Interfacial rheology of protein–surfactant mixtures

The distribution of proteins and surfactants at fluid interfaces (air–water and oil–water) is determined by the competitive adsorption between the two types of emulsifiers and by the nature of the protein–surfactant interactions, both at the interface and in the bulk phase, with a pronounced impact on the interfacial rheological properties of these systems. Therefore, the interfacial rheology is of practical importance for food dispersion (emulsion or foam) formulation, texture, and stability. In this review, the existence of protein–surfactant interactions, the mechanical behaviour and/or the composition of emulsifiers at the interface are indirectly determined by interfacial rheology of the mixed films. The effect on the interfacial rheology of protein–surfactant mixed films of the protein, the surfactant, the interface and bulk compositions, the method of formation of the interfacial film, the interactions between film forming components, and the displacement of protein by surfactant have been analysed. The last section tries to understand the role of interfacial rheology of protein–surfactant mixed films on food dispersion formation and stability. The emphasis of the present review is on the interfacial dilatational rheology.     

Are the mixtures of homologous surfactants ideal?

The interaction between homologous surfactants in mixed micelles was studied by the Regular Solution Theory of mixed micelles. The interaction is independent of the nature of the polar head groups and attractive and the interaction parameter betaM depends linearly on the difference in chain length DeltanC. The interaction becomes ideal at DeltanC=0.75+/-0.06. Above DeltanC approximately 5, the dependence remains linear but the slope increased 2.7 times. The phenomenon is explained as the effect of the reduction of the hydrocarbon/water micelle interface and a better packing of the chains in the micelle core, caused by the inclusion of a shorter homologous surfactants. This reduction can be more effective when DeltanC>or=5.     

Solid–liquid phase diagrams of binary mixtures

This study investigates the sorption of toluene and naphthalene by a sodium bentonite (BFN), an organoclay (WS35) and by their respective iron oxide hydrate composites Mag_BFN and Mag_S35. The organic matter content of WS35 and Mag_S35, determined by thermogravimetry, was used to obtain their organic matter sorption coefficients, which show that they are effective sorbents to remove organic contaminants from water, with a higher selectivity for naphthalene than for toluene sorption. The main iron oxide phase present in Mag_BFN and Mag_S35 is maghemite (γ-Fe₂O₃), which allows these sorbents to be separated from the effluent by a magnetic separation process after use.     

Thermal studies of sodium tetrahydroborate–potassium tetrafluoroborate mixtures

The results of DSC studies of NaBH₄–KBF₄ mixtures are presented. It is shown by chemical analysis, XRD analysis, IR spectroscopy, and ¹¹B and ⁹F MAS NMR that the decomposition of the mixtures starts at ~563 K to yield polyhedral borohydride compounds (predominantly B₁₂H₁₂^2-) in the solid residue. This temperature is much lower than the decomposition temperature of pure NaBH₄ (749 K). The mechanism of formation of the B₁₂H₁₂^2- anion has been proposed and confirmed. According to this mechanism, boron atoms from KBF₄ are involved in the formation of this anion.     

Non-Lorentz–Berthelot Lennard-Jones mixtures: A systematic study

Binary mixtures of two identical Lennard-Jones fluids with non-Lorentz–Berthelot combining rules have been simulated over the entire concentration range at three state points in order to examine the effect of cross interactions on the mixing properties, excess volumes and enthalpies, and partial molar volumes, and on the structure. Various combinations of deviations, in both the energy and size cross parameters, from the Lorentz–Berthelot rule, have been considered and the results analyzed using a recently proposed method based on the Tikhonov regularization. It is found that the most important is the size cross parameter and that by varying the combining rules a variety of qualitatively different behavior can be produced including, e.g., a minimum in the partial molar volumes observed otherwise only in complex mixtures of associating fluids; occurrence of this minimum seems to be associated with changes in the second coordination shell as witnessed by the pair correlation function.     

