Molecular Dynamics Simulation of Hydrogels Based on Phosphorylcholine-Containing Copolymers for Soft Contact Lens Applications.

The structure and dynamics of copolymers of 2-hydroxyethyl methacrylate (HEMA) with 2-methacryloyloxyethyl phosphorylcholine (MPC) were studied by molecular dynamics simulations. In total, 20 systems were analyzed. They differed in numerical fractions of the MPC in the copolymer chain, equal to 0.26 and 0.74, in the sequence of mers, block and random, and the water content, from 0 to 60% by mass. HEMA side chains proved relatively rigid and stable in all considered configurations. MPC side chains, in contrast, were mobile and flexible. Water substantially influenced their dynamics. The copolymer swelling caused by water resulted in diffusion channels, pronounced in highly hydrated systems. Water in the hydrates existed in two states: those that bond to the polymer chain and the free one; the latter was similar to bulk water but with a lower self-diffusion coefficient. The results proved that molecular dynamics simulations could facilitate the preliminary selection of the polymer materials for specific purposes before their synthesis.

Wetting Behaviour of Water, Ethanol, Rhamnolipid, and Triton X-165 Mixture in the Polymer-Solution Drop-Air System.

Despite the fact that the wetting properties of multicomponent mixtures including the surface active compounds play a very important role in many practical applications, they are not sufficiently known. Thus, the wettability of polytetrafluoroethylene (PTFE) and poly (methyl methacrylate) (PMMA) by the water + ethanol (ET) solution of rhamnolipid (RL) with Triton X-165 (TX165) mixture was studied. The investigations involved measuring the advancing contact angles of this solution on PTFE and PMMA by varying the concentration of TX165 while maintaining a constant concentration of ET and RL. Additionally, a thermodynamic analysis was conducted to obtain the compositions and concentrations of the ET, RL, and TX165 mixtures at the different interfaces. The composition and concentration of the interface mixed layer were considered using two different approaches to the wetting process. From these considerations, it follows that, depending on the ET concentration, it is possible to form the TX165 + RL layer at the solid-water + ET mixed solvent, as well as the water + ET-air interfaces, but not at the solid-water and water-air ones. This conclusion is in accordance with the Gibbs standard free energy of adsorption of particular components of the studied mixture at the solution-air and solid-solution interfaces.

Thermodynamic Characterization of Rhamnolipid, Triton X-165 and Ethanol as well as Their Mixture Behaviour at the Water-Air Interface.

In many industrial fields, in medicine or pharmacy, there are used multi-component mixtures of surfactants as well as more and more often mixtures containing biosurfactants. Thus, in our study the mixtures of rhamnolipid (RL), ethanol (ET) and Triton X-165 (TX165) were applied. For these mixtures the surface tension of aqueous solutions with constant concentration and composition of ET and RL as well as the variable concentration of TX165 was measured. Based on the obtained results and the literature data, thermodynamic analyses of the adsorption process of ET, RL, TX165, binary mixtures of ET + RL, ET + TX165 and RL + TX165 as well as the ternary mixtures of RL + ET + TX165 at the water-air interface were made. This analysis allows to propose a new equation for calculation of the total ethanol concentration at the water-air interface using the Guggenheim-Adam adsorption isotherm. The constants in the Langmuir and Szyszkowski equations for each component of the studied mixtures as well as the composition of the mixed monolayer at the water-air interface were also successfully analysed based on the contribution of particular surface active compounds to the water surface tension reduction as well as based on the Frumkin isotherm of adsorption.

Thermodynamic Parameters of Berberine with Kolliphor Mixtures Adsorption and Micellization.

