Phase transitions of monoglyceride emulsifier systems and pearlescent effects in cosmetic creams studied by C NMR spectroscopy and DSC

The present work investigates the phase transitions of monoglyceride emulsifier systems and pearlescent effects in cosmetic creams using ¹³C-NMR spectroscopy and DSC. The four phases of monoglyceride emulsifier systems – the coagel, gel phase, liquid-crystalline lamellar phase, and cubic phase – can be characterized in creams at appropriate temperatures by NMR spectroscopy. The phase transition temperatures were determined by DSC. Cross polarization (¹³C-CP)-magic angle spinning (MAS) measurements confirmed that the formation of the coagel is responsible for the pearlescence of creams. It could be shown that the proportions of monoglyceryl laurate and monoglyceryl myristate in the emulsifier system influence the phase transitions and the intensity of the pearlescence of creams. Furthermore, the coagel forms directly from the liquid-crystalline lamellar phase without transition through the gel phase if the cream is at a temperature higher than that of gel phase formation. These insights into the monoglyceride-emulsifier system of creams make it possible to more closely study the pearlescent effect of the coagel. Especially, the amount of emulsifier system in the coagel can be quantified. It could be shown that for a typical pearlescent cream more than 27% of the emulsifier system must be found in the coagel in order for pearlescence to be detectable optically. Moreover, the increase in the intensity of pearlescence over time after fabrication of a cream correlated with the increase in the amount of emulsifier system in the coagel. This ripening process can take up to approximately 15 months.     

芘为荧光探针研究SDS/H2O二元体系的热相变

以芘作为荧光探针, 对十二烷基硫酸钠(SDS)40 g%的水溶液在-20 ℃～30 ℃温区的相变进行了研究。该二元体系的主要相变是凝聚胶-液晶的转变, 测定其相变温度为20 ℃。自由水形成的冰层在0 ℃融化, 由此导致在化冰前后体系呈现出不同的凝聚胶相。在-17 ℃退火处理, 体系出现了新的凝聚胶相。以上出现的各相均可由I_E/I_M值清楚地表征, 从而首次证实了这种探针方法为一种成功的膜模拟体系相变的研究手段。     

Phase transitions and microstructure of emulsion systems prepared with acylglycerols/zinc stearate emulsifier

The emulsification processes, during which acylglycerols/zinc stearate emulsifier, water, and oil phase formed ternary systems, such as water-in-oil (W/O) emulsions, oil-in-water (O/W) dispersions, and unstable oil-water mixtures, were investigated in order to characterize the progressive transformations of the dispersed systems. The type, structure, and phase transitions of the systems were found to be determined by temperature and water phase content. Crystallization of the emulsifier caused the destabilization and subsequent phase inversion of the emulsions studied, at a temperature of 60-61 degrees C. The observed destabilization was temporary and led, at lower temperature, to W/O emulsions, "O/W + O" systems, or O/W dispersions, depending on the water content. Simultaneous emulsification and cooling of 20-50 wt % water systems resulted in the formation of stable W/O emulsions that contained a number of large water droplets with dispersed oil globules inside them ("W/O + O/W/O"). In water-rich systems (60-80 wt % of water), crystallization of the emulsifier was found to influence the formation of crystalline vesicle structures that coexisted, in the external water phase, with globules of crystallized oil phase. Results of calorimetric, rheological, and light scattering experiments, for the O/W dispersions obtained, indicate the possible transition of a monostearoylglycerol-based alpha-crystalline gel phase to a coagel state, in these multicomponent systems.     

Enantiomeric segregation in the gel phase of lipid bilayers

Enantiospecific interactions within a monoglyceride lipid bilayer are investigated using molecular dynamics simulations. Preferential homochiral interactions are observed in the gel phase, whereas no detectable enantiospecificity is seen in the liquid-crystal phase. On the basis of these results and available experimental data, a mechanism is proposed for the formation of the coagel phase of monoglycerides. Enantiomeric segregation in the gel phase is also discussed in terms of its possible implications for prebiological evolution and membrane raft function.     

Temperature scanning ultrasonic velocity study of complex thermal transformations in solid lipid nanoparticles

The purpose of this study was to determine whether temperature scanning ultrasonic velocity measurements could be used to monitor the complex thermal transitions that occur during the crystallization and melting of triglyceride solid lipid nanoparticles (SLNs). Ultrasonic velocity ( u) measurements were compared with differential scanning calorimetry (DSC) measurements on tripalmitin emulsions that were cooled (from 75 to 5 degrees C) and then heated (from 5 to 75 degrees C) at 0.3 degrees C min (-1). There was an excellent correspondence between the thermal transitions observed in deltaDelta u/delta T versus temperature curves determined by ultrasound and heat flow versus temperature curves determined by DSC. In particular, both techniques were sensitive to the complex melting behavior of the solidified tripalmitin, which was attributed to the dependence of the melting point of the SLNs on particle size. These studies suggest that temperature scanning ultrasonic velocity measurements may prove to be a useful alternative to conventional DSC techniques for monitoring phase transitions in colloidal systems.     

