Interactions in monolayers: a study of the behavior of poly(methyl methacrylate)-lysozyme mixed films from surface pressure-area and ellipsometric measurements.

Mixed monolayers of PMMA-lysozyme show the existence of negative deviations from the additivity of the molecular areas (A(m)) when the composition of polymer mixtures is less than X(PMMA) 0.6, regardless of the surface pressure of the monolayers. The maximum deviation occurs in the mixed monolayer with composition X(PMMA) 0.25, which is attributed to the formation of a complex consisting of one polymer molecule and three protein molecules (1:3 stoichiometry), stabilized by hydrogen bonds between the NH groups of the protein and the CO groups of the polymer as well as by van der Waals attractive forces between the hydrocarbon chains of both components. When the relative proportion of the components in the mixed films significantly differs from the value corresponding to the stoichiometry of the complex (as in mixtures with X(PMMA) > 0.6), this complex cannot be formed, causing an immiscible system where the values of the experimental molecular areas coincide with those corresponding to ideal behavior. Measurements of monolayer thickness and BAM images allow confirmation on the microscopic level of the structural characteristics deduced from the π-A isotherms.

Approach to knowledge of the interaction between the constituents of contact lenses and ocular tears: mixed monolayers of poly(methyl methacrylate) and dipalmitoyl phosphatidyl choline.

Mixed monolayers of poly(methyl methacrylate) (PMMA), the main component of hard contact lenses, and dipalmitoyl phosphatidyl choline (DPPC), a characteristic phospholipidic constituent of ocular tear films, were selected as an in vitro model in order to observe the behavior of contact lenses on the eye. Using Langmuir monolayer and Brewster angle microscopy (BAM) techniques, the interaction between both components was analyzed from the data of surface pressure-area isotherms, compressional modulus-surface pressure, and relative film thickness versus time elapsed from the beginning of compression, together with BAM images. Regardless of the surface pressure at which the molecular/monomer areas (A(m)) were recorded, the A(m) mole fractions of PMMA (X(PMMA)) plots show that the experimental results match the theoretical values calculated from additivity rule A(m) = X(PMMA)A(PMMA) + X(DPPC)A(DPPC). The application of the Crisp phase rule to the phase diagram of the PMMA-DPPC system can explain the existence of a mixed monolayer made up of miscible components with ideal behavior at surface pressures below 25 mN/m. However, at very high surface pressures, when collapse is reached (at 60 mN/m), the single collapsed components are segregated into two independent phases. These results allows us to argue that PMMA hard contact lenses in the eye do not alter the structural characteristics of the phospholipid (DPPC) in tears.

Interactions between polymers and lipid monolayers at the air/water interface: surface behavior of poly(methyl methacrylate)-cholesterol mixed films.

The behavior of mixed monolayers of cholesterol and poly(methyl methacrylate) (PMMA) with molecular weights of M(w) = 120,000 g/mol and M(w) = 15,000 g/mol was investigated at the air/water interface using Langmuir and Brewster angle microscopy techniques. From the data of surface pressure (pi)-area (A) isotherms, compressional modulus-surface pressure (C(s)(-1)-pi) curves, and film thickness, complemented with Brewster angle microscopy images, the interaction between the components was analyzed. Regardless of the surface pressure (pi = 10, 20, or 30 mN/m) at which the mean molecular/monomer areas (Am) were calculated, the Am-mole fraction plots (corresponding to X(PMMA) = 0.1, 0.3, 0.5, 0.7, and 0.9) show that all the experimental points obtained are placed on the theoretical straight line calculated according to the additivity rule. This fact, together with the existence of two collapses in the mixed monolayers and with the fact that the surface pressure of the liquid-expanded LE-L'E phase transition of PMMA does not change with the monolayer composition, demonstrates the immiscibility of the film components at the interface. The application of the Crisp phase rule to the phase diagram of PMMA-cholesterol mixed monolayers helps to explain the existence of a biphasic system, regardless of their composition and surface pressure. Besides, Brewster angle microscopy (BAM) images showed the existence of heterogeneous cholesterol domains with high reflectivity immersed in a homogeneous polymer separate phase with low reflectivity.