The Equilibria of Phosphatidylethanolamine-Cholesterol and Phosphatidylcholine–Phosphatidylethanolamine in Monolayers at the Air/Water Interface

Monolayers of phosphatidylethanolamine (PE), cholesterol (Ch), phosphatidylcholine (PC), and binary mixtures (PC-PE or PE-Ch) were investigated at the air/water interface. The surface tension values of pure and mixed monolayers were used to calculate π -A isotherms. The surface tension measurements were carried out at 20°C using an improved Teflon trough and a Nima 9000 tensiometer. The Teflon trough was filled with a subphase of triple-distilled water. Known amounts of lipid dissolved in 1-chloropropane were placed at the surface using a syringe. The interactions between phosphatidylethanolamine and cholesterol as well as phosphatidylcholine and phosphatidylethanolamine result in significant deviations from the additivity rule. An equilibrium theory to describe the behavior of monolayer components at the air/water interface was developed in order to obtain the stability constants of PC-PE and PE-Ch complexes. We considered the equilibrium between the individual components and the complex and established that phosphatidylethanolamine and cholesterol as well as phosphatidylcholine and phosphatidylethanolamine formed highly stable 1:1 complexes.     

Dynamic Study of Gemini Surfactant and Single-chain Surfactant at Air／Water Interface

Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl-trimethylammonium bromide (DTAB) at the air/water interface, respectively. In the two systems,t he surfactant concentrations are both 28 wt.%, and other conditions are also the same. After reaching the thermodynamic equilibrium, the concentration profiles, the radial distributions functions (RDF) and the mean squared displacement (MSD) are investigated. The results reveal that the surface activity of C12C2C12 surfactant is higher than DTAB surfactant.     

Interfacial Behaviors of Azocalixarene Derivatives at the Air/Water Interface and Photochromism in the Langmuir-Blodgett Films

The azocalixarenes is a novel chromogenic compound and their spectra properties have been reported. A number of them have been applied as selective ionophores in extractive process1 or as selective ligands in ion selective electrodes and optical sensors based on spectra changes2. Some amphiphilic azocalixarene derivatives with hydrophobic long alkyl chains were synthesized and their interfacial behaviors at the air / water interface have also been investigated3. However, the photochromism of t…     

Preparation of Langmuir-Blodgett Film of Oligophenylenevinylene at the Air/Water Interface and Study on its Fluorescence

Phenylenevinylene polymers and oligomers were widely investigated as active materialsused in emission layer of light emitting diodes (LEDs), recently, due to their conductingand luminescent properties1-3. Comparing with their polymers, oligophenyl ene-vin…     

Host–Guest Complexation of Amphiphilic Molecules at the Air–Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen

The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host–guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A-12C) and negatively charged oleic acid (OA), a well-known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air–water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field-induced droplet ionization mass spectrometry results have demonstrated that the host–guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes.     

Mutual influence of cetyltrimethylammonium bromide and Triton X-100 on their adsorption at the water–air interface

On the basis of surface tension values of the aqueous solution of cetyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) mixtures measured at 293 K as a function of CTAB or TX-100 concentration at constant TX-100 or CTAB concentration, respectively, the real surface area occupied by these surfactants at the water–air interface was established which is inaccessible in the literature. It appeared that at the concentration of the CTAB and TX-100 mixture in the bulk phase corresponding to the unsaturated monolayer at the water air-interface this area is the same as in the monolayer formed by the single surfactant at the same concentration as in the mixture. In the saturated mixed monolayer at this interface the area occupied by both surfactants is lower than that in the single surfactant monolayer corresponding to the same concentration in the aqueous solution. However, the decrease of the CTAB adsorption is lower than that of TX-100 and the total area occupied by the mixture of surfactants is also lower than that of the single one. The area of particular surfactants in the mixed saturated monolayer changes as a function of TX-100 and CTAB mixture concentration and at the concentrations close to CMC or higher the area occupied by both surfactants is the same. The changes of the composition of the mixed surface monolayer are connected with the synergetic effect in the reduction of the water surface tension by the adsorption of CTAB and TX-100 at the water–air interface. This effect was confirmed by the values of the standard Gibbs free energy of adsorption of both individual surfactants and their mixtures with different compositions in the bulk phase determined by using the Langmuir equation if RT instead of nRT was applied in this equation.     

