Miscibility behavior of ternary lipidphospholipid/water systems

Differential-scanning-calorimetry was applied to study the lyotropic and thermotropic properties of the two ternary systems dimyristoylcephaline (di-(C14:0)-PE)/Palmitic acid (C₁₅COOH)/water (H₂O) and dimyristoylcephaline (di-(C14:0)-PE)/palmitic acid methyl ester (C₁₅COOMe)/water (H₂O) in dispersions with excess water (50 wt.%).The phase diagrams of both systems showed that the two systems differ in their miscibility behavior. The system di-(C14:0)-PE/C₁₅COOH/H₂O is completely miscible in its high-temperature phase. In the low-temperature phase the mixing gap was found within the concentration range of C₁₅COOH and was also indicated by a maximum value of the transition enthalpy of the pseudo-binary mixtures.In the pseudo-binary system di-(C14:0)-PC/C₁₅COOMe/H₂O, the tendency towards demixing is much more pronounced. It was observed that the incorporated C₁₅COOMe melted above its normal melting point, but below the transition temperature of di(C14:0)-PE/H₂O system; therefore, the phase transition started at lower temperature. In the low-temperature phase, both lipids are partially miscible. The demixing range of the phase diagram lies within the concentration region of C₁₅COOMe. Up to the mole fraction ofXC₁₅COOMe=0.43, C₁₅COOMe can be incorporated into theL-phase of the system di-(C14:0)-PE/H₂O.     

Phase diagrams of surfactant/water/synthetic perfume ternary systems

The phase diagrams of hexadecyl polyoxyethylene ether (C₁₆POE₁₀)/water/synthetic perfume, and sodium dodecyl sulfate (SDS)/water/synthetic perfume ternary systems were prepared. The synthetic perfumes used are, d-limonene, -hexylcinnamaldehyde, -ionone, benzyl acetate, linalool, and eugenol. In a series of C₁₆POE₁₀/water/synthetic perfume ternary systems, as the hydrophilicity of synthetic perfume increases, the regions of normal and inverse micellar solution phases were found to be extended, while that of the lamellar liquid crystal phase was reduced. Moreover, every region of normal micellar solutions, inverse micellar solutions, and lamellar liquid crystal phases in SDS/water/synthetic perfume ternary systems was found to be smaller than those in C₁₆POE₁₀/water/synthetic perfume systems.     

Phase behavior of ternary mannosylerythritol lipid/water/oil systems

Due to the great importance of new therapeutic routes for morphine in pain treatment, several investigations are under development. In this way, the design of a liquid system for the oral administration of morphine would be of great help, especially in patients with difficulties in swallowing (children and elderly people). The systems studied in this work are kollidon^® SR microparticles, a biodegradable polymer classically used as excipient in the design of solid dosage forms, as vehicles for morphine. A detailed investigation of the capabilities of the polymer particles to load this drug at their surface is described. Electrophoretic mobility and optical absorbance determinations were used with this aim. The main factors determining the drug incorporation, after incubation of the microparticles in the morphine solutions, were the adsorption time, the type of electrolyte and its concentration, and the drug concentration. The optimum loading conditions were used to perform morphine release evaluations, finding that the release profiles were biphasic since the drug adsorbed was slowly released during 24 h after an initial burst release phase.     

The formation of molecular aggregation structures in ternary system: Aerosol OT/water/iso-octane

Summary The phase equlibrium diagram for the ternary system: Aerosol OT / water / iso-octane is established at 25 °C. In this diagram it is noticed that the reversed micellar solution or microemulsion phase extends in its area so far as the water content reaches 50–60 (wt.%) at which liquid crystalline phase begins to appear. On the experimental data of electric conductivity, viscosity, optical birefringence, etc. for the samples containing a definite amount of AOT (0.28 M), and various relative amounts of water and iso-octane, the mechanism of the transition of reversed micellar structures into lamellar liquid crystalline structures is discussed from the viewpoint of thermodynamics and molecular kinetic theories.

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Zusammenfassung Das Phasendiagramm vom ternären System: Aerosol OT / Wasser / Iso-octan bei 25 °C ist angegeben. In diesem Diagramm ist zu bemerken, daß die Phase der inversen mizellaren Lösung oder Mikroemulsion so weit entwickelt ist, daß ihr Wassergehalt 50–60 (gew.%) erreicht, wobei flüssige Kristalle erscheinen. Auf Grund der experimentellen Daten der elektrischen Leitfähigkeit, Viskosität, optischen Doppelbrechung usw., von den Proben mit dem bestimmten AOT-Gehalt (0,28M) wird der Mechanismus der Umwandlung von inversen mizellaren Strukturen zu lamellaren flüssigen Kristallen aus dem Gesichtspunkt der Thermodynamik und molekularkinetischen Theorie diskutiert.

