxylate, C(8)F(17)SO(2)N(C(3)H(7))(CH(2)CH(2)O)(10)H, a nonionic fluorinated surfactant in aqueous system by small-angle X-ray scattering (SAXS) technique. Structural modulation of the nonionic fluorinated micelle induced by temperature change, surfactant concentration, and the added fluorinated oils have been systematically studied. The SAXS data were analyzed by the indirect Fourier transformation (IFT), and the generalized indirect Fourier transformation (GIFT) depending on the volume fraction of the surfactant. Various plausible classical model calculations have been performed to confirm the consistency of the GIFT analysis of the SAXS data. Upon successive increase in temperature, the cylindrical micelles formed at lower temperatures undergo a continuous one-dimensional growth and ultimately near the cloud point an indication of flat planar like structural pattern is observed. The evolution in structure of particle near the demixing temperature may be due to onset of attractive interactions. The shape and size of the micelle is apparently unaffected by changing the surfactant concentration from 1 to 5 wt% at 25 degrees C. Nevertheless, addition of small amount of perfluoropolyether (PFPE) oil, of structure F(CF(2)CF(2)CF(2)O)(n)CF(2)CF(2)COOH (n approximately 21) modulate the micellar shape and size. Long cylindrical micelles eventually transform into globular like particles. The onset cylinder-to-sphere transition in the structure of micelles in the surfactant/water/oil system is probably due to amphiphilic nature of the oil, which tends to increase the spontaneous curvature. The lipophilic part of the oil tends to reside in the micellar core, whereas, the hydrophilic part goes close to the polar head group of the surfactant so that effective cross-sectional area per surfactant molecules increases and as a result spherical micelles tend to form. Perfluorodecalin (PFD) also decreases size of the micelles but its effect is poor compared to the PFPE oil.     

Structures in a microemulsion system of an ethoxylated polymethylsiloxane surfactant, water, and oil studied by NMR self-diffusion measurements

Microemulsion samples of an ethoxylated polymethylsiloxane surfactant, water, and 1-dodecanol or 1-decanol as the oil component are investigated using pulsed field gradient NMR to determine the components' self-diffusion coefficients. It is demonstrated that the structure of the liquids depends heavily on their composition, in that, for low water content, the structure is water-in-oil (w/o), gradually changing to a bicontinous structure in a concentration range ca. 40-60 wt % water, and, finally, to an oil-in-water (o/w) structure for more water rich samples. In the water poor samples, the surfactant molecules apparently do not form extended aggregates (inverted micelles). In the water rich samples, the surfactant and oil (if present) form ordinary micelles, and it is demonstrated for the binary water/surfactant system that the micelles are spherical at very low surfactant concentrations and grow into oblate (disk) shaped aggregates at surfactant concentrations above ca. 5 wt %. From density and viscosity measurements of binary mixtures of oil (1-decanol) and surfactant, it is demonstrated that these components form solutions that are not far from ideal.     

Incomplete phase inversion W/O/W emulsion and formation mechanism from an interfacial perspective

Water-in-oil-in-water (W/O/W) double emulsion can be prepared by incomplete phase inversion method using both medium chain triglycerides (MCT) and isopropyl myristate (IPM) as oil phase, Span 85-Tween 80 (HLB values of 2.5-3.0) as mixed emulsifiers. The preparation method was simple, and the final double emulsions were proved of good microstructure and particle size distribution. Owning to the addition of Tween 80 to Span 85, interfacial tension, interfacial viscosity and modulus decreased, which contributed to the phase inversion. Furthermore, formation of reverse micelles under high-speed dispersion may be a hypothesis to explain the incomplete phase inversion phenomenon.     

