Molecular organization in two-dimensional films of liquid I. Langmuir films of binary mixtures of liquid crystals with a crystalline mixtures terminal cyano group

The Langmuir films of two liquid crystal materials, 4-octyl-4'-cyanobiphenyl (8CB) and 4-pentyl-4"-cyano-p-terphenyl (5CT), and of their mixtures have been studied by recording surface pressure-area isotherms and Brewster angle microscopy (BAM) images. The pure liquid crystals revealed very different characters of the surface pressure-area isotherms indicating different organization of the molecules and different molecular interactions in the monolayer at the water-air interface. The surface pressure-area isotherms of Langmuir films formed from 8CB/5CT mixtures give evidence for phase separation of the components over the whole range of molar fractions. Similar conclusions have been drawn on the basis of BAM image analysis.     

Molecular organization in two-dimensional films of liquid I. Langmuir films of binary mixtures of liquid crystals with a crystalline mixtures terminal cyano group

The Langmuir films of two liquid crystal materials, 4-octyl-4'-cyanobiphenyl (8CB) and 4-pentyl-4"-cyano-p-terphenyl (5CT), and of their mixtures have been studied by recording surface pressure-area isotherms and Brewster angle microscopy (BAM) images. The pure liquid crystals revealed very different characters of the surface pressure-area isotherms indicating different organization of the molecules and different molecular interactions in the monolayer at the water-air interface. The surface pressure-area isotherms of Langmuir films formed from 8CB/5CT mixtures give evidence for phase separation of the components over the whole range of molar fractions. Similar conclusions have been drawn on the basis of BAM image analysis.     

Phase behavior of 2,3-disubstituted methyl octadecanoate monolayers at the air-water interface

The phase behavior of 2,3-disubstituted methyl octadecanoate monolayers at the air-water interface is studied by film balance and a Brewster angle microscope (BAM). The comparison of the surface pressure-molecular area (pi-A) isotherms with the corresponding BAM images provides information on the phase behavior of the monolayers. Variations in the phase behavior of different 2,3-disubstituted methyl octadecanoate monolayers can be correlated with the size of the headgroups, the interactions between the polar molecular moieties and the subphase, and the intermolecular interactions. The enlarging of the headgroups makes forming a condensed monolayer difficult for the molecules, even after introduction of substituents giving rise to the formation of hydrogen bonds between the molecules, which may balance the steric repulsion and stabilize the monolayers. Model calculations of the two-dimensional lattice structure of the 2,3-disubstituted methyl octadecanoates on basis of the pg and p1 space group are performed and correspond well with the experimental results.     

Incorporation and exclusion of long chain alkyl halides in fatty acid monolayers at the air-water interface

Mixed monolayers of deuterated palmitic acid C(15)D(31)COOH (dPA) and deuterated stearic acid C(17)D(35)COOH (dSA) with 1-bromoalkanes of different alkyl chain length (C(4) to C(16)) at the air-water interface were investigated. Alkanes and 1-chlorohexadecane ClC(16)H(33) (ClHex) were also studied to compare the effects of the halogen on the mixed monolayers. Surface pressure-area isotherms and Brewster angle microscopy (BAM) were used to obtain the organization and phase behavior, providing a macroscopic view of the mixed monolayers. A molecular-level understanding of the interfacial molecular organization and intermolecular interactions was obtained by using vibrational sum frequency generation (SFG) spectroscopy and infrared reflection-absorption spectroscopy (IRRAS). It was found that from the alkyl halide molecules investigated 1-bromopentadecane, BrC(15)H(31) (BrPent), 1-bromohexadecane, BrC(16)H(33) (BrHex), and ClHex incorporate into the fatty acid monolayers. Alkanes of 15- and 16-carbon chain length do not incorporate into the fatty acid monolayer, which suggests that the halogen is needed for incorporation. Isotherms and spectra suggest that BrHex molecules are squeezed out, or excluded, from the fatty acid monolayer as the surface pressure is increased, while BAM images confirm this. Additionally, SFG spectra reveal that the alkyl chains of both fatty acids (dPA and dSA) retain an all-trans conformation after the incorporation of alkyl halide molecules. BAM images show that at low surface pressures BrHex does not affect the two-dimensional morphology of the dPA and dSA domains and that BrHex is miscible with dPA and dSA. We also present for the first time BAM images of BrHex deposited on a water surface, which reveal the formation of aggregates while the surface pressure remains unchanged from that of neat water.     