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With 4 figures and 1 table     

Mesomorphic structures of protonated surfactant-encapsulated polyoxometalate complexes

Keggin-type heteropolyanions, H(3)PW(12)O(40) (HPW), Na(3)PW(12)O(40) (NaPW), H(4)SiW(12)O(40) (HSiW) and K(4)SiW(12)O(40) (KSiW), were encapsulated by a cationic surfactant, di[12-(4'-octyloxy-4-azophenyl)dodecyloxy]dimethylam monium bromide (L), through the replacement of counterions. The resulting surfactant-encapsulated polyoxometalate complexes were characterized by UV-vis, Raman, and NMR spectra in detail. The measurement results indicated that some azobenzene groups of the surfactant were protonated in the complexes HL/HPW (HL is the abbreviation of the protonated surfactant), HL/NaPW, and HL/HSiW during the process of encapsulation, whereas the protonation was not observed in L/KSiW. The thermotropic liquid crystal properties of these complexes were investigated by differential scanning calorimetry, polarized optical microscopy and variable-temperature X-ray diffraction. Interestingly, different smectic mesophases were observed between the protonated HL/HSiW and the non-protonated L/KSiW, which suggests that the protonation of azobenzene groups in HL/HSiW plays a key role in the liquid crystalline organization. However, protonated HL/HPW and HL/NaPW exhibit a similar smectic B phase to that of the de-protonated one, L/HPW. A competitive balance between the phase separation and the volume minimization of surfactants was proposed to explain the self-organized liquid crystal structures of these protonated and non-protonated complexes. To the best of our knowledge, the present investigation provides a specific example for protonated hybrid materials with stable liquid crystal properties.     

Diffusion-controlled formation of porous structures in ternary polymer systems

We propose a theory for the appearance of two-phase structures during the formation of polymer membranes from a casting solution immersed in a coagulant bath. Our model is based on diffusion induced phase separation at the spinodal in the ternary nonsolvent-solvent-polymer system. A simplified treatment of the interdiffusion process by the diffusion layer method permits the formulation of criteria for the formation of two-phase structures in the course of the solvent-coagulant exchange. Our criteria are expressed in terms of the composition dependence of the chemical potentials in the stable and metastable region of the ternary phase diagram. Comparison with experimental results shows qualitative similarities with theoretical predictions.     

Determination of hydrogen ion activities in various ternary water/methanol/dioxane solvent systems

The practical pH values for solutions in ternary water/methanol/dioxane solvents measured by a pH meter standardized with aqueous buffer solutions do not lie on the conventional scale of hydrogen ion activity referred to the standard state in the corresponding medium (pa^*_H). These values can be converted to pa^*_H by the introduction of a correction term δ = $\text{E}\text{?}$_j ? log(_mγ_H) (where $\text{E}\text{?}$_j is a term incorporating the liquid junction potential, which depends on the solvent composition and _mγ_H is the medium effect on hydrogen ion). Values of δ were determined for various ternary solvents at 25°C and were found to be constant in each medium independent of the solute composition.     

Determination of hydrogen ion activity in various binary dimethylformamide/water and ternary dimethylformamide/dioxane/water solvent systems

The practical pH values in dimethylformamide/water and dimethylformamide/dioxane/water solvent mixtures measured by a pH meter standardized against aqueous buffer solutions do not lie on the conventional scale of hydrogen ion activity referred to the standard state in the corresponding medium (pa^*_H). The values can be converted to pa^*_H by introducing a correction term δ. Values of δ were determined at 25°C. Simple interpolation equations are derived to express the variation of δ with solvent composition. In the ternary mixtures, the results show that the composite medium effect, described by a parameter b=dδ/du, (where u depends on the solvent composition), depends on the ratio of the organic solvent concentrations.     

