Transmembrane potential in vesicles formed by catanionic surfactant mixtures in an aqueous salt solution.

The transmembrane potential plays a key role in a multitude of natural and synthetic systems because it is the driving force for the flow of mobile charged species across the membranes. We develop a molecular thermodynamic theory to study the transmembrane potential of metastable and equilibrium vesicles as a function of the vesicle structural parameters, and salinity and acidity of the surrounding aqueous solution. We show that addition of salt to the external solution may reverse the sign of the transmembrane potential, indicating the reversal of sign of the net charges accumulated in the vesicle interior and exterior. We discuss maxima/minima of the transmembrane potential as a function of added salt and propose a simple formula to estimate the location of these extrema. We demonstrate that a vesicle brought to equilibrium with an acidic environment may take up and hold alkaline solution in its interior. We also show that bending of a symmetrically charged planar membrane leads to a buildup of the transmembrane potential. The catanionic vesicles considered in this work are composed of a series of classical surfactants and model surfactants differing in their molecular structure. These vesicles may serve as a simple prototype for capsules formed by the amphiphilic membranes of a more complex structure, e.g., in nanoreactors or drug-delivery systems.

Thermodynamic properties of gaseous BaSnO2 and Ba2 O2 studied by Knudsen effusion mass spectrometry.

RATIONALE: BaSnO3 is an interesting technical and industrial ceramic, with uses in many areas of electronic technology. Currently, there is great interest in this ceramic material because of its potential as a transparent conductive oxide. Due to its good chemical stability, it is also used as a surface processing material in the synthesis of electroluminophores. When heated, the stannates of alkaline earth metals can pass into the vapor phase with or without dissociation. Until the present investigation, gaseous salts where SnO plays the role of an anion-forming oxide had been unknown. The formation enthalpy of gaseous Ba2 O2 also needed to be determined. METHODS: Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species, equilibrium constants and enthalpies of the studied gas-phase reactions, as well as the formation and atomization enthalpies of gaseous BaSnO2 and Ba2 O2 : a mixture of BaO and SnO2 was evaporated from a platinum effusion cell. For the evaporation of gold (pressure standard), a molybdenum effusion cell was used. A theoretical study of gaseous BaSnO2 and Ba2 O2 was performed by several quantum chemistry methods. RESULTS: Ba, BaO, Ba2 O2 , SnO and BaSnO2 were found to be the main species in the vapor over the BaO-SnO2 mixture in the temperature range of 1680-1920 K. The standard formation enthalpies of gaseous BaSnO2 and Ba2 O2 were determined on the basis of the equilibrium constants of the studied gas-phase reactions. Energetically favorable structures of these gaseous species were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous Ba2 O2 was clarified; in addition, the formation enthalpies of gaseous SrSnO3 and CaSnO3 were estimated. CONCLUSIONS: The thermal stability of gaseous BaSnO2 was confirmed by Knudsen effusion mass spectrometry. The reaction enthalpies of gaseous BaSnO2 from gaseous barium and tin oxides were theoretically evaluated and the obtained values were found to be in reasonable agreement with the experimental ones.

Molecular thermodynamic modeling of a bilayer perforation in mixed catanionic surfactant systems.

Perforated bilayers play an essential role in biology and in surface science. Here, we extend the classical aggregation model of catanionic surfactant mixtures to describe perforations in a self-assembled bilayer in aqueous salt. The model predicts that changing solution salinity and anionic-to-cationic surfactant ratio may lead to the spontaneous formation of pores in the bilayer and to the assembly of a micellar network. We estimate the dimensions of an optimal pore as a function of solution salinity and aggregate composition and show that with an increase of concentration of the deficient surfactant in a catanionic mixture, both the diameter and the thickness of the optimal pore decrease. This decrease is stronger for pores enriched in surfactant having a longer tail than for the pores enriched in the oppositely charged surfactant with a shorter tail. Our model helps to quantify the driving forces for the formation of a pore in a catanionic bilayer and to understand its role. For the aqueous mixtures C16TAB/SOS/NaBr and DTAB/SDS/NaBr, our predictions are in reasonable although not quantitative agreement with available cryo-TEM and SANS data. Predicted radii of perforations are in the range of those obtained from SANS data for perforated bilayer disks.

Driving Force for Spontaneous Perforation of Bilayers Formed by Ionic Amphiphiles in Aqueous Salt.

Spontaneous perforation of amphiphilic membranes is important in both living matter and technology because of an impact on functions of biological membranes and shape transitions of self-assembling structures. Nevertheless, no definite molecular mechanism has been established so far even for simple ionic surfactant systems. We show that spontaneous perforation of a bilayer formed by an ionic amphiphile is driven by electrostatics. Creation of large pores with a concave-convex geometry of the rim is promoted by lower electrostatic free energy than that for a flat nonperforated bilayer. The opposite effect comes from the elasticity of the hydrocarbon tails of the amphiphile that prefer flat geometry of a nonperforated bilayer. The balance between electrostatics and tail deformation controls the appearance of pores; this balance is modulated by added salt that screens the electrostatic interactions. We illustrate the proposed mechanism with the aid of classical aggregation model that has been extended by including an analytical description of the electrostatic contribution for the toroidal rim of a pore. Numerical solution of the linearized Poisson-Boltzmann equation confirms the role of electrostatic forces in formation of pores. For the ionic surfactants of CnTAB family, we predict shape transitions including bilayer perforations and formation of branched micellar networks induced by changing salinity or temperature and demonstrate the effect of surfactant's molecular parameters on these transitions.