Organized collapse structures in mixtures of chiral ethyl 2-azido-4-fluoro-3-hydroxystearates

Monolayers of enantiomeric compounds as well as diastereomeric mixtures and racemic/diastereomeric mixtures of ethyl 2-azido-4-fluoro-3-hydroxystearates have been investigated using surface pressure-area isotherms and Brewster angle microscopy. All monolayers collapse out of the liquid-expanded phase, forming 3D collapse structures which were visualized with scanning force microscopy. The enantiomeric compound and the diastereomeric mixtures form unique fiber-like network structures with heights between 20 and 40 nm. Interestingly, the shape of the enantiomeric fiber structures is straight, whereas the diastereomeric mixtures exhibit curved fibers of different sizes. The racemic mixture however forms circular 10 nm high and 20-50 microm broad structures. The shape of unconventional collapse structures could be changed by using distinct ratios of diastereomeric or racemic/diastereomeric mixed compounds.     

Biodegradable poly(dl-lactide)/poly(ε-caprolactone) mixtures: Miscibility at the air/water interface

Mixtures of biodegradable polymers, poly(dl-lactide) and poly(ε-caprolactone) monolayers at the air/water interface have been studied. Surface pressure-area isotherms of poly(dl-lactide), poly(ε-caprolactone) and their mixtures were obtained by monolayer compression at constant temperature. The behavior of the mixed monolayers was analyzed according to the classical addition rule. Good agreement was observed between experimental and ideal behavior except for one composition where a negative deviation was observed. The polymer monolayer miscibility was corroborated by comparison between the surface pressure-area isotherms of the random copolymers (dl-lactide-co-ε-caprolactone) and their mixtures at the same compositions. Brewster angle microscopy (BAM) shows homogeneity in the monolayers in the whole range of compositions. These results also confirm the miscibility of the mixtures.     

Monolayer characteristics of mixed octadecylamine and stearic acid at the air/water interface

Mixed monolayers of stearic acid (SA) and octadecylamine (ODA) at the air/water interface were investigated in this article. The miscibility of the two compounds was evaluated by the measurement of surface pressure-area per molecule (pi-A) isothems and the direct observation of Brewster angle microscopy (BAM) on the water surface. The two compounds were spread individually on the subphase (method 1) or premixed first in the spreading solvent and then cospread (method 2). The effect of spreading method on the miscibility of the two compounds was also studied. The results show that the mixed monolayers prepared by method 1 cannot get a well-mixed state. The isotherms of mixed monolayers preserve both characteristics of SA and ODA and exhibit two collapse points. The calculated excess surface area is very small. Besides, distinguished domains corresponding to those of pure SA and ODA can be inspected from the BAM images. Such results indicate that SA and ODA cannot get a well-mixed phase via 2-dimensional mixing. On the contrary, in the mixed monolayer prepared by cospreading, the two compounds exhibit high miscibility. In the pi-A isotherms, the individual characteristics of SA and ODA disappear. The calculated excess area exhibits a highly positive deviation which indicates the existence of special interaction between the two compounds. The low compressibility of isotherm implies the highly rigid characteristic of the mixed monolayer. which was also sustained by the striplike collapse morphology observed from the BAM. The rigid characteristic of SA/ODA mixed monolayer was attributed to the formation of "catanionic surfactant" by electrostatic adsorption of headgroups of SA and ODA or to the formation of salt by acid-base reaction.     