The poor solubility of berberine (Ber) in water limits its practical use. Its solubility can be increased, among other ways, by the addition of surfactants. Of the surfactants, Kolliphor® ELP (ELP) and Kolliphor® RH 40 (RH40) can be very useful in this respect. The increase of Ber's solubility in water in the presence of ELP and RH40 should be reflected in the composition of the surface layers at the water-air interface and the micelles. The determined composition is reflected in the Gibbs energy of interactions of berberine with ELP and RH40 through the water phase and the standard Gibbs free energy, enthalpy, and entropy of adsorption and micellization. These energies were determined from the equations proposed by us, based on the Gibbs surface excess concentration of the Ber mixture with ELP and RH40, the activity of these compounds in the surface layer at the water-air interface and in the micelles obtained by the Hua and Rosen method, and the contributions of Ber, ELP, and RH40 to the reduction in the water surface tension. For this determination, the measurements of the surface tension of the aqueous solution of the Ber mixture with ELP or RH40 and that of the Ber mixture with these two surfactants, as well as the density and conductivity were performed. Moreover, the fluorescence emission spectra for the Ber + surfactant mixtures were recorded.

Adsorption and volumetric properties of some nonionic surfactants and their mixtures with quercetin and rutin.

The adsorption and volumetric properties of the Triton X-114 (TX114), Tween 80 (T80), quercetin (Q) and rutin (Ru) at the different temperatures in relation to above properties of the TX114 and T80 mixtures with quercetin and rutin in the absence and presence of alcohol were discussed based on the studies reported in the literature. The adsorption isotherms of the mixtures of the nonionic surfactants with flavonoids in the presence and absence of alcohol were analyzed based on the isotherms of the surface tension of the particular mixture components and thermodynamic parameters of the adsorption of these components at the water-air interface. The surface tension isotherms of the particular component of the mixtures were taken into account while considering the surface tension isotherms of the mixtures and the composition of the mixed surface layer at the water-air interface. Different ways of the mixed surface layer composition determination were shown. The values of the surface tension and composition of the mixed surface layers obtained using different methods were discussed in the light of the intermolecular interactions and their contribution to the surface tension of the surfactants mixture with flavonoids and alcohol. The composition of the mixed monolayer and the bulk phase were compared and the differences between them were explained. The behaviour of the nonionic surfactants and flavonoids in the presence and absence of alcohol was analyzed in relation to the micelle formations and molar volumes of the mixtures and their components. Moreover, the micelles composition and their size as well as the thermodynamic parameters of the micellization process were analyzed.

Tellurite Glasses from the 70TeO2-5XO-10P2O5-10ZnO-5PbF2(X= Pb, Bi, Ti) System Doped Erbium Ions-The Influence of Erbium on the Structure and Physical Properties.

In this article, we present research on the influence of erbium ions on the structure and magneto-optical properties of 70TeO2-5XO-10P2O5-10ZnO-5PbF2 (X = Pb, Bi, Ti) tellurite glass systems. Structural changes occurring in the glasses during doping with erbium ions were investigated using positron annihilation lifetime spectroscopy (PALS) and Raman spectroscopy. The X-ray diffraction (XRD) method was used to confirm the amorphous structure of the investigated samples. Based on the Faraday effect measurements and calculated values of Verdet constant, the magneto-optical properties of the glasses were determined.

Behavior of Auramine O in the Aqueous Solution of Two Kolliphors and Their Mixture.

The studies on the behavior of Auramine O (AuO) at the water-air interface and in the bulk phase of the aqueous solution of Kolliphor® ELP (ELP) and Kolliphor® RH 40 (RH40) and their mixture were based on the results obtained from the measurements of the contact angle of water, formamide and diiodomethane on the polytetrafluoroethylene covered by the AuO layer, the surface tension of the aqueous solution of AuO, AuO + ELP, AuO + RH40, AuO + ELP + RH40, density and fluorescence intensity. Based on the obtained results, it was possible to determine components and parameters of the AuO surface tension, concentration and composition of the mixed monolayer, including AuO, ELP and RH40, as well as that of the mixed micelles, and to determine the Gibbs standard free energy of adsorption, micellization and AuO solubilization. The obtained results also showed that surface tension isotherms of the studied solutions can be described by the Szyszkowski equation and the exponential function of the second order and predicted by the Fainerman and Miller equation. In addition, the mixed surface layer composition can be predicted based on the contribution of the components of this layer to the water surface tension reduction.

Wetting Properties of Rhamnolipid and Surfactin Mixtures with Triton X-165.