Theoretical Investigation of the Photoexcited NO2+H2O reaction at the Air–Water Interface and Its Atmospheric Implications

The atmospheric role of photochemical processes involving NO₂ beyond its dissociation limit (398 nm) is controversial. Recent experiments have confirmed that excited NO₂^* beyond 420 nm reacts with water according to NO₂^*+H₂O→HONO+OH. However, the estimated kinetic constant for this process in the gas phase is quite small (k≈10⁻¹⁵–3.4×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹) suggesting minor atmospheric implications of the formed radicals. In this work, ab initio molecular dynamics simulations of NO₂ adsorbed at the air–water interface reveal that the OH production rate increases by about 2 orders of magnitude with respect to gas phase, attaining ozone reference values for NO₂ concentrations corresponding to slightly polluted rural areas. This finding substantiates the argument that chemistry on clouds can be an additional source of OH radicals in the troposphere and suggests directions for future laboratory experimental studies.     

Solubility of Ketoconazole in Polyethylene Glycol 200 + Water Mixtures at 298.2–318.2 K

The solubility of ketoconazole in binary mixtures of polyethylene glycol 200 (PEG 200) + water is reported at temperatures ranging from 298.2 to 318.2 K. The Jouyban–Acree model and its combined version including the van’t Hoff equation were used for correlating the reported data; the obtained mean relative deviations are 9.5 and 9.9 %, respectively. Also, two previously trained versions of the Jouyban–Acree model were used for predicting the reported data points in which the prediction errors were 34.6 and 31.0 %.     

Solution Thermodynamics of Piroxicam in some Ethanol + Water Mixtures and Correlation with the Jouyban–Acree Model

The solubility of piroxicam (PIR) in several ethanol + water mixtures was determined at five temperatures from 293.15 to 313.15 K. The thermodynamic functions; Gibbs energy, enthalpy, and entropy of solution and of mixing were obtained from these solubility data and the drug properties of fusion by using the van’t Hoff and Gibbs equations. The greatest solubility value was obtained in pure ethanol. A non-linear enthalpy–entropy relationship was observed from a plot of enthalpy versus Gibbs energy of solution. Accordingly, the driving mechanism for PIR solubility in water-rich mixtures is the entropy, probably due to water-structure loss around the drug’s non-polar moieties by ethanol, whereas, in ethanol-rich mixtures the driving mechanism is the enthalpy, probably due to better PIR solvation by the co-solvent molecules. The solubilities and the derived thermodynamic properties in mixed solvents were correlated using the Jouyban–Acree model.     

Micellization and surface activity of Triton X-100 in water–orthophosphoric medium

The adsorption isotherms of Triton X-100 for air/water–orthophosphoric acid interfaces were determined by the stripping method. The surface chemical parameters, Γ_max, F and ΔG°_A, and the aggregation ones, CMC and the ΔG_M, are determined in different H₂O/H₃PO₄ mixtures. For concentrations higher than 4 M, the values of the CMC, ΔG_M, Γ_max and ΔG°_A increase with increasing acid concentrations due to the occurring changes in the medium structure. ©2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASsurface tension / non-ionic surfactant / micellization / orthophosphoric acid     

Voltammetric Probing of Molecular Assemblies of Ubiquinone-10 at the Air–Water Interfaces

The redox properties of ubiquinone 10 (UQ10) placed at the air–water interface were studied using the horizontal touching method with a thin mercury film (TMFE) working electrode and cyclic voltammetry. Changes of pH of the subphase affected the formal potential of the ubiquinone/ubiquinol system exhibiting the participation of protons in the overall reduction of UQ10. The protonation of the semiquinone transition product was found to be the rate determining step. This explains the dependence of the rate constant value on pH. The highest values of rate constants were found at pH over 13. Under these conditions the mechanism of the process is different. The concentration of protons is small, and the availability of the counter ions (i.e., K⁺) becomes crucial for the kinetics of reduction. Their role is to neutralize the negative charge of the redox group following its reduction. The logarithm of rate constants was found to decrease linearly with the increase of surface concentration of ubiquinone. This reflects the influence of intermolecular interactions in the monolayer on the kinetics of the electrode process.     

Synthesis of Calix[4]arene Derivatives Containing a Nucleobase and their Interaction with Complementary Nucleosides at the Air–Water Interface

Amphiphilic calix[4]arene derivatives with a nucleobase on the lower rim have been synthesized in good yields by the condensation of calix[4]arenediamine {5,11,17,23-tetra-tert-butyl-25,27-bis(2-aminoethoxy)-26,28-dihydroxycalix[4]arene} with uracilo-N-acetic acid, thymino-N-acetic acid and adenino-N-propionic acid in the presence of CDI in DMF. Monolayers of the amphiphilic calix[4]arene-nucleobase derivatives on the surface of pure water, the aqueous subphases containing complementary nucleosides, were studied by film balance measurement and relaxation experiments. LB films deposited from all subphases were investigated by UV spectra and FT-IR spectroscopy. All the results indicate that the interaction between the nucleobases in the headgroup of amphiphilic p-tert-butylcalix[4]arene derivatives and the complementary nucleosides in the subphase takes place through multiple hydrogen bonding and the nucleosides can be transferred to solid substrates along with their monolayers.     