Anisotropic aggregation and phase transition in Langmuir monolayers of methyl/ethyl esters of 2,3-dihydroxy fatty acids

We studied interfacial properties of a series of methyl and ethyl esters of enantioenriched syn-2,3-dihydroxy fatty acids with different chain lengths at the air-water interface, using a Langmuir type film balance and a Brewster angle microscope (BAM). After analyzing their surface pressure (Pi)-area (A) isotherms, we inferred that these molecules existed as an E conformation in the liquid-expanded (LE) phase of monolayers, and the E conformation of molecules changed into a Z conformation during the LE-LC transition in a monolayer. BAM images evidenced the formation of elongated LC aggregates. This is possibly induced by the intermolecular hydrogen bonds, leading to the anisotropic growth of LC domains, on the basis of the FT-IR spectroscopy data. The enthalpy change of the LE-LC phase transition is considered to result from the three types of intermolecular interactions at the air-water interface during compression of these amphiphiles. These findings are discussed in terms of various physical factors that influenced intermolecular interactions and macroscopic aggregations of these amphiphiles.     

Rigid films of an anionic porphyrin and a dialkyl chain surfactant

The 2D complex formed at the air-water interface between the dialkyl chain cationic surfactant, dihexadecyldimethylammonium bromide, and the anionic porphyrin, tetrakis-(4-sulfonatophenyl) porphine, was studied using surface pressure-area isotherms as well as X-ray and neutron reflection measurements. The surface structure of these films was determined by the use of simultaneously constrained analysis of the neutron and X-ray reflectometry data and BAM images. Isotopic contrast variation methods were employed to enhance the information content of the neutron reflection data. The rigid complex forms at the interface due to the electrostatic interaction between the cationic headgroups of the surfactant and the anionic functional groups at the meso position of the porphyrin. The surface pressure-area isotherms show three distinct regions on compression: an initial condensed phase that ends with a pressure peak at 36 mN m-1, a second plateau region of high compressibility, and a final condensed phase. BAM images show that at the beginning of the plateau region in the isotherm there is complete surface coverage by a monolayer. The constrained simultaneous fitting of neutron and X-ray data measured just prior to and after the pressure peak shows a structurally similar 2D complex at the interface. Modeling of X-ray reflectometry data also reveals that in the final high-pressure phase the film has folded to form a trilayer. The conclusion is that the plateau region of the isotherm is due to the formation of trilayer surface coverage through localized buckling or folding, and that after this is complete there is some condensation before final film collapse.     

Semifluorinated chains at the air/water interface: studies of the interaction of a semifluorinated alkane with fluorinated alcohols in mixed langmuir monolayers

Mixtures of a semifluorinated alkane 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-henicosafluorotriacontane (abbr. F10H20) and different alcohols were investigated at the air/water interface using surface pressure-area isotherms complemented with BAM images. In our studies, octadecanol and its fluorinated derivatives differing in the degree of fluorination were researched. To verify the influence of an iso branching of the fluorinated segment in an alcohol molecule, the properties of perfluorooctyldecanol and perfluoro-iso-nonyldecanol in mixtures with F10H20 were compared. From the isotherms datapoints, the excess of free energy of mixing (DeltaG(exc)) together with the interaction parameter (alpha) were calculated. On the basis of the additivity rule and BAM images, phase diagrams for all of the investigated systems were constructed. It occurs that F10H20 mixes with the fully hydrogenated alcohol, octadecanol, within the whole range of alcohol mole fractions, whereas it is completely immiscible with its perfluorinated analogue. Regarding the mixtures of F10H20 with semifluorinated alcohols, it turned out that these systems exhibit limited miscibility, i.e., are miscible at a low semifluorinated alcohol proportion, whereas upon increasing alcohol content, the systems start to demix. It may be concluded that the molecular packing in mixed monolayers is the key factor determining the miscibility of F10H20 of the investigated alcohols.     