The wetting properties of the rhamnolipid and surfactin mixtures with Triton X-165 were considered based on the contact angle measurements of their aqueous solution on the polytetrafluoroethylene (PTFE), polymethyl methacrylate (PMMA) and quartz (Q) surfaces. The obtained contact angle isotherms were described by the exponential function of the second order as well as by Szyszkowski equation in some cases. Using the contact angle isotherms of individual biosurfactants and TX165 as well as the earlier obtained isotherms of their surface tension the contact angle isotherms of the biosurfactants mixtures with TX165 were deduced. As follows the presence of the maxima on the contact angle isotherms of the biosurfactants mixtures with TX165 is justified. They do not prove negative adsorption of the biosurfactant and TX165 at the interfaces. However, the mutual exchange of the biosurfactant and TX165 molecules is observed in the layers at the interfaces. The concentration of the studied mixtures at the PTFE-solution interface was established to be close to that at the solution-air one but that at the PTFE-air is equal to zero. However, the concentration of the studied mixtures at the PMMA-solution and quartz-solution is greater than zero. The concentration at the PMMA(quartz)-air and PMMA(quartz)-solution interfaces is smaller than that at the solution-air one.

Thermodynamic Analysis of the Adsorption and Micellization Activity of the Mixtures of Rhamnolipid and Surfactin with Triton X-165.

The surface tension of aqueous solutions of Triton X-165 with rhamnolipid or surfactin mixtures was measured. The obtained results were applied for the determination of the concentration and composition of the Triton X-165 and biosurfactants mixture at the water-air interface as well as the contribution of the particular component of the mixtures to water surface tension reduction and the mutual influence of these components on the critical micelle concentration. The determination of these quantities was based on both the commonly used concepts and a new one proposed by us, which assumes that the composition of the mixed monolayer at the water-air interface depends directly on the pressure of the monolayer of the single mixture component and allows us to determine the surface concentration of each mixture component independently of surface tension isotherms shape. Taking into account the composition of the mixed monolayer at the water-air interface, the standard Gibbs adsorption free energy was considered. The obtained results allow us to state that the concentration of both mixture components corresponding to their saturated monolayer and the surface tension of their aqueous solution can be predicted using the surfactants' single monolayer pressure and their mole fraction in the mixed monolayer determined in the proposed way.

Mutual Influence of Some Flavonoids and Classical Nonionic Surfactants on Their Adsorption and Volumetric Properties at Different Temperatures.

Due to the increasing practical use of mixtures of flavonoids with nonionic surfactants the presented studies were based on the measurements of surface tension and conductivity of aqueous solution of the quercetin (Q) and rutin (Ru) in the mixtures with Triton X-114 (TX114) and Tween 80 (T80) as well as the contact angle of model liquids on the PTFE surface covered by the quercetin and rutin layers. Based on the obtained results components and parameters of the quercetin and rutin surface tension were determined and the mutual influence of Q and Ru in the mixtures with TX114 and T80 on their adsorption and volumetric properties were considered. It was found, among others, that based on the surface tension isotherms of the aqueous solution of the single flavonoid and nonionic surfactant, the surface tension isotherms of the aqueous solution of their mixture, the composition of the mixed monolayer at the water-air interface as well as the CMC of flavonoid + nonionic surfactant mixture can be predicted. The standard Gibbs energy, enthalpy and entropy of the adsorption and aggregation of the studied mixtures were also found, showing the mechanism of the adsorption and aggregation processes of the flavonoid + nonionic surfactant mixture.

Adsorption Properties and Composition of Binary Kolliphor Mixtures at the Water-Air Interface at Different Temperatures.