Analysis of the phase diagram and microstructural transitions in phospholipid microemulsion systems using high-resolution ultrasonic spectroscopy

In the present work, high-resolution ultrasonic spectroscopy was applied to analyze a pseudoternary phase diagram for mixtures consisting of water/isopropyl myristate/Epikuron 200 and a cosurfactant (n-propanol). Changes in the ultrasonic velocity and attenuation in the megahertz frequency range were measured in the course of titration of the oil/surfactant/cosurfactant mixture with water at 25 degrees C. The ultrasonic titration profiles showed several phase transitions in the samples, which allowed the construction of an "ultrasonic" phase diagram. Quantitative analysis of the ultrasonic parameters enabled the characterization of various phases (swollen micelles, microemulsion, coarse emulsion, and pseudo-bicontinuous) as well as the evaluation of the state of the water and the particle size. The particle size obtained for the microemulsion region ranged from 5 to 14 nm over the measured concentrations of water/isopropyl myristate/Epikuron 200 and n-propanol, which agreed well with the previous literature data.     

Temperature-induced phase separation in pseudoternary mixtures of Triton X-100–butanol–kerosene–water

The transparent Winsor IV domain in the phase diagram of the mixtures of emulsifier (Triton X-100 and butanol), oil (kerosene), and water is found to be 34% of the total phase diagram in presence of emulsifier with surfactant:cosurfactant::1:1, and is water dominant. Increase in cosurfactant/surfactant ratio inverts the Winsor IV domain to become oil rich. The plot of conductance of the microemulsions prepared by substituting water by brine against water content depicts the existence of three distinct phases like oil-in-water, bicontinuous, and water-in-oil microemulsion in the phase diagram. The phase contrast micrographs of the mixtures of different compositions in these three different phases reveal the existence of microdroplets of oil dispersed in water and water dispersed in oil. Further, the dynamic light scattering studies of these solutions reveal an inhomogeneity in the size distribution of the droplets. A temperature-induced clouding in the microemulsion domain leading to phase separation has been observed. Additives like glucose, sucrose, and sodium chloride decrease the cloud point (CP), while addition of ammonium thiocyanate increases it. A quantitative relationship of the clouding temperature with the composition of the microemulsion has been established. With increase in oil and emulsifier, the cloud point of the microemulsion increases. The separated phases after the clouding have been used for preconcentration of water-soluble metal ions as well as oil-soluble dyes. The turbid systems on heating led to separation into three isotropic phases which are found to be stable at ambient temperature. The stability of these phases is ascribed to the formation of stable microemulsions by mass transfer from one phase to other.     

X-ray investigation of the role of the mixed emulsifier in the structure formation in o/w creams

The aim of this research work was to clarify the role of the mixed emulsifier in the structure formation and water binding mode in the case of o/w creams prepared with different surfactants. The swelling behavior of mixed emulsifiers was examined by means of direct investigation methods such as transmission electron microscopy (TEM) and X-ray diffraction. The detailed structure image of the creams was created with the help of the latter. The influence of the structure of the hydrophilic gel phase, and the structural changes during storage were studied with rheological methods. On the basis of the results, it can be stated that the investigated creams had different structures from those mentioned in the literature: surfactant did not create a mixed bilayer with the structure to furnish fatty amphiphile; instead, micelles were formed. These results correlated well with the results of the rheological tests.     

Effect of pressure on the thermotropic phase behavior of surfactant assemblies in water

The temperature (T)—pressure (P) phase diagrams of aqueous solutions of a homologous series of cationic surfactants, tetradecyl- (C14TAB), hexadecyl- (C16TAB), and octadecyltrimethylammonium bromide (C18TAB), have been determined by observing the sudden change of the transmittance accompanying the phase transition under high pressure up to 160 MPa. Regarding three kinds of phase transitions which have been previously assigned by the differential scanning calorimetry (DSC) (S. Kaneshina and M. Yamanaka, J. Colloid Interface Sci.131, 493, 1989), all the transition temperatures were linearly elevated by applying pressure. The volume changes associated with the transitions were estimated from the Clapeyron—Clausius equation by using the values of the T—P slopes on the phase diagrams and of the transition entropies taken from the DSC study. A chemical potential vs pressure profile, of which slope reflects the partial molar volume, among the states of surfactant assemblies, i.e., micelle, gel, and coagel, was drawn schematically on the basis of the transition volumes. The phase boundary between the coagel phase and the micellar solution should be the critical solution line of the surfactant, representing the pressure dependence on the Krafft temperature. In the C18TAB-water system, the phase boundary line between the metastable gel and the supercooled micelle had a break point at 45 MPa, suggesting the existence of a new pressure-induced mesophase above 45 MPa. The metastable gel phase of C14TAB disappeared in the pressure range up to 160 MPa.     