Thermal studies of potassium tetrahydroborate−sodium tetrafluoroborate mixtures

The KBH₄?NaBF₄ mixture was studied by thermal analysis (differential scanning calorimetry). Chemical analysis, X-ray powder diffraction analysis, IR spectroscopy, and ¹¹B and ¹⁹F MAS NMR spectroscopy showed that the primary stage of the complex pyrolysis process is a metathesis reaction between components to form a new mixture, NaBH₄?KBF₄, the decomposition of which with the release of gaseous products and the formation of polyhedral borohydride compounds (mainly B₁₂H₁₂ ^2-) in the solid residue begins at a temperature of about 563 K. At a certain ratio between reactants in the initial mixture KBH₄?NaBF₄, the B₁₂H₁₂ ^2- anion can form with the material participation of the BF₄ ^- anion.     

Cloud point phenomenon in aqueous mixtures of cationic-anionic surfactants

It used to be held that the cloud point phenomenon was only a characteris-tic of nonionic surfactants alone. Such phenomenon is rarely observed in ionicsurfactants. The present study shows that the mixture of cationic-anionic surfac-tants not only has a krafft point which is the characteristic of an ionic surfactant,but also exhibits the cloud point phenomenon obviously at certain concentrations.     

A dielectric study of 1-alcohol — tetraethyl orthosilicate mixtures

Dielectric properties of mixtures of 1-alcohols (ethanol, 1-butanol and 1-hexanol) and tetraethyl orthosilicate (TEOS) were determined by means of the time domain method (TDS). To all spectra were fitted a model function containing a sum of three debye relaxation terms with fixed ₂ and ₃. Initially, to 2–3 mole%, TEOS did not influence static permittivity nor main relaxation time of the alcohol. For higher concentrations there is a linear decrease in both these parameters. Qualitatively the effects of TEOS are comparable with those of a nonpolar hydrocarbon on the alcohol structure.     

Path dependence of surface–tension scaling in binary mixtures

A mean-field free-energy functional for an n-component mixture with an integral non-local interaction is introduced and then written explicitly for a binary mixture. We use this functional to calculate the liquid–vapor surface tension with parameters chosen to model CO₂/n–C₄H₁₀ and CO₂/n–C₁₀H₂₂, and we examine the scaling of the surface tension as a function of the difference in density between the liquid and vapor phases as various critical points are approached. Each critical point is approached on either a constant-temperature or constant-pressure path; we investigate the path dependence of the scaling behavior. For the constant-temperature paths in the CO₂/n–C₄H₁₀ mixture, we compare our calculated results with experimental data. We find no significant dependence of the scaling on the path to the critical point. We note that the asymptotic scaling holds for a larger range of densities the higher the temperature of the critical point.     

Acid-base and complexation properties of α-L-alanin in water-formamide mixtures

The constants of copper (II) complexation with α-L-alanine in water and water-formamide solvents were determined potentiometrically at 298 K; the dissociation constants for alanine amino group was also determined. It was found that the stability of the [CuAla]⁺ complex is significantly reduced with an increase in the formamide content in solution. The heat balance of the Cu²⁺-alanine-water-formamide system was considered for the process of Cu(NO₃)₂ transfer from water to an aqueous solution of alanine using the earlier determined K _stab and thermochemical data.     