Dielectric relaxation behavior of ternary systems of water/toluene/Triton X-100: the effects of water and oil contents on microemulsion structure

Dielectric relaxation studies were conducted on the ternary systems of the nonionic surfactant Triton X-100 (a nonionic surfactant with a polyoxyethylene chain)/toluene/water in the frequency range from 40 Hz to 110 MHz. The contents of water and toluene were varied separately while the ratios of the other two components were fixed. Remarkable dielectric relaxations were observed around 1 MHz and dielectric intensity shows different variation with the increase of the contents of water or toluene. Dielectric parameters were obtained by fitting the data using the Cole–Cole equation with one dispersion term. The reverse micelles, water-in-oil, and oil-in-water micro-regions of the microemulsions were identified by the dependence of conductivity of the dispersed phase and continuous phase on the contents of water or toluene. Hanai theory and the corresponding analysis method were used to calculate the phase parameters of the constituent phases. The analysis results suggest that the dielectric relaxation probably arises from the interfacial polarization.     

Self-assembly and influence of the organic counterion in the ternary systems dodecylamine/acrylic acid/water and dodecylamine/methacrylic acid/water

Due to complete proton transfer from the acid to the amine, a reaction between an equimolar mixture of dodecylamine and (meth)acrylic acid leads to the formation of dodecylammonium (meth)acrylate. The latter can be considered as a surfactant with a polymerizable organic counterion. The ternary phase diagrams of the two systems dodecylamine/acrylic acid/water and dodecylamine/methacrylic acid/water are described. Both systems can form isotropic solutions and lyotropic liquid crystalline lamellar phases. Moreover, the system with the methacrylate counterion can also form a cubic phase in the water-rich part of the phase diagram. The difference in the self-organization observed for the two systems is explained by the greater bulkiness and hydrophobicity of the methacrylate. Whereas the acrylate counterion behaves rather like a classic inorganic counterion, the methacrylate counterion resides in the outermost part of the aggregates, giving rise to a change in the surface curvature.     

Acid-base equilibria in ternary water/methanol/dioxane solvent systems : Determination of pKa values of some aliphatic monocarboxylic acids

The thermodynamic acidity constants of n-butanoic, n-pentanoic, n-hexanoic, and n-heptanoic acids were determined at 25°C in ternary water/dioxane/methanol mixtures. The results obtained show that the composite medium effect, expressed by a parameter b = dpK′/du (u being a variable expressing the solvent composition), depends on the ratio of the organic co-solvent concentrations. In the ternary mixtures, superposition of the various effects detected in the corresponding binary solvents (water/dioxane and water/methanol) enables simple interpolation formulae to be used to estimate the pK_a values in solution with any ratio of the three solvents.     

Phase diagrams and structures of lecithin/water systems with branched lecithin components

The influence of chain branching on the phase transition parameters and structures of the homologous series of 1-(x-methylpalmitoyl)-2-hexadecyllecithins in the water-saturated two-phase region (50 wt.% water) were studied by differentialscanning-calorimetry as a function of the position x of methyl branching. With increasing x a linear decrease in the enthalpies and alternating temperatures of main transition were observed. The phase diagram of the ternary system 1-(3-methyl-palmitoyl)-2-hexadecyllecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase (L -phase). However, in the low-temperature phase (gel phase), the components are partially miscible only. It follows that gel phases with interdigitated chains and those with tilted chains are not completely miscible. The phase diagram of the ternary system 1,2-di-(8-methylpalmitoyl)-lecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase and low-temperature phase. Within the concentration range between the mole fraction x=0.91 and x=0.97, a drop-like course in the phase diagram was obtained.     

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.     

Towards understanding the nucleation mechanism for multi-component systems: an atomistic simulation of the ternary nucleation of water/n-nonane/1-butanol

Inspired by the previous finding of some unusual vapour/liquid nucleation results on the ternary water/n-nonane/1-butanol system, atomistic simulations were carried out for a detailed investigation of this mixture. These simulations reproduced the experimentally-reported non-ideal nucleation behaviour for this system, including both onset activities and the average compositions of the critical nuclei. Close examination of the nucleation free energy data and the structure of the critical nuclei reveals two types of phase separation. One occurs internally inside the cluster via formation of a multi-layered structure. The other takes place externally, leading to the coexistence of multiple nucleation channels, characterized by critical clusters of different compositions. Such mechanistic and structural heterogeneity is the microscopic origin of the complex nucleation behaviour observed for this ternary mixture.     