The studies on the adsorption properties and composition of the adsorbed monolayer at the water-air interface of the binary Kolliphor® ELP (ELP) and Kolliphor® RH 40 (RH40) mixtures based on the measurements of the surface tension (γLV) of their aqueous solution in the temperature range from 293 to 318 K were carried out. The γLV isotherms were described by the exponential function of the second order and the Szyszkowski equation as well as predicted by Fainerman and Miller equation. The obtained γLV isotherms were analyzed using the exponential function of the second order, the Szyszkowski, Fainerman and Miller as well as independent adsorption equations. The γLV isotherms were also used for determination of the Gibbs surface excess concentration of RH40, ELP and their mixture (Γ) at the water-air interface as well as the mixed monolayer composition. Based on Γ and the constant a in the Szyszkowski equation, the standard thermodynamic functions of adsorption were considered. From the consideration dealing with the γLV isotherms obtained by us, it results, among others, that these isotherms for the non-ideal solution of macromolecular surfactants mixture can be predicted using the Fainerman and Miller equation. From this consideration, it also results that a simple method proposed by us, based on the isotherms of RH40 and ELP, allows us to predict the composition of their mixed monolayer in the whole concentration range of RH40 and ELP in the bulk phase.

Adsorption Properties of Hydrocarbon and Fluorocarbon Surfactants Ternary Mixture at the Water-Air Interface.

Measurements were made of the surface tension of the aqueous solutions of p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene glycols) having 10 oxyethylene groups in the molecule (Triton X-100, TX100) and cetyltrimethylammonium bromide (CTAB) with Zonyl FSN-100 (FC6EO14, FC1) as well as with Zonyl FSO-100 (FC5EO10, FC2) ternary mixtures. The obtained results were compared to those provided by the Fainerman and Miller equation and to the values of the solution surface tension calculated, based on the contribution of a particular surfactant in the mixture to the reduction of water surface tension. The changes of the aqueous solution ternary surfactants mixture surface tension at the constant concentration of TX100 and CTAB mixture at which the water surface tension was reduced to 60 and 50 mN/m as a function of fluorocarbon surfactant concentration, were considered with regard to the composition of the mixed monolayer at the water-air interface. Next, this composition was applied for the calculation of the concentration of the particular surfactants in the monolayer using the Frumkin equation. On the other hand, the Gibbs surface excess concentration was determined only for the fluorocarbon surfactants. The tendency of the particular surfactants to adsorb at the water-air interface was discussed, based on the Gibbs standard free energy of adsorption which was determined using different methods. This energy was also deduced, based on the surfactant tail surface tension and tail-water interface tension.

Properties of some nonionic fluorocarbon surfactants and their mixtures with hydrocarbon ones.

The adsorption of Zonyl FSN-100 (FSN100, having an average 14 oxyethylene units and 6 -CF2 groups) and Zonyl FSO-100 (FSO100, having an average 10 oxyethylene units and 5 -CF2 groups) as well as of their mixtures with p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene glycols) having 10, 16 and 8 oxyethylene groups in molecule (TX100, TX165, TX114) and cetyltrimethylammonium bromide (CTAB) at the solution-air and polytetrafluoroethylene (PTFE)-solution and polymethyl methacrylate (PMMA)-solution interfaces as well as the composition of the surface mixed layer was discussed based on the literature data. The adsorption properties of nonionic fluorocarbon surfactants were compared to those of the classical ones on the basis of the Gibbs standard free energy of adsorption determined by different ways and the intermolecular interactions of the surfactant molecules through the water phase. The synergetic effect in the reduction of the water surface tension by the mixture of fluorocarbon and classical nonionic surfactant was shown and explained by the comparison of the composition of the mixed surface layer to those in the bulk phase. The composition of the mixed fluorocarbon and classical surfactant layer at the solution-air interface was compared to that formed at the PTFE-solution and PMMA-solution interfaces. The changes of the surface tension of the aqueous solution of the fluorocarbon surfactants and their mixtures with classical hydrocarbon ones and their adsorption were analyzed taking into account the PTFE and PMMA surface wettability. This analysis was also based on the components and parameters of the head and tail of the surfactants surface tension as well as those of PTFE and PMMA. Apart from adsorption and wetting properties the aggregation of the fluorocarbon surfactants and their mixtures was discussed. A specific attention was paid to the possibility of two CMC values in the case of nonionic fluorocarbon surfactants as well as the synergism in CMC of mixtures of nonionic fluorocarbon and hydrocarbon surfactants.

Partitioning of Selected Anisole and Veratrole Derivatives between Water and Anionic Surfactant Micelles.