Phase behavior of DOPE/TritonX100 (reduced) in dilute aqueous solution: aggregate structure and pH-dependence

The phase behavior of dilute mixtures of dioleoylphosphatidylethanolamine (DOPE) and reduced TritonX100 (TX100(r)) has been investigated at pH 7.4 and 10. Using simple turbidity measurements and optical observations, together with cryo-transmission electron microscopy (cryo-TEM), we estimate the phase boundaries. We show that at both pH 7.4 and 10, a very large amount of surfactant is needed for the onset of micelle formation (X(TX100(r)) approximately 0.60-0.70) as well as for a complete solubilization of DOPE into mixed micelles (X(TX100(r)) > 0.94). We find that the micelles that are formed at high TX100(r) concentrations are of spherical shape. Increasing the pH from 7.4 to 10 has a comparably small effect on the transition from a lamellar (Lalpha) to a micellar (L1) phase. However, the reversed hexagonal phase (H(II)) that is present at low surfactant content at pH 7.4 is absent at pH 10. This is due to the partial negative charge of DOPE at pH 10. We determine the fraction of charged DOPE (alpha = 0.34) at pH 10 in a 150 mM NaCl buffer using zeta-potential (zeta-potential) measurements in combination with a Poisson-Boltzmann (PB) model. The intrinsic pK(a) of the primary amino group of DOPE, in a pure DOPE membrane, is estimated to 9.15 +/- 0.2.     

Phase diagrams and microstructure of aggregates in mixed ionic surfactant/foam booster systems

The phase behavior and microstructure of surfactant systems containing a new alkanolamide-type foam booster, dodecanoyl N-methyl ethanolamide (NMEA-12), were investigated by means of phase study and small angle X-ray scattering. Different from other similar alkanolamides, NMEA-12 possesses a low melting point and forms a lyotropic liquid-crystalline phase (L(alpha) phase) at room temperature. This is attributed to the attached methyl group, which increases the fluidity of the molecule. In the SDS/NMEA-12/water system, hexagonal and lamellar (L(alpha)) liquid-crystalline phases are obtained at significantly low surfactant concentrations. The stability of these phases decreases when SDS is replaced with a nonionic surfactant (C12EO8). However, for both ionic and nonionic surfactants, the effective area per surfactant molecule at the interface shrinks upon addition of NMEA-12, indicating that the surfactant layer is getting more compact. The possible implications of these results on the potential applications of NMEA-12 as foam stabilizer are discussed.     

Destruction of perfluoroalkyl surfactant aggregates by beta-cyclodextrin

A water 1H NMRD and 19F NMR spectroscopy study has proved, for the first time, that perfluoroalkyl surfactant micelles can be completely destroyed upon addition of beta-cyclodextrin to form successively 1:1 and 2:1 (beta-CD:R(F)) inclusion complexes.     

Nanoemulsification in the vicinity of phase inversion: Disruption of bicontinuous structures in oil/surfactant/water systems

Oil/surfactant/water systems may undergo phase inversion upon tuning the preferred curvature of the surfactant layer. The longstanding relationship between nanoemulsification and phase inversion is discussed in view of recent mechanistic advances. The name “phase inversion emulsification” is shown to result from a historical confusion. Both nanoemulsification and phase inversion are controlled by the properties of the surfactant layer but phase inversion is shown to be unnecessary to obtain nanoemulsions. Nanoemulsions can be obtained in the vicinity of phase inversion through the disruption of equilibrium bicontinuous networks. A first pathway involves a change of the interaction between the surfactant layer and water at a precise location in the parameter space and under shear. A non-equilibrium micellar solubilization of oil, named superswelling, leads to an ideal nanoemulsion after quenching. All the surfactant is used to cover the interfaces and none is wasted in the continuous phase. The sub-PIT (Phase Inversion Temperature) method falls within this category. A second pathway involves the addition of water to a water-deprived system. Oil phase separates within a bicontinuous sponge phase matrix at a precise location in the parameter space and leads to a nanoemulsion upon further addition of water. Larger droplets are obtained and some surfactant is wasted, which demonstrates that this pathway is different and less efficient, although easier to implement. It is shown that the identification of the two access states in the nanoemulsification pathways, the superswollen microemulsion and the separating sponge phase, is essential when using surfactant blends. On the contrary, phase inversion is not only irrelevant but also damaging to the success of the emulsification process.