On the dissolution of vapors and gases.

The captive bubble technique in combination with axisymmetric drop shape analysis (ADSA-CB) and with micro gas chromatography is used to study the dynamics of dissolution of different gases and vapors in water in situ. The technique yields the changes in the interfacial tension and bubble volume and surface. As examples, the dissolution of methanol and hexane vapors, inhaled anesthetic vapors, and gases, that is, diethyl ether, chloroform, isoflurane, enflurane, sevoflurane, desflurane, N2O, and xenon, and as nonimmobilizers perfluoropentane and 1,1,2-trichloro-1,2,2-trifluoro-ethane (R113) were investigated. The examination of interfacial tension-time and bubble volume-time functions permits us to distinguish between water-soluble and -insoluble substances, gases, and vapors. Vapors and gases generally differ in terms of the strength of their intermolecular interactions. The main difference between dissolution processes of gases and vapors is that, during the entire process of gas dissolution, no surface tension change occurs. In contrast, during vapor dissolution the surface tension drops immediately and decreases continuously until it reaches the equilibrium surface tension of water at the end of dissolution. The results of this study show that it is possible to discriminate anesthetic vapors from anesthetic gases and nonimmobilizers by comparing their dissolution dynamics. The nonimmobilizers have extremely low or no solubility in water and change the surface tension only negligibly. By use of newly defined molecular dissolution/diffusion coefficients, a simple model for the determination of partition coefficients is developed.

Interfacial properties of pulmonary surfactant layers.

The composition of the pulmonary surfactant and the border conditions of normal human breathing are relevant to characterize the interfacial behavior of pulmonary layers. Based on experimental data methods are reviewed to investigate interfacial properties of artificial pulmonary layers and to explain the behavior and interfacial structures of the main components during compression and expansion of the layers observed by epifluorescence and scanning force microscopy. Terms like over-compression, collapse, and formation of the surfactant reservoir are discussed. Consequences for the viscoelastic surface rheological behavior of such layers are elucidated by surface pressure relaxation and harmonic oscillation experiments. Based on a generalized Volmer isotherm the interfacial phase transition is discussed for the hydrophobic surfactant proteins, SP-B and SP-C, as well as for the mixtures of dipalmitoylphosphatidylcholine (DPPC) with these proteins. The behavior of the layers depends on both the oligomerisation state and the secondary structure of the hydrophobic surfactant proteins, which are controlled by the preparation of the proteins. An example for the surface properties of bronchoalveolar porcine lung washings of uninjured, injured, and Curosurf treated lavage is discussed in the light of surface behavior. An outlook summarizes the present knowledge and the main future development in this field of surface science.

Effects of oligomerization and secondary structure on the surface behavior of pulmonary surfactant proteins SP-B and SP-C.

The relationship among protein oligomerization, secondary structure at the interface, and the interfacial behavior was investigated for spread layers of native pulmonary surfactant associated proteins B and C. SP-B and SP-C were isolated either from butanol or chloroform/methanol lipid extracts that were obtained from sheep lung washings. The proteins were separated from other components by gel exclusion chromatography or by high performance liquid chromatography. SDS gel electrophoresis data indicate that the SP-B samples obtained using different solvents showed different oligomerization states of the protein. The CD and FTIR spectra of SP-B isolated from all extracts were consistent with a secondary structure dominated by alpha-helix. The CD and FTIR spectra of the first SP-C corresponded to an alpha-helical secondary structure and the spectra of the second SP-C corresponded to a mixture of alpha-helical and beta-sheet conformation. In contrast, the spectra of the third SP-C corresponded to antiparallel beta-sheets. The interfacial behavior was characterized by surface pressure/area (pi-A) isotherms. Differences in the oligomerization state of SP-B as well as in the secondary structure of SP-C all produce significant differences in the surface pressure/area isotherms. The molecular cross sections determined from the pi-A isotherms and from dynamic cycling experiments were 6 nm(2)/dimer molecule for SP-B and 1.15 nm(2)/molecule for SP-C in alpha-helical conformation and 1.05 nm(2)/molecule for SP-C in beta-sheet conformation. Both the oligomer ratio of SP-B and the secondary structure of SP-C strongly influence organization and behavior of these proteins in monolayer assemblies. In addition, alpha-helix --> beta-sheet conversion of SP-C occurs simply by an increase of the summary protein/lipid concentration in solution.

Beta-casein bilayer adsorption at the solution/air interface: experimental evidences and theoretical description.

Ellipsometric and surface pressure studies of beta-casein adsorption layers at the water/air interface support the idea of a model that assumes the formation of a second layer adjacent to the primary adsorption layer. A thermodynamic model describes the concentration behavior of the surface pressure and the adsorbed amount with one and the same set of model parameters over the entire concentration range studied.

