Neutron reflectivity experiments on the interface of pure D2O against thin films of perdeuterated polystyrene (d-PS) spin-coated onto silicon blocks were performed to study the intrinsic structure of the interface of water against hydrophobic substrates. The experiments reveal nonvanishing scattering contrast at the polymer/water interface, although the two materials (d-PS and D2O) have closely similar scattering length densities. Organic (nondeuterated) contaminants or macroscopic air bubbles trapped at the polymer/water interface can be ruled out as the origin of this observation. From a systematic study of this system, it is concluded that the source of the nonvanishing contrast is a depletion of water in the boundary layer against the hydrophobic surface. It is conjectured that this depletion layer represents a precursor layer of submicroscopic gas bubbles recently observed by Tyrrell and Attard. The existence of such gas nanobubbles in the present system is confirmed by atomic force microscopy (AFM) of the surface of d-PS coatings in contact with bulk water. The thickness of the precursor gas layer as determined by neutron reflectometry is 2−5 nm, depending on the level of air saturation of the water sample and on the time elapsed after contacting it with the hydrophobic surface.

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The sequential adsorption of oppositely charged polyelectrolytes called the "layer by layer" technique is a method for formation of ultrathin films with controlled thickness and interfacial properties. Composition of polyelectrolyte solutions, pH, and electrolyte concentration are important parameters governing formation of multilayer films. Since pH is the factor controlling charge of weak polyelectrolytes, the structure of multilayers should be sensitive to its value. In this paper we focused on formation of PE multilayer films composed from weak and strong polyelectrolytes. We used weak, branched polycation polyethyleneimine (PEI, 70 kDa) and strong polyanion poly-4-styrenesulfonate (PSS, 70 kDa) to form films by the layer-by-layer technique on the surface of silicon wafers under two deposition conditions: pH = 6 when PEI was strongly charged and pH = 10.5 when the charge density of PEI was low. Thicknesses of films were measured by single wavelength ellipsometry, and the results were confronted with ones concerning mass of the adsorbed films obtained by quartz crystal microbalance. We found that, depending on pH of the solutions, combination of weakly and strongly charged polyelectrolytes gave either linear or nonmonotonic increase of film thickness with a number of deposited PE layers. We observed a good correlation between multilayer film thickness and adsorbed mass. The atomic force microscopy images of surface topography of PEI/PSS films demonstrated large differences between films deposited at pH = 6 and 10.5. Additionally the cyclic voltamperometry was used to determine the differences in permeability of films formed at various pH conditions.

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The surface properties of human meibomian lipids (MGS), the major constituent of the tear film (TF) lipid layer, are of key importance for TF stability. The dynamic interfacial properties of films by MGS from normal eyes (nMGS) and eyes with meibomian gland dysfunction (dMGS) were studied using a Langmuir surface balance. The behavior of the samples during dynamic area changes was evaluated by surface pressure-area isotherms and isocycles. The surface dilatational rheology of the films was examined in the frequency range 10(-5) to 1 Hz by the stress-relaxation method. A significant difference was found, with dMGS showing slow viscosity-dominated relaxation at 10(-4) to 10(-3) Hz, whereas nMGS remained predominantly elastic over the whole range. A Cole-Cole plot revealed two characteristic processes contributing to the relaxation, fast (on the scale of characteristic time τ < 5 s) and slow (τ > 100 s), the latter prevailing in dMGS films. Brewster angle microscopy revealed better spreading of nMGS at the air-water interface, whereas dMGS layers were non-uniform and patchy. The distinctions in the interfacial properties of the films in vitro correlated with the accelerated degradation of meibum layer pattern at the air-tear interface and with the decreased stability of TF in vivo. These results, and also recent findings on the modest capability of meibum to suppress the evaporation of the aqueous subphase, suggest the need for a re-evaluation of the role of MGS. The probable key function of meibomian lipids might be to form viscoelastic films capable of opposing dilation of the air-tear interface. The impact of temperature on the meibum surface properties is discussed in terms of its possible effect on the normal structure of the film.

We studied the properties of polyelectrolyte multilayer films prepared using the technique of polyelectrolyte deposition from solution (dipping) or supplying the solutions to the surface by spraying. The quality of films obtained by those two techniques was compared to find out whether the well-established dipping procedure can be replaced with the spraying technique. Neutron and X-ray reflectometric studies were performed on the samples of interest. We found that multilayers prepared by dipping are thicker, denser and less rough than films having the same number of layers, i.e., having the same number of deposition cycles, obtained by spraying.

Polyelectrolyte multilayer (PE) deposition and S-layer technology have been combined to make novel robust biomimetic surfaces and membranes. Isolated subunits of the bacterial cell surface layer from Bacillus sphaericus CCM2177 SbpA was self-assembled on PE multilayer supports, with the composition of the multilayer playing a crucial role in determining the structure of the resulting supported protein layers. Flat substrates were studied using atomic force microscopy and neutron reflectometry; protein on suitable PE combinations showed a crystalline structure with lattice constants equal to those found in vivo on bacterial surfaces. The mechanical stability of the S-layer is higher when recrystallized on PEs than directly on silicon supports. The recrystallization process was subsequently used to coat colloidal particles, permitting the determination of zeta potentials before and after coating. Hollow capsules could also be coated in the same way, as proven by various techniques. Our results suggest that electrostatic interactions via divalent cations are important for the assembly process. The results also demonstrate that the versatility of the PE multilayer membranes can be successfully combined with the well-defined surface chemistry and structure of 2D protein crystals.