Interfacial properties of chitosan lactate at the liquid/air interface

The interfacial properties (dynamic and equilibrium surface tension, viscosity and elasticity moduli) of chitosan lactate have been studied at the liquid/air interface by the oscillating drop shape method. Isotherms of dynamic surface tension of chitosan lactate are similar to dependences for other polyelectrolyte solutions, in particular for proteins. Chitosan is a weak cationic polyelectrolyte which can change its conformation from a linear rod to a chaotic and compacted coil. Therefore, the experimental dependence of the equilibrium surface tension on concentration of chitosan lactate was analyzed with the adsorption model proposed earlier for proteins. This model accounts the possibility of polyelectrolyte molecules existence in surface layer in n states with different molar surface varying from the maximum value at very low surface coverage by polyelectrolyte molecules to a minimum value at high surface coverage. Good agreement between the calculated and experimental values of surface tension was observed. The dependences of the elasticity and viscosity moduli of chitosan lactate solutions on the drop oscillations frequency are conditioned by the influence of exchange processes both between the surface layer and the bulk solution and in the surface layer itself. An increase of the solution concentration intensifies the exchange processes, and an increase of the oscillation frequency suppresses them. It is shown that the dependence of the surface viscoelasticity modulus of chitosan lactate is extreme in nature with a pronounced maximum. The reason for such behavior is the possibility of changing the molar surface area of the polyelectrolyte at the interface dependent on the amount of adsorption and its structural properties. Attempt of theoretical description of the viscoelasticity modulus within the framework of model accounting mono- or bilayer adsorption did not lead to a satisfactory result, possibly due to barrier adsorption mechanism of chitosan. But bilayer model provide qualitative description of extreme behavior of surface viscoelasticity on concentration. The values of the surface viscoelasticity modulus of chitosan lactate occupy an intermediate position in comparison with the data available in the literature for globular and flexible-chain proteins, that is consistent with their molecular structure. In addition, the work shows the applicability of the adsorption model, developed earlier for proteins in the framework of a nonideal two-dimensional solution theory, for describing the surface properties of other polyelectrolytes. This makes it possible to obtain qualitative and quantitative information about the processes occurring in the systems under study.

Effect of Oxyethylene Groups of Fatty Alcohol Polyoxyethylene Ether Sodium Sulfates on Equilibrium and Dynamic Surface Tension in Relation to Wetting Properties

The effect of hydrophilic chain of surfactants fatty alcohol polyoxyethylene ether sodium sulphates (AEnS, n = 2, 3, 7) on surface properties and wetting properties was investigated by the measurement of equilibrium surface tension, dynamic surface tension and dynamic contact angle. The fatty alcohol polyoxyethylene ether sodium sulphates with different head group sizes were used. From the results of equilibrium surface tension measurements, we could obtain the critical micellisation concentration, adsorption efficiency, maximum surface excess concentration and Langmuir equilibrium adsorption constant at air/liquid interface. The dynamic surface tension results showed that the adsorption of aqueous solutions at the air/liquid interface follows a mixed-diffusion kinetic adsorption mechanism. In conclusion, for both studied surfactant, the longer the oxyethylene chains, the higher the maximum rate of surface tension reduction, the higher the diffusivity and wetting properties in terms of contact angle.

A pH-Responsive Foam Formulated with PAA/Gemini 12-2-12 Complexes

In the search for responsive complexes with potential applications in the formulation of smart dispersed systems such as foams, we hypothesized that a pH-responsive system could be formulated with polyacrylic acid (PAA) mixed with a cationic surfactant, Gemini 12-2-12 (G12). We studied PAA-G12 complexes at liquid–air interfaces by equilibrium and dynamic surface tension, surface rheology, and X-ray reflectometry (XRR). We found that complexes adsorb at the interfaces synergistically, lowering the equilibrium surface tension at surfactant concentrations well below the critical micelle concentration (cmc) of the surfactant. We studied the stability of foams formulated with the complexes as a function of pH. The foams respond reversibly to pH changes: at pH 3.5, they are very stable; at pH > 6, the complexes do not form foams at all. The data presented here demonstrate that foam formation and its pH responsiveness are due to interfacial dynamics.

Predictive Model for the Surface Tension Changes of Chemical Solutions Used in a Clean-in-Place System

The paper presents the results concerning the influence of concentration and storage time on the equilibrium surface tension of chemical solutions used in a clean-in place (CIP) system. Standard cleaning solutions (prepared under laboratory conditions) and industrial solutions (used in a CIP system in a brewery) were subjected to tests. Solutions from the brewery were collected after being regenerated and changes in equilibrium surface tension were studied during a three-month storage. In the statistical analysis of the solutions, standard deviations were determined in relation to the averages, and a Tukey’s multiple comparison test was performed to determine the effect of dependent variables on the surface tension of solutions. From the results, a nonlinear regression model was developed that provided a mathematical description of the kinetics of changes in the wetting properties of the solutions during their storage. A linear–logarithmic function was adopted to describe the regeneration. Numerical calculations were performed based on the nonlinear least squares method using the Gauss–Newton algorithm. The adequacy of the regression models with respect to the empirical data was verified by the coefficient of determination R and the standard error of estimation Se. The results showed that as the concentration of the substance in the cleaning solution increased, its wetting properties decreased. The same effect was observed with increased storage time as the greatest changes occurred during the first eight weeks. The study also showed that the use of substances to stabilize the cleaning solutions prevented deterioration of their wetting properties, regardless of the concentration of the active substance or storage time.