Interfacial behaviour and mechanical properties of spread lung surfactant protein/lipid layers.

The surface behaviour of spread dipalmitoyl phosphatidyl choline (DPPC), lung surfactant protein C (SP-C), and their mixtures were characterised using a captive bubble surfactometer. The surface tension was determined by using axisymmetric bubble shape analysis. Surface dilatational rheological behaviour was characterised by sinusoidal oscillation of the bubble volume and at frequencies 0.006-0.025 Hz. The pi/A isotherms of DPPC, SP-C, and their mixtures were described with a generalised equation of state. Monolayer cycling of mixed DPPC/SP-C layers yields isotherms with a plateau in the range of 50-53 mN/m. When the surface pressure becomes higher SP-C is squeezed out of the film, but it re-enters the film upon expansion. Surface dilatational elasticities of DPPC films had a maximum at about 30 mN/m. At higher surface pressures, the films became brittle and the elasticity decreased. A slightly pronounced maximum was found at a surface pressure exceeding 55 mN/m. The dilatational viscosity had two distinct maxima, corresponding with those in the elasticity curves, i.e. one before the minimum area demand, and one in the range of over-compression. This was explained by the formation of a second ordered complex structure in the range of film over-compression. SP-C films show continuously increasing dilatational elasticities and viscosities with a maximum at f approximately 0.02 Hz. Mixed monolayers, DPPC+2 mol% SP-C, had dilatational elasticities increasing with surface pressure. In contrast to DPPC alone, an elasticity maximum appeared in the range of the squeeze out plateau. The dilatational viscosity had two distinct maxima as observed for DPPC, whereas the maximum before the squeeze out plateau is very broad like that of SP-C. The viscosity decreased for frequencies higher 0.02 Hz favouring elastic properties of the film. Our data provide experimental evidence that SP-C mixed with DPPC yield higher elasticities and viscosities as compared with films formed by the single components. This behaviour is likely to support breathing cycles, especially for the turn from inspiration to expiration and vice versa.

Effect of the Nonstationary Viscous Flow in the Capillary on Oscillating Bubble and Oscillating Drop Measurements.

The dynamic behavior of a bubble or drop oscillating at the tip of a capillary immersed in a surfactant solution is considered. The pressure variation in the cell and the nonstationary flow in the capillary are taken into account. The amplitude- and phase-frequency characteristics of the system are obtained, which contain information about the relaxation processes at the interface and in the bulk phases. Their dependency on the system geometry, the bulk properties of contacting media, and the viscoelastic properties of the interface is analyzed. Copyright 2000 Academic Press.

Bubble Oscillations in a Closed Cell.

A theoretical analysis is given to describe the behavior of an oscillating bubble in a closed measuring cell taking into account the finite liquid compressibility and the cell deformation. The results show that the behavior of a closed liquid cell can differ significantly from that of open cells. For example, under the same conditions two stable meniscus positions can be obtained in a closed cell. In a closed cell a meniscus larger than a hemisphere can be stable even when the gas compartment is open, while in an open cell such a meniscus is always unstable. For closed cells the meniscus can jump between the two equilibrium positions either randomly or under the influence of regular factors, such as external pressure, temperature, and surface tension changes. Relationships are obtained for the description of the pressure response on external harmonic perturbations which make it possible to determine the complex dilatational elasticity as a function of frequency. It is shown that the measured signal can depend on the cell properties, which should be taken into account in the interpretation of experimental data. Copyright 2000 Academic Press.

Surface Behavior of Spread Sodium Eicosanyl Sulfate Monolayers.

The surface behavior of spread sodium eicosanyl sulfate monolayers is characterized by determining the dilational moduli from different pi/A isotherms and from surface stress relaxation experiments in the short-time range (<10 min). The elasticities derived from the pi/A isotherms differ depending on the experimental conditions. The quasi-equilibrium isotherm displays a plateau in the range of coexistence of the condensed and the expanded phases and strong increases caused by the formation of a solid-like phase. In contrast, nonequilibrium pi/A isotherms yield effective elasticities showing a maximum within the phase coexistence range. The formation of a solid phase cannot be detected because of the onset of monolayer collapse. Different stress relaxation experiments were carried out for monolayer compression and dilation using transient drop volume jumps. Depending on the experimental run, these experiments lead to consistent and complementary results with those derived from pi/A isotherms under comparable conditions. The stress recoveries yield a relaxation time, a dilation viscosity, and a parameter characterizing the homogeneity of the relaxation process. The stress relaxation is interpreted accounting for both the nonequilibrium between the monolayer and the bulk phase and the nonequilibrium within the monolayer. The influence of alkylsulfate hydrolysis on the presented results was checked. It was found that within the time scale of the experiments no influence of hydrolysis could be detected. Copyright 1998 Academic Press.