Aqueous sodium oleate–sodium dehydrocholate mixtures at low concentration

The aqueous mixed system sodium dehydrocholate (NaDHC)–sodium oleate (NaOL) was studied by several methods to determine the influence of the hydrophobic structure of both surfactants in the mixed micellization and the formation of the mixed monolayer adsorbed at the air–water interface. The molecular area at the critical micelle concentration in pure surfactant solutions suggests that the adsorbed oleate chain was folded to allow the double bond in the middle of the molecule to remain in contact with water, and that the NaDHC molecule was situated with its plane laying parallel to the water surface, allowing the three carbonyl groups in the hydrocarbon backbone to form hydrogen bonds with water. The interaction was repulsive at the surface, and in the mixed monolayer some molecules must move away the less hydrophilic groups from water (double bond of NaOL, carbonyl groups of NaDHC). The interaction in mixed micelles was strongly attractive, showing a preferential composition roughly equimolar. The hydrolysis in mixed micelles was augmented in comparison with pure surfactants systems, which could be explained by assuming the existence of a more hydrophobic mixed micelle core. The mixed micelle degree of ionization was below that of the pure micelles, thus indicating a high surface charge density.     

Room temperature ionic liquids and their mixtures—a review

Room temperature ionic liquids are salts that are liquid at room temperature and their use as catalysts and catalytic support has been studied extensively. They are also being considered as “green solvents” for various separation processes. Recent measurements reported on the properties of pure ionic liquids and their mixtures, including gas and liquid solubility in common organic solvents will be reviewed. While some property values are in good agreement, some show large differences. These values will be compared and reasons for the discrepancies will be conjectured. Since traditional approaches to predicting the properties of fluid liquids require extensive LLE and VLE measurements, alternative predictive methods need to be explored. The predictions of the properties of mixtures of ionic liquids using COSMOtherm, an approach based on unimolecular quantum chemical calculations of the individual molecules, will be presented.     

FT-IR studies of molecular interactions in formamide–methanol mixtures

FT-IR spectra of formamide (FA)–methanol (MeOH) mixtures have been measured by ATR technique. Factor analysis applied to the spectra has shown two kinds of intermolecular complexes differing in a manner of polarization of component molecules. The composition of the complexes changes monotonically with the composition of the mixtures. The spectra in the CO stretching region have been analyzed separately using both: the factor analysis and the difference spectra method. Four different environments of carbonyl group of formamide has been revealed over the whole range of the mixture composition. The mean number of formamide molecules disturbed by one methanol molecule via carbonyl group in the formamide-rich region has been found as equal to 1.5. Presumable structures for the molecular complexes have been proposed to explain the results of the analyses.     

Molecular dynamics of ��-CD in water/co-solvent mixtures

Molecular dynamics (MD) simulations on ??-cyclodextrin (??-CD) in water, ethanol (EtOH), methanol (MeOH) and mixtures of these solvents have been carried out at 300 K over a time period of 15 ns using the AMBER force field. The hydrated X-ray crystallographic structure has four water molecules inside the cavity, defined by a more precise boundary for the ??-CD cavity. From the simulations, 2?C4 encapsulated water molecules are most probably found. In an ethanol co-solvent system, the ??-CD cavity is occupied with one ethanol molecule located in two discrete sites: below and above the O4(n) plane, which is in agreement with experimental results. In all systems, the average values of tilt angles of the obtained structures are higher than the tilt angles of the X-ray structures. The investigations of the alcohol orientations in co-solvent mixtures reveal the hydrophobic environment of the cavity and the hydrophilic atmosphere at both rims of ??-CD.     

Phase separation in mixtures of thermotropic liquid crystals and flexible polymers

The spinodal equation and the concentration-induced anisotropic-isotropic transition equation of the mixtures of thermotropic liquid crystals and flexible polymers have been studied by using the molecular field theory The calculations of the phase diagrams of this system show that,besides the isotropic classic spinodal curve,there ex ists an anisotropic spinodal curve which has not been reported in literature.These two spinodal curves can be linked up by the concentration-induced anisotropic-isotropic transition line.In the various phase regions,demixing may take place due to different phase separation mechanisms.The phase equilibrium curve cannot always join the.spinodal curve at a critical point.These results are considered very meaningful for the understanding of the special properties of liquid crystal/polymer composites and very useful for controlling the morphology and the performance of PDLC materials     

