Dynamic interfacial tension of surfactant solutions.

The dynamics of surfactant interfacial layers was first discussed more than a century ago. In 1946 the most important work by Ward and Tordai was published which is still the theoretical basis of all new models to describe the time dependence of interfacial properties. In addition to the diffusion controlled adsorption mechanism, many other models have been postulated in literature, however, well performed experiments with well defined surfactant systems have shown that the diffusional transport is the main process governing the entire formation of surfactant adsorption layers.

Quantum chemical clarification of the alkyl chain length threshold of nonionic surfactants for monolayer formation at the air/water interface.

A theoretical basis is provided for the experimental fact that for various surfactant classes the alkyl chain length threshold varies for the formation of condensed monolayers. The existence of the alkyl chain length threshold for a surfactant enabling the formation of monolayers is determined by the entropy increment to the Gibbs' energy, assessed by using the quantum chemical semiempiric method PM3. The value of the clusterization threshold is not stipulated by the surfactant solubility in water, rather by the electron-donor and electron-seeking properties of the head groups.

Quantum chemical analysis of thermodynamics of 2D cluster formation of alkanes at the water/vapor interface in the presence of aliphatic alcohols.

Using the quantum chemical semi-empirical PM3 method it is shown that aliphatic alcohols favor the spontaneous clusterization of vaporous alkanes at the water surface due to the change of adsorption from the barrier to non-barrier mechanism. A theoretical model of the non-barrier mechanism for monolayer formation is developed. In the framework of this model alcohols (or any other surfactants) act as 'floats', which interact with alkane molecules of the vapor phase using their hydrophobic part, whereas the hydrophilic part is immersed into the water phase.

Adsorption of proteins at the aqueous solution/alkane interface: Co-adsorption of protein and alkane.

The equations of state, adsorption isotherms and functions of the distribution of protein molecules in liquid interfacial layers with respect to molar area and the equations for their viscoelastic behavior are presented. This theory was used to determine the adsorption characteristics of β-casein and β-lactoglobulin at water/oil interfaces. The experimental results are shown to be describable quite adequately by the proposed theory with consistent model parameters.

Thermodynamics of adsorption of ionic surfactants at water/alkane interfaces.

On the basis of experimental data for the homologous series of alkyltrimethylammonium bromides (CnTAB) the equilibrium surface tension isotherms at three types of liquid-fluid interfaces are discussed: solution/air, solution/alkane vapor and solution/liquid alkane interfaces. It is shown that the adsorption characteristics can be described at all three interfaces by the same thermodynamic approach. In the presence of alkane molecules (in the liquid alkane phase or in the alkane vapor phase) the CnTAB adsorption layers can be best described by a co-adsorption of the alkane molecules.

Adsorption of alkyltrimethylammonium bromides at water/alkane interfaces: competitive adsorption of alkanes and surfactants.

The adsorption of members of the homologous series of alkyl trimethylammonium bromides (C(n)TAB) is studied at water/alkane interfaces by drop profile analysis tensiometry. The results are discussed in terms of a competitive adsorption process of alkane and surfactant molecules. A thermodynamic model, derived originally for the adsorption of surfactant mixtures, is adapted such that it describes a competitive adsorption of the surfactant molecules from the aqueous phase and alkane molecules from the oil phase.

Viscoelasticity moduli of aqueous C14EO8 solutions as studied by drop and bubble profile methods.

The drop and bubble profile methods are used to study the viscoelasticity modulus of C14EO8 aqueous solutions within a wide concentration range. To determine the equilibrium concentration of the surfactant in the drop bulk, the correction is introduced for the surfactant losses caused by its adsorption on the drop surface. It is shown that with this correction the frequency dependencies of the viscoelasticity modulus measured by either of the two experimental techniques are almost the same.

Effect of water hardness on surface tension and dilational visco-elasticity of sodium dodecyl sulphate solutions.

The complementary drop and bubble profile analysis and maximum bubble pressure tensiometry are used to measure the dynamic surface tension of aqueous SDS solutions in the presence of hardness salts (CaCl(2) and MgCl(2) in the ratio of 2:1 at concentrations of 6 and 40FH). The presence of hardness salts results in an essential increase of the SDS adsorption activity, which indicates the formation of Ca(DS)(2) and Mg(DS)(2) in the SDS solutions. The surface tension isotherms of SDS in presence of Ca(DS)(2) and Mg(DS)(2) are described using the generalised Frumkin model.

Adsorption layer characteristics of mixed oxyethylated surfactant solutions.

