A. V. Akentiev

Dilational surface viscoelasticity of polymer solutions

A review of recent results on the dilational surface viscoelastic properties of aqueous solutions of non-ionic polymers is given. In the frequency range from 0.001 up to 1000 Hz the methods of transverse and longitudinal surface waves and the oscillating barrier method were applied. Viscoelastic behavior of adsorbed polymer films significantly differs from the behavior of films formed by only conventional surfactants of low molecular weight. For example, the dynamic surface elasticity of the former systems is low and almost constant in a broad concentration range. One can observe the increase of the surface elasticity only at extremely low concentrations and/or in the range of semi-dilute solutions. If the surface stress relaxation in conventional surfactant solutions is usually determined by the diffusional exchange between the surface layer and the bulk phase, the relaxation processes in the polymer systems proceed mainly inside the surface layer. Possible mechanism of the latter relaxation is discussed.

Surface Dynamic Elasticity of Poly(ethylene oxide) Monolayers on a Water Surface

The methods of transverse and longitudinal surface waves and of oscillating barrier were used to measure a surface dynamic elasticity of poly(ethylene oxide) films spread on aqueous substrate within the frequency range of 0.001–520 Hz. Unlike the adsorption films, the main relaxation processes in the spread poly(ethylene oxide) films are observed at higher frequencies. A comparison of static and dynamic values of the surface elasticity shows that the surface film at surface polymer concentrations higher than 0.4 mg/m2 cannot be considered already as purely two-dimensional film. It was found that the surface tension (surface pressure) can be insufficiently sensitive to conformational transformations in the surface polymer films.

Relation between rheological properties and structural changes in monolayers of model lung surfactant under compression

rSP-C surfactant monolayers spread on a native physiological model substrate show two plateau regions in the pi/A-isotherm. The first corresponds to the main phase transition in the monolayer from a LE to a LC phase. Its course is non-horizontal because of the complex composition of the lung surfactant. The second plateau, which is much more pronounced, cannot be attributed to a change of the phase state. Brewster angle microscopy images taken in this region show a sharp apparent decrease of the aggregation degree from the LE to the LC state. This process can be considered as a change in the monolayer orientation relative to the direction of the propagated light. Such a change can be the result of monolayer folding and formation of a thicker layer, which is supported by results of rheological measurements. The dilatation elasticity obtained from oscillating barrier and longitudinal wave measurements reveals a pure elastic behaviour with a steep increase in the second plateau region. Because of the insolubility of the pure lipid components, a possible explanation is squeezing protein components of rSP-C or its complexes with lipids out of the monolayer into the bulk.

Spread Films of Synthetic Polyelectrolyte-Surfactant Complexes : Dilational Viscoelasticity and Effect on Water Evaporation

Data are presented on the dynamic surface properties of films formed from sodium polystyrenesulfonate-dodecyltrimethylammonium bromide (PSS-DTAB) and poly(diallyldimethylammonium chloride)-sodium dodecyl sulfate (PDADMAC-SDS) complexes by the spreading of the above substances onto a water surface from their concentrated solutions. These films are shown to be stable up to surface pressures of 20 mN/m (PSS-DTAB) and 37 mN/m (PDADMAC-SDS). In the latter case, when the limiting surface pressure is reached, microaggregates are formed in the surface layer along with the film dissolution. The surface films in question markedly decelerate water evaporation, and this phenomenon cannot be explained in terms of the classical Goddard model of the structure of films prepared from polyelectrolyte-surfactant complexes and, at the same time, is in good agreement with a recently proposed model that takes into account hydrophobic interactions.

Influence of Lipid Core Material on Physicochemical Characteristics of an Ursolic Acid-Loaded Nanostructured Lipid Carrier: An Attempt To Enhance Anticancer Activity

The impact of saturation and unsaturation in the fatty acyl hydrocarbon chain on the physicochemical properties of nanostructured lipid carriers (NLCs) was investigated to develop novel delivery systems loaded with an anticancer drug, ursolic acid (UA). Aqueous NLC dispersions were prepared by a high-pressure homogenization-ultrasonication technique with Tween 80 as a stabilizer. Mutual miscibility of the components at the air-water interface was assessed by surface pressure-area measurements, where attractive interactions were recorded between the lipid mixtures and UA, irrespective of the extent of saturation or unsaturation in fatty acyl chains. NLCs were characterized by combined dynamic light scattering, transmission electron microscopy (TEM), atomic force microscopy (AFM), differential scanning calorimetry, drug encapsulation efficiency, drug payload, in vitro drug release, and in vitro cytotoxicity studies. The saturated lipid-based NLCs were larger than unsaturated lipids. TEM and AFM images revealed the spherical and smooth surface morphology of NLCs. The encapsulation efficiency and drug payload were higher for unsaturated lipid blends. In vitro release studies indicate that the nature of the lipid matrix affects both the rate and release pattern. All UA-loaded formulations exhibited superior anticancer activity compared to that of free UA against human leukemic cell line K562 and melanoma cell line B16.