Temperature dependence of the organization and molecular interactions within phospholipid/diacetylene Langmuir films

Surface pressure-area isotherms and Brewster angle microscopy images of mixed binary films of dimyristoylphosphatidylcholine (DMPC) and the diacetylene 10,12-tricosadiynoic acid (TRCDA) were recorded at different temperatures and mole ratios to investigate the molecular interactions and cooperative properties of the films. The experiments revealed that segregation, on the one hand, and significant intermolecular interactions, on the other hand, both contribute to the thermodynamic properties of the phospholipids and the diacetylene assemblies. In particular, the data demonstrate that higher temperatures and greater percentage of DMPC promote repulsion between the liquid-condensed phospholipid monolayer and the TRCDA domains. In contrast, at high TRCDA mole ratios, film contraction occurred (lower molecular areas) due to TRCDA multilayer formation (at high temperature) or intermolecular affinities (at low temperature).     

Influence of hydrophobic alkylated gold nanoparticles on the phase behavior of monolayers of DPPC and clinical lung surfactant

The effect of hydrophobic alkylated gold nanoparticles (Au NPs) on the phase behavior and structure of Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) and Survanta, a naturally derived commercial pulmonary surfactant that contains DPPC as the main lipid component and hydrophobic surfactant proteins SP-B and SP-C, has been investigated in connection with the potential implication of inorganic NPs in pulmonary surfactant dysfunction. Hexadecanethiolate-capped Au NPs (C(16)SAu NPs) with an average core diameter of 2 nm have been incorporated into DPPC monolayers in concentrations ranging from 0.1 to 0.5 mol %. Concentrations of up to 0.2 mol % in DPPC and 16 wt % in Survanta do not affect the monolayer phase behavior at 20 °C, as evidenced by surface pressure-area (π-A) and ellipsometric isotherms. The monolayer structure at the air/water interface was imaged as a function of the surface pressure by Brewster angle microscopy (BAM). In the liquid-expanded/liquid-condensed phase coexistence region of DPPC, the presence of 0.2 mol % C(16)SAu NPs causes the formation of many small, circular, condensed lipid domains, in contrast to the characteristic larger multilobes formed by pure lipid. Condensed domains of similar size and shape to those of DPPC with 0.2 mol % C(16)SAu NPs are formed by compressing Survanta, and these are not affected by the C(16)SAu NPs. Atomic force microscopy images of Langmuir-Schaefer-deposited films support the BAM observations and reveal, moreover, that at high surface pressures (i.e., 35 and 45 mN m(-1)) the C(16)SAu NPs form honeycomb-like aggregates around the polygonal condensed DPPC domains. In the Survanta monolayers, the C(16)SAu NPs were found to accumulate together with the proteins in the liquid-expanded phase around the circular condensed lipid domains. In conclusion, the presence of hydrophobic C(16)SAu NPs in amounts that do not influence the π-A isotherm alters the nucleation, growth, and morphology of the condensed domains in monolayers of DPPC but not of those of Survanta. Systematic investigations of the effect of the interaction of chemically defined NPs with the lipid and protein components of lung surfactant on the physicochemical properties of surfactant films are pertinent to understanding how inhaled NPs impact pulmonary function.     

Adsorption behavior of glucose oxidase on a dipalmitoylphosphatic acid monolayer and the characteristics of the mixed monolayer at air/liquid interfaces

A dipalmitoylphosphatic acid (DPPA) monolayer at the air/liquid interface is used as a binding layer to incorporate glucose oxidase (GOx) from the subphase. The effects of the adsorption time of GOx on the behavior of the mixed DPPA/GOx monolayer and the relevant structure of the mixed LB film were studied using the characteristics of the pressure-area (pi-A) isotherm, Brewster angle microscopy (BAM), and atomic force microscopy (AFM). The experimental results show that two equilibrium states of GOx adsorption exist in the presence of a DPPA monolayer. The first equilibrium stage occurs at tens of minutes after spreading of DPPA, and a surface pressure of ca. 7.5 mN/m is obtained. The second equilibrium stage approaches slowly, and a higher equilibrium surface pressure (ca. 16 mN/m) was obtained at ca. 8 h after the first stage. The BAM and AFM images show that, after the second equilibrium stage is reached, a more condensed phase and rough morphology are obtained on the mixed DPPA/GOx monolayer, indicating a higher amount of GOx incorporated into the mixed film. For the first equilibrium stage of GOx adsorption, DPPA molecules can still pack regularly and closely under compression, suggesting that GOx molecules are mainly located beneath the DPPA monolayer at the compressed state. A more uniform phase was detected on a film prepared after the first equilibrium stage was reached. The present result indicates that distinct structures and properties of mixed DPPA/GOx films can be prepared from the various stages of GOx adsorption.     