Phase behavior of tetradecane–hexadecane mixtures confined in SBA-15

Phase behavior of tetradecane–hexadecane mixtures (n-C₁₄H₃₀–C₁₆H₃₄, C₁₄–C₁₆) confined in SBA-15 (pore diameters 3.8, 7.8, and 17.2 nm) has been studied by differential scanning calorimetry. Phase diagram of the confined C₁₄–C₁₆ mixtures is greatly influenced by the pore size, which is simple compared with that for the bulk. Melting points of C₁₄ and C₁₆ confined in SBA-15 display a linear relation with pore size. Meanwhile, the C₁₄–C₁₆ mixtures have shown a similar melting behavior as pure C₁₄ and C₁₆. Melting temperatures of three C₁₄–C₁₆/SBA-15 systems have been fitted as a function of mole fraction x _C16.     

Polymers imprinted with PAH mixtures—comparing fluorescence and QCM sensors

Molecular imprinting with binary mixtures of different polycyclic aromatic hydrocarbons (PAH) is a tool for design of chemically highly sensitive layers for detection of these analytes. Sensor responses increase by one order of magnitude compared with layers imprinted with one type of template. Detection limits, e.g. for pyrene, reach down to 30 ng L(-1) in water, as could be observed with a naphthalene and pyrene-imprinted polyurethane. Comparing sensor characteristics obtained by QCM and fluorescence reveals different saturation behaviours indicating that, first, single PAH molecules occupy the interaction centres followed by gradual excimer incorporation at higher concentrations finally leading to substantial quenching, when all accessible cavities are occupied. The plateau in the mass-sensitive measurements suggests that up to 80% of the cavities generated in the MIP are re-occupied. Displacement measurements between chrysene and pyrene revealed that for imprinted layers with very high pyrene sensitivities the signals of both PAH are additive, whereas in materials with lower pyrene uptake the two analytes replace each other in the interaction sites of the polymer.     

Micellisation thermodynamics of sodium lauroylsarcosinate in water–alcohol binary mixtures

Aggregation of sodium lauroylsarcosinate (SLS) in aqueous solutions of methanol, ethanol, propanol and ethylene glycol at 288–313 K has been determined from conductivity measurement in the range 0–20% v/v of additives. The precise values of the critical micelle concentration (CMC) and the degree of counter-ion dissociation of micelles were obtained at each temperature by fitting the specific conductivity-surfactant concentration curve to the integrated form of the Boltzmann-sigmoid equation. The CMC was found to increase with increase in additive concentrations in the case of methanol and ethylene glycol, while it decreases with increase in ethanol and propanol concentration. The equilibrium model of micelle formation was applied to obtain the thermodynamic parameters of micellisation. The Gibbs free energies were observed to vary only slightly with temperature and additive concentrations. Enthalpy–entropy compensation was observed for all the systems with a constant compensation temperature of ≈300 K and negative compensation enthalpy.     

Gamma-ray absorption using rubber—lead mixtures as radiation protection shields

In the present study five samples of special rubber–lead were fabricated each of them consists of lead and rubber with different weight ratios. The fabrication was carried out through the process of mixing under compression pressure. Gamma-ray transmission method was employed to determine the linear attenuation coefficient for narrow collimated mono-energetic beams of gamma-rays emitted from ²⁴¹Am 0.059, ¹⁵²Eu 0.13 and ¹³⁷Cs 0.662 MeV. The linear attenuation coefficient of standard rubber–lead shield was also experimentally determined. The percentage of lead in standard rubber–lead shield was determined through the calibration curve or by a simple computer program written in MATLAB. All prepared samples are characterized as flexible and gives a good homogeneity. samples no. 4 & 5 offers the best performance as a radiation protection shields. The results showed an inverse proportionality between the linear attenuation coefficient μ_{l and E}, and μ_l has a direct proportionality with mixing ratios (sample density). The results showed an inverse proportional between the half value layers and the average linear attenuation coefficients of the various samples.