Thermodynamic study of gaseous tin molybdates by high-temperature mass spectrometry.

RATIONALE: Molybdenum and tin are components of various construction materials which are often used at high temperature and in an oxidizing atmosphere. Oxides of molybdenum and tin, with their high reactivity, can, in their turn, form a number of gaseous compounds. To predict the possibility of the existence of gaseous associates formed by tin and molybdenum oxides it is important to know their thermodynamic characteristics. Until the present investigation only a few gaseous salts of tin were known. METHODS: High-temperature Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species over the SnO(2) -MoO(3) system. The formation enthalpies of gaseous SnMoO(4), Sn(2) MoO(5) and SnMo(2)O(7) were derived. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using a molybdenum effusion cell containing the samples under study and pure gold as the reference substance. A theoretical study of gaseous tin molybdates was performed by several quantum chemical methods: wave function based explicitly correlated F12 methods and DFT M0(6) methods. RESULTS: In the temperature range of 1200-1400 K, SnO, Sn(2)O(2), SnMoO(4), Sn(2) MoO(5), SnMo(2)O(7), MoO(3), Mo(2)O(6) and Mo(3)O(9) were found to be the main vapor species over the samples studied. On the basis of the equilibrium constants of gaseous reactions, the standard formation enthalpies of gaseous SnMoO(4) (-699 ± 29 kJ/mol), Sn(2) MoO(5) (-1001 ± 38 kJ/mol) and SnMo(2)O(7) (-1456 ± 60 kJ/mol) at 298 K were determined. Energetically favorable structures were found and vibrational frequencies were evaluated in the harmonic approximation. CONCLUSIONS: The stability of gaseous species, SnMoO(4), Sn(2) MoO(5) and SnMo(2)O(7), was confirmed by high-temperature mass spectrometry. A number of gas-phase reactions involving tin-containing gaseous salts were studied. The enthalpies of reactions of gaseous tin molybdates were evaluated theoretically and the obtained values are in agreement with those obtained experimentally.

Gaseous titanium molybdates and tungstates: thermodynamic properties and structures.

RATIONALE: Titanium is a component of various construction materials, which is often used at high temperature and in an oxidizing atmosphere. Thermally stable even at high temperatures, titanium compounds may appear in the condensed phase. To predict the possibility of existence of gaseous associates formed by titanium oxides it is important to know their thermodynamic characteristics. Until the present investigation no gaseous salts of titanium were known. METHODS: Measurements were performed by high-temperature Knudsen effusion mass spectrometry with a MS-1301 mass spectrometer. Vaporization was carried out using molybdenum and tungsten effusion cells containing samples of pure Au, Ti3O5 and SiO2. A theoretical study of gaseous titanium molybdates and tungstates in different spin states was performed by quantum chemical density functional theory (DFT) B3LYP and M06 methods. RESULTS: On the basis of the equilibrium constants of gaseous reactions, the standard formation enthalpies of gaseous TiMoO3 (-424 ± 28 kJ/mol), TiWO3 (-400 ± 22 kJ/mol), TiMoO4 (-795 ± 29 kJ/mol), TiWO4 (-750 ± 24 kJ/mol), TiMoO5 (-1146 ± 23 kJ/mol) and TiWO5 (-1125 ± 22 kJ/mol) at 298 K were determined. Energetically favorable structures were localized and vibrational frequencies were evaluated in the harmonic approximation. Natural atomic charges, bond orders, and valence indices were calculated for all relevant structures. CONCLUSIONS: The stability of gaseous species TiMoOn and TiWOn (n = 3, 4, 5) was confirmed by high-temperature mass spectrometry. A number of gas-phase reactions involving titanium-containing gaseous salts were studied. Enthalpies of reactions of gaseous TiXOn (X = Mo, W; n = 3, 4, 5) formation were evaluated theoretically and the obtained values are in agreement with the experimental ones.

High-temperature mass spectrometric determinations of relative ionization cross-sections of gaseous TiO, TiO2, VO, VO2, YO, HfO and GeO molecules.

RATIONALE: Accurate values of electron ionization cross-sections of high-temperature vapor species are of importance in mass spectrometric investigations as well as in a variety of other fields. However, the present experimental techniques are subject to many inherent difficulties or are limited in applicability and so far have yielded relatively few reliable values. Theoretical calculations are not sufficiently accurate. So the need for experimental ionization cross-section data for these species is very important. METHODS: Measurements were performed by high-temperature Knudsen effusion mass spectrometry with a MS-1301 mass spectrometer. Vaporization was carried out using molybdenum effusion cells containing samples of pure Au, V2O3, Ti3O5, GeO2 and Y2O3-HfO2 systems. RESULTS: The VO, VO2, TiO, TiO2, YO, HfO and GeO vapor species were identified over the samples studied. The partial pressures of Au and the oxides were measured by a complete isothermal vaporization method. The relative ionization cross-sections σ(Au)/σ(i) were determined for the gaseous oxides studied. The results were compared with the literature data. CONCLUSIONS: The inapplicability of the 'additivity rule' is shown. This finding is in good agreement with a tendency to changing ionization cross-sections in the Periodic Table row of gaseous M, МО and МО2 species.