Miscibility of gramicidin A-ethyl nonadecanoate in langmuir monolayers in the presence of salts dissolved in the subphase

The behavior of binary mixed Langmuir monolayers from gramicidin A (GA) and ethyl nonadecanoate (EN), spread on aqueous subphases containing NaCl and CaCl2, was investigated on the basis of the analysis of surface pressure-average area per molecule (pi-A) isotherms complemented with Brewster angle microscopy (BAM) images. Compression modulus versus surface pressure (C(S-1)-pi) curves indicate the existence of interactions in the GA-EN mixed monolayers at low surface pressures (below 5 mN m(-1)). However, for mixtures in which the ester is the predominant component, both GA and EN are miscible within regions from fully expanded to collapse. To examine the interactions between both components in the studied system, values of the mean molecular area per molecule (A12) were plotted as a function of molar fraction of gramicidin A (X(GA)). A12-X(GA) plots exhibit negative deviations from ideality at high surface pressures, wherein beta-helices of GA are vertically oriented in respect to the interface. However, at surface pressures below the plateau transition, which is due to reorientation of GA, the binary system obeys the additive rule. Brewster angle microscopy (BAM) was applied for a direct visualization of the monolayers morphologies. The obtained images prove that for molar ratios of GA > or = 0.3 and at surface pressures above 5 mN m(-1), both components are immiscible at the interface. The observed negative deviations from the additively rule were attributed to the formation of a three-dimensional phase in the mixed film, which provokes its contraction at the interface.     

Conformational changes of a calix[8]arene derivative at the air-water interface

The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules.     

Interactions of a fluoroaryl surfactant with hydrogenated, partially fluorinated, and perfluorinated surfactants at the air/water interface

A novel surfactant containing pentafluorophenyl moiety attached at the terminal position of undecanol (11,11-difluoro-11-(pentafluorophenyl)undecan-1-ol, abbr. PBD) was synthesized and employed for the Langmuir monolayer characterization and miscibility studies with a semifluorinated alkane (perfluorodecyleicosane, abbr. F10H20) and four alcohols differing in the degree of fluorination in their hydrophobic chains: octadecanol (C18OH), perfluorooctyldecanol (F8H10OH), perfluoroisononyldecanol (iF9H10OH) and 1H,1H-perfluorooctadecanol (F18OH). Pure monolayers of all of the investigated surfactants as well as their mixtures were investigated with surface pressure-area isotherms complemented by Brewster angle microscopy (BAM) images. PBD was found to form stable Langmuir monolayers of liquid-expanded character. Characteristic dendritic structures were formed at the very early stage of compression and remained up to the vicinity of collapse, where 3D crystallites appeared. 2D miscibility studies revealed that PBD forms mixed monolayers with the investigated semifluorinated alkane (F10H20) as well as with perfluorinated alcohol (F18OH) within the whole composition range, do not mix with octadecanol to the fully hydrogenated alcohol, whereas it is partially miscible (up to a certain surface pressure value) with the studied semifluorinated alcohols. The analysis of the miscibility derived from the surface pressure-area isotherms (collapse pressure vs composition dependencies) agrees well with BAM images. Molecular interactions in the investigated systems have been quantified with interaction parameter, alpha.     