In the presented work, bubble profile analysis tensiometry is used to study the equilibrium surface tensions and the rheological behavior of solutions of mixed oxyethylated alcohols (C(12)EO(5)/C(14)EO(8)) and their mixtures with polyethylene glycol octylphenyl ethers (Triton X45/Triton X165). For the analysis of the experimental data, a new theoretical model for mixtures of two nonionic oxyethylated surfactants was employed which assumes two states of surfactant molecules with different molar areas in the surface layer and an intrinsic compressibility of the molecules in the state of closest packing. The theoretical models allow an accurate description of the experimental equilibrium surface tensions for all studied mixed solutions.

Vaginal microbiocoenosis and cytology of prepubertal and adolescent girls: their role in health and disease.

Background: Clinicians and investigators often do not appreciate the importance of vaginal microbiocoenosis and vaginal cytology in the health of prepubertal and adolescent girls.

Data Sources: Based on recent publications in human medicine and our own experience with vaginal cytology and microbiology in children and adolescent girls, we review the principles of vaginal microbiocoenosis and cytology and their roles in disease prevention in prepubertal and adolescent girls.

Results: The main role of vaginal microbiocoenosis and cytology in diagnosing as well as developing vulvovaginitis is demonstrated.

Adsorption layer characteristics of mixed SDS/C(n)EO(m) solutions. 3. Dynamics of adsorption and surface dilational rheology of micellar solutions.

The dynamic surface tensions of mixed SDS/C(12)EO(5) and SDS/C(14)EO(8) micellar solutions measured over a wide time range (0.1 ms to 10,000 s) at various mixing ratios are described satisfactorily by a theoretical model for the kinetics of adsorption of surfactant mixtures using the surfactant adsorption parameters obtained for premicellar mixed solutions. Additional relations used for the description of the adsorption kinetics from micellar solutions were expressions of the effective diffusion coefficient of monomers accounting for the disintegration of micelles.

Adsorption layer characteristics of mixed SDS/C(n)EO(m) solutions. II. Dilational viscoelasticity.

Bubble profile analysis tensiometry is used to study the surface rheological behavior of mixed SDS/C(12)EO(5) and SDS/C(14)EO(8) solutions. The experimental dependencies of the viscoelasticity modulus and phase angle are studied in a wide range of surfactant concentrations of the individual sodium dodecyl sulfate (SDS) and C(m)EO(n) solutions and SDS/C(n)EO(m) mixtures at various mixing ratios. By generating harmonic oscillations of the bubble area at low oscillation amplitudes, the relaxation behavior at oscillation frequencies between 0.

Adsorption layer characteristics of mixed sodium dodecyl sulfate/C(n)EO(m) solutions 1. Dynamic and equilibrium surface tension.

Bubble profile analysis tensiometry is used to study the dynamic and equilibrium surface tensions of mixed sodium dodecyl sulfate (SDS)/C(12)EO(5) and SDS/C(14)EO(8) solutions. For the data analysis, a new theoretical model was employed, which assumes different adsorption mechanisms for each type of surfactants. In particular, the adsorption behavior of oxyethylated surfactants was described by the so-called reorientation model, which assumes two states of surfactant molecules with different molar areas in the surface layer, and additionally an intrinsic compressibility of the adsorbed layer.

Dynamic surface tension of saliva: general relationships and application in medical diagnostics.

Maximum bubble pressure and pendent drop profile analysis tensiometry are used to study the dynamic surface tension and rheological characteristics of saliva samples taken from volunteers of various sexes and age, and children with caries. The tensiometric characteristics of the secretions released by parotid, submandibular and sublingual glands are studied, and age-related and sex-related changes of some tensiometric characteristics of saliva are found. The differences are most essential for the tensiometric characteristics of saliva samples taken from caries-free children as compared with those taken from children with caries.

Equation of state for monolayers with additional phase transition between condensed phases of different compressibility.

An improved model for the equation of state for Langmuir monolayers proposed in J. Phys. Chem.

Surface dilational viscoelasticity of C14EO8 micellar solution studied by bubble profile analysis tensiometry.

The experimental dependences of viscoelasticity modulus and phase angle as a function of frequency for various C 14EO8 concentrations at the critical micelle concentration (cmc) of 7 micromol/L and far above the cmc (up to 70 x cmc) were studied using the buoyant bubble profile analysis method. With increasing C14EO8 concentration the viscoelasticity modulus decreases and the phase angle increases. At the highest surfactant concentrations, the phase angle was more than 45 degrees .

Thermodynamics and rheology of mixed protein-surfactant adsorption layers.