The UV absorption spectra of six structurally related derivatives of anisole and veratrole, i.e., anisaldehyde, (E)-anethole, estragole, veratraldehyde, methyleugenol and (E)-methylisoeugenol, were recorded at various concentrations of the anionic surfactants, either sodium lauryl sulfate (SLS) or sodium lauryl ether sulfate (SLES) at T = 298 K. In addition, conductivity and density measurements were made for the SLS and SLES solutions to determine the volumetric properties of the studied surfactants. Next, using the W. Al-Soufi, L. Pineiro and M. Novo model (APN model) including the pseudo-phase model for micellar solubilization, the values of micelle-water partition coefficients for each perfume-surfactant system were determined. In addition, the relations between the molecular structures of the solute and the head group of the surfactant and the value of the micelle-water partition coefficient as well as the octanol-water one were discussed.

Temperature Effect on the Adsorption and Volumetric Properties of Aqueous Solutions of Kolliphor®ELP.

Density, viscosity and surface tension of Kolliphor® ELP, the nonionic surfactant aqueous solutions were measured at temperature T = 293-318 K and at 5K interval. Steady-state fluorescence measurements have been also made using pyrene as a probe. On the basis of the obtained results, a number of thermodynamic, thermo-acoustic and anharmonic parameters of the studied surfactant have been evaluated and interpreted in terms of structural effects and solute-solvent interactions. The results suggest that the molecules of studied surfactant at concentrations higher than the critical micelle concentration act as structure makers of the water structure.

Adsorption and Aggregation Properties of Some Polysorbates at Different Temperatures.

Measurements of the surface tension of aqueous solutions of polysorbates (Tween 20, Tween 60 and Tween 80) at 293, 303 and 313 K were made. On the basis of the obtained results the Gibbs surface excess concentration of the Tweens at the water-air interface and critical micelle concentrations were determined. Knowing the Gibbs surface excess concentration and taking into account the difference between the limiting area occupied by water and Tween molecules at the water-air interface, the fraction occupied by Tween molecules was established. The limiting area occupied by the Tween molecule was calculated by applying the Joos equation. The area determined in such a way was confirmed by the calculations of cross section of Tween molecules based on the bond lengths and the angles between them as well as the average distance between the molecules, taking into account their different conformations. This area was used for calculation of the standard Gibbs energy of adsorption using the Langmuir equation. The standard Gibbs energy of Tweens adsorption at the water-air interface was also calculated from the hydrophobic part of Tween molecule-water interface tension and that of hydrophobic part. Using the determined values of standard Gibbs energy of adsorption at different temperatures, the standard enthalpy and entropy values were deduced. The standard thermodynamic functions of micellization were also determined and compared to the Gibbs energy of Tween molecules interactions through the water phase.

Macroscopic and Microscopic Properties of Some Surfactants and Biosurfactants.

The adsorption of surfactants at the water-air and solid-water interfaces and their wetting properties decide their practical applications. Therefore the adsorption of monorhamnolipid, surfactin, n-octyl-ß-d-glucopyranoside, n-dodecyl-ß-d-glucopyranoside, n-dodecyl-β-d-maltoside, sucrose monodecanoate, sucrose monododecanoate, Tween 20, Tween 60, and Tween 80 at the water-air, polytetrafluoroethylene-water, polyethylene-water, poly(methyl methacrylate)-water, polyamide-water, and quartz-water interfaces, their tendency to form micelles as well as their wetting properties, were considered in the light of their microscopic properties. For this purpose, the components and parameters of the surfactant tail and head, water and solids surface tension, and surfactant contactable area with adherent medium were applied for prediction of surfactant-surfactant and surfactant-solid interactions through the water phase with regard to their adsorption, micellization, and wetting processes. Next, the Gibbs free energy of interactions was compared to the Gibbs free energy of surfactant adsorption at the water-air and solid-water interfaces as well as the micellization. It appeared that from the surfactant-surfactant and surfactant-solid interactions through the water phase determined on the basis of the tail and head of surfactant surface tension, it is possible to predict the surfactant tendency to adsorb at the water-air and solid-water interfaces, as well as to form micelles.

Effect of two hydrocarbon and one fluorocarbon surfactant mixtures on the surface tension and wettability of polymers.