Polymerization of a cysteinyl peptidolipid Langmuir film

The surface pressure-area isotherm of a cysteinyl peptidolipid on a pure water subphase (pH 5.8) was compared with that on a water subphase saturated with oxygen and buffered with ammonium bicarbonate (pH 7.8). A reduction of the limiting molecular area was observed for the isotherm measured on the subphase saturated with oxygen. Hysteresis in the compression-decompression cycles of the Langmuir film was also observed. Taking into consideration the chemical structure of the peptidolipid, we rationalized that the free sulfhydryl groups of the peptidolipid were oxidized in the presence of oxygen in the alkaline subphase to form intermolecular disulfide bonds at the air-water interface. The surface topography of the peptidolipid Langmuir film was observed by epi-fluorescence microscopy and the Langmuir-Blodgett film by environmental scanning electron microscopy (ESEM). The micrographs showed evidence of the polymerization of the cysteinyl peptidolipid at the air-water interface. Furthermore, the XPS spectra of the Langmuir-Blodgett films also proved the existence of disulfide bonds. The control peptidolipid C(18)-Ser-Gly-Ser-OH showed identical surface pressure-area isotherms in the presence or absence of an oxygen-saturated subphase.     

Role of electrostatic interactions for the domain shapes of Langmuir monolayers of monoglycerol amphiphiles

The role of electrostatic interaction in the domain morphology of amide, ether, ester, and amine monoglycerol monolayers (abbreviated as ADD, ETD, ESD, and AMD, respectively) with systematic variation in the molecular structure of the headgroup region is investigated. Experimental studies using Brewster angle microscopy (BAM) and grazing incidence X-ray diffraction (GIXD) show that the characteristic features of the condensed monolayer phase, such as domain morphology, crystallinity, and lattice parameters, are very different for these monoglycerols. Therefore, the intermolecular interactions of the four amphiphilic monoglycerols are investigated in detail. First, the dipole moments of four monoglycerols of similar structure but with different functional groups are calculated by a semiempirical quantum mechanical technique. The dipole moments for monoglycerols follow the sequence AMD < ETD < ESD < ADD for the population of conformers of compounds investigated. The dipolar repulsion energies for the amphiphilic monoglycerols are also calculated for different possible mutual orientations between the dipoles. The calculated dipolar energies also follow the same trend for different possible headgroup orientations. These results can explain the domain shape of the monoglycerols observed experimentally. Second, ab initio calculations on the basis of the HF/6-31G** method are performed for representative monoglycerol headgroup segments. The results show that the intermolecular interaction energy related to dimer formation follows the order ETD < ESD < AMD < ADD segments, similar to that observed in experiment except in the case of the AMD segment. The relative importance of intra- and intermolecular hydrogen bonding in dimers is analyzed. The enhanced role of the intermolecular interaction relative to intramolecular interaction in the case of AMD contributes to the relatively high intermolecular interaction energy for the particular conformation of the dimer of AMD segment as observed from ab initio calculation. The present work shows that the variations in headgroup molecular structure alter drastically the domain shape, and the theoretical calculations conclusively reveal the important role of the electrostatic interactions for the mesoscopic domain architecture.     

HPLC study of the adsorption from solutions on two silicagels

Summary In this paper, we report and discuss the adsorption isotherms of hydro-organic mixtures and of compounds used as mobile phase in reversed phase and normal phase high performance liquid chromatography (RP-HPLC and NP-HPLC, respectively). This work is the first attempt to study the solid-liquid interface between two types of chromatographic silica surfaces and pure organic adsorbates from water and from organic eluents by HPLC. Frequently, among the dynamic techniques the method of choice for the measurement of an adsorption isotherm is frontal analysis. We suggest here the combination of the technique based on peak asymmetry calibration and peak profiles, which allows calculations directly from integration data. The group of systems studied permits the analysis of the intermolecular interactions on the silica surface. Particular attention was given to the system methanol-water and the measurement of the adsorption ofn-octanol from methanol on RP-silica was also carried out.     

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.