Structural Changes of the Lipid Model Systems in the Presence of Enzymes or Silver Nanoparticles

This work aimed to study the interaction of silver nanoparticles (AgNP) and lipases with models of biological membranes based on natural phospholipid and cholesterol. The crude phosphatidylcholine from egg yolk (PCe1) and synthetic cholesterol (Chol) were obtained from Sigma-Aldrich. Porcine pancreatic lipase (PPL) was obtained by purification from the hog pancreas. AgNP dispersion was prepared by the well-known citrate method. Measurement of surface tension (ST) was carried out using a BPA-1P device. The equilibrium surface tension (eST) was obtained by calculating the ST-time isotherms using the ADSA program. The particle sizes were determined by the dynamic light scattering method. An addition of AgNPs led to a pronounced decrease in both ST and eST (whereas almost no changes occurred by lipase addition), and AgNPs destructed the large lipid particles. The average lipid particle diameter values changed drastically, whereas the effective particle diameter values were almost the same by lipase addition. Thus, the interactions of AgNPs or lipase with the mixture of natural phospholipid and cholesterol have had entirely different features. These effects are interesting for modeling the interactions of inorganic and organic compounds with biological membranes.

Thermodynamics, Kinetics and Dilational Visco‑Elasticity of Adsorbed CnEOm Layers at the Aqueous Solution/Air Interface

The adsorption behaviour of linear poly(oxyethylene) alkyl ether (CnEOm) is best described by a reorientation model. Based on a complete set of experimental data, including the adsorption kinetics, the equilibrium surface tension isotherm and the surface dilational visco-elasticity, the thermodynamic and kinetic adsorption parameters for some CnEOm at the water/air interface were determined. For the study, six CnEOm surfactants were selected (n = 10, 12 and 14 and m = 4, 5 and 8) and were studied by bubble profile analysis and maximum bubble pressure tensiometry. A refined theoretical model based on a reorientation-adsorption model combined with a diffusion-controlled adsorption kinetics and exchange of matter allowed us to calculate the surface layer composition by adsorbing molecules in different orientations. It turns out that at larger surface coverage, the adsorption rate decreases, i.e., the apparent diffusion coefficients are smaller. This deceleration can be explained by the transition of molecules adsorbed in a state of larger molar surface area into a state with smaller molar surface area.

Dynamic surface tension of xylem sap at the air-water interface

<p>The surface tension (ST) of xylem sap at the water-air interface is a crucial phenomenon, influencing many physiological events such as air seeding and embolism, by which xylem vessels become air-filled and cease to function. Refilling of embolized, may relies on sap’s surface activity at the interface. It is commonly assumed that the ST of xylem sap is equal to the ST of pure water (72 mN/m). However, xylem sap is a complex solution and consists of surface-active molecules that may adsorb and accumulate at the water-air interface and thereby reduce the ST of water as a function of their aqueous concentration. However, when a new water-air interface is formed, equilibrium ST is not reached instantaneously. Specifically, amphiphilic molecules are kinetically adsorbed and undergo orientation at the interface following diffusion from the bulk solution. Dynamic ST of xylem sap and liquid-solid interactions, describing the surface phenomena of the xylem of vascular plants is currently not fully understood. This is mainly due to a lack of quantitative knowledge on the rate and extent of dynamic and equilibrium ST of sap. In this regard, the main objective of this study is to quantify the dynamic and equilibrium ST of xylem sap as a function of their aqueous concentration. We extracted xylem sap from lemon trees and measured ST as a function of time using the pendant drop technique. The dynamic ST data were analyzed using empirical and diffusion-control mathematical models which adequately described the exponential-like decay of the ST as a function of time. The results showed reduced ST of water in the xylem sap, indicating significant surface activity, reaching equilibrium ST values as low as 42 mN/m. The rate of ST decay was higher in high sap concentration and reduced in diluted one. The results of dynamic and equilibrium ST and the corresponding model will be presented and their implications for xylem hydraulic functioning will be discussed.</p><p> </p><p>Keywords: Dynamic surface tension, Equilibrium surface tension, Diffusion, Xylem sap.</p><p> </p>

ADSORPTION AND DILATIONAL RHEOLOGICAL PROPERTIES OF CHITOSAN LACTATE AT THE LIQUID-GAS INTERFACE

Методом формы осциллирующей капли исследованы адсорбционные и дилатационные реологические характеристики (модуль упругости и вязкости) лактата хитозана на границе раздела жидкость - газ. Определены зависимости динамического и равновесного поверхностного натяжения от концентрации лактата хитозана в растворе. Установлено, что полученные зависимости сходны с таковыми для поверхностноактивных высокомолекулярных соединений. Изучены зависимости поверхностных упругости и вязкости лактата хитозана от частоты осцилляций и концентрации. Показано, что лактат хитозана способен образовывать упругие адсорбционные слои со значениями модуля вязкоупругости сопоставимыми для биополимеров белковой природы. The adsorption and dilatational rheological characteristics (the elasticity and viscosity modulus) of chitosan lactate at the liquid-gas interface are investigated by the oscillating drop shape method. The dependences of the dynamic and equilibrium surface tension on the concentration of chitosan lactate in solution have been determined. It was found that the dependences obtained are similar to those for surface-active high-molecular weight compounds. The dependences of the surface elasticity and viscosity of chitosan lactate on the oscillation frequency and concentration have been studied. It has been shown that chitosan lactate is capable of forming elastic adsorption layers with the values of the viscoelastic modulus comparable to that of protein biopolymers.