The advancing contact angle of water, formamide and diiodomethane on polytetrafluoroethylene (PTFE) and polymethyl methacrylate (PMMA) surfaces covered with the film of ternary mixtures of surfactants including p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethyleneglycols), Triton X-100 (TX100) and Triton X-165 (TX165) and the fluorocarbon surfactants, Zonyl FSN-100 (FSN100) or Zonyl FSO-100 (FSO100) was measured. The obtained results were used for the surface tension of PTFE and PMMA covered with this film determination from the Young equation on the basis of van Oss et al. and Neumann et al. approaches to the interfacial tension. The surface tension of PTFE and PMMA was also determined using the Neumann et al. equation and the contact angle values for the aqueous solutions of the above mentioned ternary surfactants mixtures which were taken from the literature. As follows from our calculations mainly the presence of the fluorocarbon surfactant in the mixture considerably changes the surface properties of PTFE and PMMA causing that in contrast to hydrocarbon surfactants and their mixtures there is no linear dependence between adhesion and surface tension in the whole range of concentration of the ternary mixtures of surfactants including the fluorocarbon one. The behavior of fluorocarbon surfactants at the polymer-air and polymer-water interfaces is quite different from those of hydrocarbons. In the case of fluorocarbon surfactants not only adsorption but also sorption can occur on the polymer surface.

Wettability of polymeric solids by ternary mixtures composed of hydrocarbon and fluorocarbon nonionic surfactants.

Contact angle (θ) measurements on poly(tetrafluoroethylene) (PTFE) and polymethyl methacrylate (PMMA) surface were carried out for the systems containing ternary mixtures of surfactants composed of: p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycols), Triton X-100 (TX100), Triton X-165 (TX165) and Triton X-114 (TX114), and fluorocarbon surfactants, Zonyl FSN100 (FSN100) and Zonyl FSO100 (FSO100). The aqueous solutions of ternary surfactant mixtures were prepared by adding TX114, FSN100 or FSO100 to binary mixtures of TX100+TX165, where the synergistic effect in the reduction of the surface tension of water (γ(LV)) was determined. From the obtained contact angle values, the relationships between cosθ, the adhesion tension and surface tension of solutions, cosθ and the reciprocal of the surface tension were determined. On the basis of these relationships, the correlation between the critical surface tension of PTFE and PMMA wetting and the surface tension of these polymers as well as the work of adhesion of aqueous solutions of ternary surfactant mixtures to PTFE and PMMA surface were discussed. The critical surface tension of PTFE and PMMA wetting, γ(C), determined from the contact angle measurements of aqueous solutions of surfactants including FSN100 or FSO100 was also discussed in the light of the surface tension changes of PTFE and PMMA under the influence of film formation by fluorocarbon surfactants on the surface of these polymers. The γ(C) values of the studied polymeric solids were found to be different for the mixtures composed of hydrocarbon surfactants in comparison with those of hydrocarbon and fluorocarbon surfactants. In the solutions containing fluorocarbon surfactants, the γ(C) values were different taking into account the contact angle in the range of FSN100 and FSO100 concentration corresponding to their unsaturated monolayer at water-air interface or to that saturated.

A study of the interactions of ternary surfactant systems at the water-air interface.

Surface tension measurements were carried out for the systems containing ternary mixtures of cetyltrimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycols), Triton X-100 (TX100) and Triton X-165 (TX165). The aqueous solution of ternary surfactant mixtures were prepared by adding the third surfactant to the binary mixture of the surfactants where the synergetic effect in the reduction of the surface tension of water were determined to compare the influence of the third surfactants on the adsorption of this binary mixture at the water-air interface. The obtained results and calculations indicate that the synergetic effect in the reduction of the surface tension of water was deepened after adding the third surfactant to the binary mixture at the composition at which this effect was observed. The best synergetic effect in the gamma(LV) reduction was determined on the basis of the values of the molecular interaction parameter for aqueous solutions of ternary mixtures of CTAB+TX165 (alpha CTAB = 0.2) (gamma(LV) = 50 mN/m, C = 4.3 x 10(-5) M) +TX100 (C=10(8)-10(-2) M).