Scanning probe microscopy of adsorption layers of sodium polystyrenesulfonate/dodecyltrimethylammonium bromide complexes

Scanning probe microscopy is used to study adsorption films of sodium polystyrenesulfonate/dodecyltrimethylammonium bromide complexes, which are transferred from aqueous solution surfaces to the mica surface by the Langmuir-Blodgett method. It is established that the results obtained at surfactant concentrations below critical micelle concentration agree with the conclusions on the structure of the films dased on the data of the dilatational surface rheology (Noskov, B.A., Loglio, G., Miller, R., J. Phys. Chem. B, 2004, vol. 108, p. 18615). At low concentrations of the low-molecular-mass surfactant, a thin adsorption film containing a large number of holes is formed on the surface of an aqueous solution. As the surfactant concentration is increased to reach the region of a dramatic reduction in the dynamic surface elasticity, the morphology of the film drastically changes; i.e., dense three-dimensional aggregates are formed on the solution surface.

Double-Tailed Cystine Derivatives as Novel Substitutes of Phospholipids with Special Reference to Liposomes

Cystine-based gemini surfactants with dodecyl, tetradecyl, hexadecyl, and octadecyl hydrocarbon chains were synthesized, and their interactions with unsaturated (soy phosphatidylcholine, SPC)/saturated (hydrogenated SPC, HSPC) soy phosphatidylcholines in the forms of a monolayer and a model liposome were estimated for different combinations of the components in the mixed systems. Studies of Langmuir monolayers at the air-aqueous buffer interface revealed condensation of the monomolecular films with the addition of surfactants. The effect of surfactants decreased according to the following order: octadecyl > hexadecyl > tetradecyl > dodecyl homologs. The nonideal mixing between the components was estimated using the deviation of the experimental molecular area from the ideal area per molecule. The excess molecular area increased with the increase in the surfactant chain length and phospholipid saturation. The 50 mol % mixture of cystine derivatives and phospholipids formed thermodynamically stable monolayers. The surfactants increased the rigidity of SPC monolayers and decreased that of HSPC monolayers, as observed by the studies of surface dialational rheology. The film structure at the air-water interface could differentiate the SPC- and HSPC-comprising systems through the formation of organized regions, especially at a higher surface pressure. The constriction of surfactant/phospholipid hybrid vesicles was observed with an increase in the length of surfactant hydrocarbon chains. The negative zeta potential of vesicles took the highest values and did not change with time for 20 and 50 mol % surfactant. The spherical shape of the vesicles was confirmed by transmission electron microscopy. Differential scanning calorimetry revealed an increase in fluidity of HSPC bilayers and rigidity of SPS bilayers under the influence of surfactants. These effects were confirmed by fluorescence spectroscopy. All of the vesicle formulations were found to be nontoxic from the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazolium bromide assay, suggesting their potential as a novel membranous system for the delivery of drugs, genetic materials, vaccines, and other therapeutic agents.

Effect of preparation conditions on properties of polylactide and polystyrene and their composite microparticles made by emulsion solvent evaporation method

In this study, polylactide and polystyrene microparticles have been prepared by emulsion solvent evaporation method. Effects of polymer nature, stirring speed, emulsifier, and concentration of the components on the size, size distribution and morphology of polymeric microparticles have been investigated. 11-Acryloyl-aminoundecanoic acid and its polymer poly(11-acryloyl-aminoundecanoic acid) were tested for comparison with traditional emulsifiers such as sodium dodecylsulfate. Interfacial tension measurement was applied to compare these emulsifiers. Dynamic light scattering and scanning electron microscopy were used to analyze microparticles. Polylactide/polystyrene composite microparticles have been prepared as well; their surface morphology has been studied.

Dynamic elasticity of films formed by poly( N -isopropylacrylamide) microparticles on a water surface

Surface dilatational dynamic elasticity ε of films formed by cross-linked poly(N-isopropylacrylamide) microparticles on a water/air interface has been determined as a function of polymer surface concentration Γ. The experimental dependences exhibit two maxima of ε at surface pressures π of nearly 6 and 35 mN/m. In the region of the second maximum, the pattern of the dependence is governed by a method used to vary Γ. At π > 25 mN/m, film compression leads to the formation of a metastable monolayer, while the gradual addition of a microparticle dispersion results in the establishment of equilibrium between the monolayer and surface aggregates. In the region of π values corresponding to the second maximum of ε, slow relaxation processes with a characteristic time substantially longer than 10 s occur in the system. At π > 35 mN/m, the film collapses due to the displacement of microgel particles from the water surface.

Evaporation of aqueous solutions of organic acids through spread films of sodium polystyrene sulfonate/dodecyl trimethyl ammonium bromide complex

Abstract The Wilhelmy plate technique was used to determine surface tension isotherms of aqueous solutions of formic and acetic acids with concentration up to 30 vol% and with a film of solution of sodium polystyrene sulfonate/dodecyl trimethyl ammonium bromide complex spread to the surface. The formation conditions of films with the extreme concentration of the complex were determined. Such films reduce the evaporation rate of binary liquids by 3-6% and demonstrate selective properties increasing the water content in the vapor by 2-5 abs%.