Microstructural investigation of monoglyceride-water coagel systems by NMR and CryoSEM

Monoglyceride coagels consist of a network of plate-like crystals and are formed from a swollen gel state (alpha-gel). In order to resolve the transition mechanism, coagels were prepared with monoglycerides that differ in fatty acid composition (monomyristate and palmitate/stearate, respectively). Rheology provided information on kinetics of coagel formation and the strength of the resulting crystal network. From NMR measurements, the surface-to-volume ratio, tortuosity, and dimensionality of the network were obtained. These findings were in line with qualitative and quantitative structural information obtained from CryoSEM. As a model for the behaviour of non-monoglyceride species, the dynamics of (perdeuterated) palmitic acid was monitored in both alpha-gels and coagels. The experimental data support a two-stage mechanism. In the first stage, two-dimensional separation of D- and L-isomers in the monoglyceride bilayers of the alpha-gel occurs. This process depends primarily on lateral diffusion rate of the monoglycerides. Palmitic acid can be accommodated in the alpha-gel bilayer, but in the coagels it is separated into relative mobile and mechanically weak junction zones between the crystal plates. In the second stage of coagel formation, the crystal plates also grow in the third dimension. Both monoglyceride type and concentration determine the kinetics of this process.     

Exploration of high‐resolution ultrasonic spectroscopy as an analytical tool to study demixing and remixing in poly(N‐isopropyl acrylamide)/water solutions

The ultrasonic properties of poly(N‐isopropyl acrylamide) (PNIPAM)/water solutions, determined with high‐resolution ultrasonic spectroscopy (HR‐US), change during demixing and remixing. All HR‐US measurements are discussed with respect to modulated temperature differential scanning calorimetry results. The lower critical solution temperature type of phase behavior, in combination with the glass‐transition/composition curve of PNIPAM/water, determines the evolution of the ultrasonic signals. Three different temperature regions can be distinguished: a homogeneous region and a heterogeneous region, the latter subdivided into zones without and with interference of partial vitrification of the PNIPAM‐rich phase. During phase separation, the ultrasonic velocity decreases because of a change in the hydration structure around the polymer chains, whereas the ultrasonic attenuation increases as aggregation sets in. Isothermal measurements clearly show time dependence for both the velocity and the attenuation. The observed timescales are different and can be related to a changing polymer/water interphase and aggregate formation, respectively. Partial vitrification of the PNIPAM‐rich phase slows the demixing kinetics and especially the remixing kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1283–1295, 2005     

Structural phase transitions in pentacosane C25H52

The pentacosane undergoes a series of structural phase transitions in addition to the melting transition according to an x-ray scattering study. A phenomenological theory is developed to describe the structural phase transitions between different phases observed in pentacosane. We present a detailed analysis of the different phases and analyze the temperature anomalies of the elastic constants and heat capacity. The thermodynamic anomalies on the different phase transitions are described by the coupling between the order parameters and the elastic strains. The theoretical predictions are found to be in good qualitative agreement with experimental results.     

Thermal study of the interaction of crystalline surfactant with water; The dioctadecyldimethylammonium chloride-water system

Dioctadecyldimethylammonium chloride (DOAC) was completely dehydrated under high vacuum and at a temperature above its transition temperature (96.7°C) which was first discovered by us. Thermoanalytical studies on DOAC-water systems indicate that two successive phase changes of coagel → gel and gel → liquid crystal appear due to the increasing structural disorders of polar head groups and hydrocarbon chains, respectively. Furthermore, it is revealed that three types of water exist, i.e., bound, intermediate and free. On the basis of a bilayer-lamellar structure model, a predominant role of the intermediate water in these transitions is pointed out.     

八甲基环四硅氧烷正离子细乳液开环聚合动力学

以十二烷基苯磺酸钠(SDBS)为乳化剂,硫酸或盐酸为催化剂,八甲基环四硅氧烷(D4)为单体,十六烷为共稳定剂,超声预乳化,制备了聚硅氧烷细乳液,研究了超声时间、催化剂用量、乳化剂用量和温度对聚合动力学的影响.结果表明,在一定酸度范围内,聚合速度与硫酸浓度0.81次方、与盐酸浓度1.02次方、与乳化剂浓度-0.66次方成正比,反应的表观活化能为40.56kJ/mol.     