The behaviour of mixed protein-surfactant surface layers at liquid interfaces has been described essentially qualitatively, until only very recently thermodynamic models were derived for interfacial layers formed by proteins and non-ionic or ionic surfactants, which represent the basis also for a quantitative understanding of the respective adsorption dynamics and dilational rheology of liquid interfaces. On the basis of experimental data obtained from single drop and bubble studies and optical methodologies like ellipsometry and BAM, a clear picture can be drawn now about liquid surface layers relevant for a broad field of applications.

Equation of state for the phase coexistence region of insoluble monolayers under consideration of the entropy nonideality.

The equation of state for the monolayer with a fluid (G, LE)/condensed (LC) phase transition derived earlier (Fainerman, V.B.; Vollhardt, D.

Dilational rheology of serum albumin and blood serum solutions as studied by oscillating drop tensiometry.

Oscillating drop experiments with a drop profile analysis tensiometer provide the dilational elasticity and viscosity of surface layer. Model experiments for blood serum, composed of HSA and the non-ionic surfactant C(14)EO(8), are used to demonstrate the theoretical approach for calculating the visco-elasticity of mixed adsorption layers from the adsorption characteristics of the single components. Experiments with real serum samples taken from patients choledocholithiasis-based benign obstructive jaundice before and after re-canalisation of the biliary tract demonstrate that the visco-elasticity of the respective adsorption layers is very sensitive of the successful surgery.

Optimisation of calculation methods for determination of surface tensions by drop profile analysis tensiometry.

The standard technique for measuring surface or interfacial tension by drop profile analysis requires two main steps: (i) acquisition of drop/bubble images and determination of the profile coordinates via edge detection techniques; (ii) fitting of the theoretical drop/bubble profile to the experimental coordinates using the interfacial tension gamma as adjustable parameter. As to edge detection technique, usually the position of the maximum grey level gradient is assumed to be the drop edge. In order to increase the accuracy of edge detection the procedure of fitting a normal distribution function to the experimental grey level gradients yields accurate results when the drop edge is located into the distribution centre.

Studies of the rate of water evaporation through adsorption layers using drop shape analysis tensiometry.

With modified measuring procedure and measuring cell design in the drop profile tensiometer PAT, it became possible to study the rate of water evaporation through adsorbed or spread surface layers. This method was employed to measure the rate of water evaporation from drops covered by adsorbed layers of some proteins and surfactants, in particular n-dodecanol. It was shown that the formation of dense (double or condensed) adsorbed layers of protein and the formation of 2D-condensed n-dodecanol layer decrease the water evaporation rate by 20-25% as compared with pure water.

Application of the maximum bubble pressure technique for dynamic surface tension studies of surfactant solutions using the Sugden two-capillary method.

Exact knowledge of the dead time as part of the bubble lifetime in the maximum bubble pressure method is an important prerequisite for accurate dynamic surface tension measurements. The duration of the dead time depends essentially on the capillary geometry and affects significantly the measured surface tensions of concentrated surfactant solutions. Increase of the dead time leads to a significant surface tension decrease of a freshly formed bubble surface due to the significantly higher residual adsorption of the surfactant molecules.

Molecular recognition kinetics of nonsurface active pyrimidine derivatives dissolved in the aqueous subphase by an amphiphilic melamine type monolayer: A theoretical approach.

Experimental studies show a drastic change of the characteristic features (Pi-A isotherms, morphology of the condensed phase domains) of the 2C11H23-melamine monolayers by molecular recognition of the pyrimidine derivatives uracil and thymine, largely affected by the reaction kinetics of the recognition process. A new approximate additive theoretical model is introduced for describing the molecular recognition kinetics. The theoretical approach is based on two assumptions: (i) first-order reaction kinetics for the molecular recognition of the nonsurface active pyrimidine derivatives dissolved in the aqueous subphase by the melamine type monolayer and (ii) applicability of the Pi-A isotherm equations derived previously for the description of melamine type monolayers in the fluid (gaseous, LE) state and the phase transition region to the condensed state.

Kinetics of the desorption of surfactants and proteins from adsorption layers at the solution/air interface.

It is shown by experiments that the DeSNa desorption kinetics is governed by a pure diffusion mechanism, while the desorption of more surface active surfactants such as C13DMPO and Triton X-100 obeys a mixed mechanism. The BLG desorption kinetics, as shown by experiments, is determined by a barrier mechanism. From the analysis of the temperature dependence of the BLG desorption kinetics it is possible to calculate the activation energy of this process, which is quite close to the free energy of BLG adsorption.