Hierarchically structured multifunctional porous interfaces through water templated self-assembly of ternary systems

Herein, a facile water-assisted templating approach, the so-called breath figures method, has been employed to prepare multifunctional and hierarchically structured porous patterned films with order at different length scales (nano- and micrometer). Tetrahydrofuran solutions of ternary blends consisting on high molecular weight polystyrene, an amphiphilic block copolymer, polystyrene-b-poly[poly(ethylene glycol) methyl ether methacrylate] (PS(40)-b-P(PEGMA300)(48)), and a fluorinated copolymer, polystyrene-b-poly(2,3,4,5,6-pentafluorostyrene) (P5FS(21)-b-PS(31)), have been used to obtain films varying the proportion of the three components. Confocal micro-Raman spectroscopy and atomic force microscopy demonstrated the preferential location of the different functionalities in the films. Because of the breath figures mechanism, the amphiphilic copolymer yield pores enriched in hydrophilic functionality while the fluorinated copolymer remained mixed with the PS matrix and eventually also forming self-assembled nanostructures at the surface. As a consequence, two levels of order can be observed, i.e., micrometer size pores with nanostructured domains due to the block copolymer self-assembly. In addition, the distribution of the amphiphilic copolymer within the holes is not regular being located principally on the edges of the cavities. This can be attributed to the coffee stain phenomenon occurring in the water droplets as a consequence of the segregation of the block copolymers to the droplets and their self-assembly.     

Morphologies of three-phase emulsions of the ternary nonionic amphiphile/oil/water systems and their determination by electrical method

Equations have been developed for the electrical and thermal conductivities of dispersions of two different phases of low conductivity in a third, conductive phase. These equations predict the conductivity of the dispersion from the volume fractions and conductivities of the constituent phases. Electrical conductivity measurements on dispersions of three liquid phases, i.e., three-phase emulsions, were made over a wide range of volume fractions of each dispersed phase and used to test the equations. The equations predict accurately dispersion conductivities from the measured volume fractions and conductivities of the constituent phases without any adjustable parameters. The predicted values are in excellent agreement with the measured conductivities of three-phase emulsions in the nonionic amphiphile/oil/water systems. This leads to the determination of three-phase emulsion morphologies. When the ratio Kd of the emulsion-drop conductivity to the continuous phase conductivity is O(10(-1)) 相似文献   

Self-organization of the ternary didecyldimethylammonium bromide/octyl-beta-D-glucopyranoside/water system

The spontaneous and thermodynamically stable mixed vesicles constituted by a double-chain cationic surfactant with 10 carbon atoms hydrophobic tail, didecyldimethylammonium bromide (di-C(10)DMAB), and a nonionic single-chain surfactant, octyl-beta-d-glucopyranoside (OBG), have been characterized in aqueous media by means of a series of experimental techniques, as well as a theoretical approach. Conductivity data allow for the determination of the concentrations at which the monomer-to-vesicle (CVC) and/or vesicle-to-micelle (CMC) transitions occur. Electrophoretic mobilities, obtained from laser-doppler-electrophoresis experiments, permit the determination of zeta-potentials and, from them, the surface charge density of the vesicle aggregates. Cryogenic transmission electron microscopy (cryo-TEM) provides pictures of the vesicles, their size and shape being, thus, determined. Finally, the sensitivity of the emission spectra of some fluorescent probes, such as the cationic TNS and the nonionic PRODAN, to the polarity of the environment, allow for a complete study of different pre- and post-vesicle microdomains, of variable rigidity and micropolarity. This, in turn, yield interesting information about the vesicle surface and bilayer, as well as, about the existence of clusters and/or nanoaggregates prior to the formation of vesicles, as was proposed by us in a previous paper.     

Changes in two-phase emulsion morphology in temperature-amphiphile concentration or fish diagram for ternary amphiphile/oil/water systems

We examined the morphologies of two-phase emulsions in the ternary 2-butoxyethanol/n-decane/water system at various temperatures and water-to-oil ratios (WORs). The two-phase emulsion morphologies depended on temperature, WOR, and amphiphile concentration, and the results are presented in a temperature-amphiphile concentration coordinate system or a "fish" diagram. The observations made in this work contradict the predictions by the phase-inversion-temperature (PIT) concept. At WOR<1, a vertical inversion line was observed at TT(uc) (upper critical endpoint temperature) and at low amphiphile concentrations, only B/T emulsions appeared, irrespective of temperature. At WOR>1, the situation was reversed; T/B emulsions at TT(uc), and T/B emulsions at low amphiphile concentrations, irrespective of temperature. At WOR=1, two horizontal inversion lines, one each at TT(uc), were observed. The morphologies of the two-phase emulsions were B/T or T/B emulsions at low amphiphile concentrations, and at higher amphiphile concentrations T/B at TT(uc). All these findings along with three-phase emulsion data result in complete emulsion morphology diagrams in the temperature-amphiphile concentration space or fish diagram.