Concentration Dependences of the Surface Tension and Density of Solutions of Acetone–Ethanol–Water Systems at 293 K

Russian Journal of Physical Chemistry A - Concentration dependences of the surface tension and density of solutions of three-component acetone–ethanol–water systems and the bounding...     

Solubility and Solution Thermodynamics of Some Sulfonamides in 1-Propanol + Water Mixtures

The solubilities of sulfadiazine (SD), sulfamerazine (SMR) and sulfamethazine (SMT) in some 1-propanol + water co-solvent mixtures were measured at five temperatures from 293.15 to 313.15 K over the polarity range provided by the aqueous solvent mixtures. The mole fraction solubility of all these sulfonamides was maximal in the 0.80 mass fraction of 1-propanol solvent mixture (δ _solv = 28.3 MPa^1/2) and minimal in water (δ = 47.8 MPa^1/2) at all temperatures studied. The apparent thermodynamic functions Gibbs energy, enthalpy, and entropy of solution were obtained from these solubility data by using the van’t Hoff and Gibbs equations. Apparent thermodynamic quantities of mixing were also calculated by using the ideal solubilities reported in the literature. Nonlinear enthalpy–entropy relationships were observed for these drugs in the plots of enthalpy versus Gibbs energy of mixing. The plot of ?_mix H° versus ?_mix G° shows different trends according to the slopes obtained when the mixture compositions change. Accordingly, the mechanism for the solution process of SD and SMT in water-rich mixtures is enthalpy driven, whereas it is entropy driven for SMR. In a different way, in 1-propanol-rich mixtures the mechanism is enthalpy driven for SD and SMR and entropy driven for SMT. Ultimately, in almost all of the intermediate compositions, the mechanism is enthalpy driven. Nevertheless, the molecular events involved in the solution processes remain unclear.     

Adsorption Kinetics of Alkyl Polyglucoside at the Air—Solution Interface

The air-solution equilibrium tension γe and dynamic surface tension γt,of nonionic surfactant alkyl polyglucoside have been studied. γe was measured by the Wilhelmy method with Rruess K12 tensiometer. The CMC and the surface excesses T were determined from the surface tension vs. concentration curve. The γt decays were measured in the range 0.2-20s using a maximum bubble pressure instrument and analyzed with the Ward and Tordai equation.     

Synthesis of Novel Amphiphilic Poly （ester-amine） Dendrimers and Their Recognition of Hg2＋ at the Air／Water Interface

Two novel amphiphilic poly(ester-amine)dendrimers were synthesized and characterized by 1H NMR,13C NMR and IR spectra.Their properties of Langmuir film were investigated at the air/water interface.The relationship between the surface pressure and area isotherms of the dendrimers was found to be dependent on the nature of subphases,Interaction between HgCl2 and the dendrimers was observed,indicating that the amphiphilic dendrimers could act as a sensor for Hg^2 .     

Surface Tension Measurements for Binary Mixtures of Chlorobenzene or Chlorocyclohexane + Tetrahydrofuran at 298.15 K

Surface tensions (σ) for the binary mixtures chlorocyclohexane + tetrahydrofuran and chlorobenzene + tetrahydrofuran at 298.15 K and 1.013 bar have been determined as a function of the mole fraction. In order to analyze the surface tension behavior, the extended Langmuir (EL) and Shereshefsky models were used and parameters of the models were obtained for these mixtures. The standard Gibbs energy of adsorption (\( - \Delta G^{\circ} \)) was calculated using both models. The Gibbs energy change for replacing 1 mol of solute with 1 mol of solvent in the surface region (?G _S), and the excess number of molecular layers of solute in the surface region, were calculated using Shereshefsky’s model. The magnitudes of ?G _S and \( - \Delta G^{\circ} \) are discussed in terms of the nature and type of intermolecular interactions in the binary mixtures.     

Molecular Orientation of a Nematic Liquid Crystal Induced by Mixing with Tetraalkylcalix[4]resorcinarenes at the Air–Water Interface

O-Octacarboxymethoxylated tetraalkylcalix[4]resorcinareanes (CRA-CMs) formed stable monolayers on a water surface, whereas their -A isotherms were affected by the length of the alkyl residues. A double-layered structuring was observed for CRA-CM having four undecyl substituents (11CRA-CM) by compression, though CRA-CM with four eicosyl residues formed a stable monomolecular film. 11CRA-CM possessed the ability to form a host–guest monolayer film with liquid crystalline 4,4'-dihexylazobenzene at the air/water interface, leading to perpendicular orientation of C6Azo. The host–guest mixed monolayers displayed a double-layered structuring by compression.