Impact of Various Parameters Over the Stability of Water-in-Vegetable Oil Emulsion

Theory regarding emulsification, its coalescence and impact of emulsifier over its stability has been updated. For the verification of the proposed theory, water-in-oil emulsion was prepared by mixing water and soybean oil in the presence and absence of emulsifier, monoglyceride. The effect of different parameters like emulsification time, contents of water, and concentration of emulsifier has been investigated on the emulsification and coalescence process of the emulsion. It was noted that the emulsion quality was highest if the mixture was homogenized for about 15 minutes and the water contents were 40% v/v. The addition of monoglyceride up to 0.5% w/v gave the most stable emulsion having higher quality than other composition. The results obtained were compared with the proposed theory and found to have good compositions.      

Sn-containing liquid crystalline side group homopolymers with two glass transitions

Three homologous tin-containing homopolymers with a terminal CN-dipole in the side group have been synthesized and characterized by dynamical calorimetry, polarization microscopy, X-ray and dielectric methods. AFM was used to evaluate the texture at room temperature. Four different phase transitions were detected by DSC. The high temperature phases were identified by polarization microscopy as SmA and SmC. AFM-measurements show focal-conic domains at room temperature and confirm so the smectic nature of all phases. X-ray measurements on nonoriented samples give hints to a phase segregation on nanometer scale. Dielectric investigation and temperature-modulated DSC (TMDSC) confirm clearly phase separation by appearance of two glass transitions related to the liquid order of the main chains and the liquid crystalline of the side groups.     

High temperature structures and orientational disorder in compressed solid nitrogen

An experimental study of the phase transitions at high temperature in compressed solid nitrogen has been performed using Raman spectroscopy. Knowledge of the equilibrium phase diagram in the region of the ordered epsilon phase and the two disordered delta and deltaloc phases, at pressures between 10 and 20 GPa, has been extended up to 500 K. The Raman scattering line shape and line width of the active vibrons has been measured accurately, along isobaric scans, across the phase transitions. Analysis of the width and of its different behavior with increasing temperature in the three phases led to more precise conclusions about the nature of the disorder in the different phases. Observation of an evident shoulder in the nu2 band of the deltaloc phase suggests the possibility that sites of two different symmetries may be occupied by the disk molecules in this structure.     

Ultrasound Emulsification—An Overview

Fundamentals and applications of ultrasound emulsification are reviewed. The importance of cavitation is stressed, as also is power input to the multiphase fluid. The influence of surfactants, polymeric stabilizers, temperature, pressure, and ultrasonic parameters such as frequency, residence time, acoustic intensity, and energy density are described. The effects of other physicochemical parameters such as emulsifier concentration, disperse phase volume fraction, and viscosity are discussed. Applications to both water-in-oil and oil-in-water emulsions are discussed.     

Raman scattering spectra of sodium n-butyl(n-hexyl) phosphate aggregates and conformation about the phosphodiester PO bonds in coagel phases

A new double-chain surfactant molecule, sodium n-butyl(n-hexyl)phosphate (BHP), having an asymmetric molecular structure, has been synthesized. For anhydrous BHP in the solid state and the BHP---H₂O system in the lyotropic liquid crystalline and coagel states, the Raman scattering spectra arising from the accordion vibrational mode were studied in the temperature range −170 to 25°C. For anhydrous BHP, the GG form about the phosphodiester P---O bonds was preferentially stabilized at lower temperature. In the coagel phase of the BHP---H₂O system, preferential stabilization of a specific conformation about the P---O bonds occurred and which molecular form was stabilized was dependent on the water content: for the 8:2 BHP---H₂O sample in the coagel the GT form was stabilized, while for the 7:3 BHP---H₂O coagel sample the TT form was preferentially stabilized. The stabilization of such a specific conformation was also reflected in the higher-frequency region.     

Quinaldine: Accessing two crystalline polymorphs via the supercooled liquid

Quinaldine (2-methyl quinoline) is a liquid at room temperature, which can be supercooled to reach finally the glassy state. By heating the glass above the glass transition temperature T(g) = 180 K the sample performs two subsequent transitions into, likewise, dielectrically active phases. Thus, the reorientational relaxations of these phases as well as the kinetics of the phase transitions can be tracked in a highly resolved way by dielectric spectroscopy. X-ray diffraction analysis clearly shows two structurally different crystalline phases in addition to the supercooled liquid. Calorimetric measurements support the notion of first order phase transitions, occurring irreversibly in the supercooled regime, and suggest that the intermediate crystalline phase is metastable, too. Analyzing the quite distinct dielectric relaxation strengths, we discuss the possible nature of the two crystalline phases. Additionally, a very similar behavior to quinaldine is observed for 3-methyl quinoline, indicating a broad field of polymorphism among the quinoline derivatives.