Theoretical description of mixed film formation at the air/water interface : carboxylic acids–fatty amines

Thermodynamic parameters of mixed monolayer formation of aliphatic amines CnH2n+1NH2 and carboxylic acids CnH2n+1COOH (n = 6–16) are calculated using the quantum chemical semiempirical PM3 method. Four types of mixed dimers and tetramers amine–acid are considered. The total contribution of interactions between the hydrophilic parts of amine and acid into clusterization Gibbs energy is slightly lower than the corresponding interactions for individual surfactants. It suggests a synergetic interaction between the regarded amphiphilic compounds as proved by experimental data in the literature. Two types of competitive film formation are possible: mixed 2D film 1, where the molecules of the minor component are single distributed among the molecules of the prevailing second component (mixture of components on molecular level), and 2D film 2 with a domain structure comprised of pure component “islands” linked together. The dependence of the Gibbs energy of clusterization per monomer for 2D film 1 on the component mole fraction shows that the maximum synergetic effect is typical for the case that both surfactants have the same even number of carbon atoms in the hydrocarbon chain and form an equimolar mixture. Formation of 2D film 1 is more preferable than that of 2D film 2, if the difference of the hydrocarbon chain lengths is not larger than 5 methylene units. The limiting mole fraction of carboxylic acids in such mixed monolayers is 66.7%

Cooperative effects in surfactant adsorption layers at water/alkane interfaces

In the present work, the properties of dodecyl dimethyl phosphine oxide (C12DMPO) at the water/decane interface are studied and compared with those obtained earlier at the interface to hexane. To simulate the interfacial behavior, a two-component thermodynamic model is proposed, which combines the equation of state and Frumkin isotherm for decane with the reorientation model involving the intrinsic compressibility for the surfactant. In this approach, the surface activity of decane is governed by its interaction with C12DMPO. The theory predicts the influence of decane on the decrease of the surface tension at a very low surfactant concentration for realistic values of the ratio of the adsorbed amounts of decane and surfactant. The surfactantrsquo;s distribution coefficient between the aqueous and decane phases is determined. Two types of adsorption systems were used: a decane drop immersed into the C12DMPO aqueous solution, and a water drop immersed into the C12DMPO solution in decane. To determine the distribution coefficient, a method based on the analysis of the transfer of C12DMPO between water and decane is also employed

Lipase-catalyzed Reactions at Interfaces of Two-phase Systems and Microemulsions

This work describes the influence of two polar lipids, Sn-1/3 and Sn-2 monopalmitin, on the activity of lipase in biphasic systems and in microemulsions. In previous communications, we have shown that Sn-2 monoglycerides can replace Sn-1,3 regiospecific lipases at the oil–water interface, causing a drastically reduced rate of lipolysis. We here demonstrate that even if the lipase is expelled from the interface, it can catalyze esterification of the Sn-2 monoglyceride with fatty acids in both macroscopic oil–water systems and in microemulsions, leading to formation of di- and triglycerides