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.     

The modification of the triple helical structure of gelatin in aqueous solution I. The influence of anionic surfactants,pH-value,and temperature

The modification of the triple helical structure in aqueous gelatin solutions by changing pH and adding alkyl sulphates at 298 K and after rechilling the solution to 283 K was investigated by CD-measurement. At 298 K the triple helical content at the IEP of the gelatin has its maximum value. It is only weakly affected by adding sodium dodecyl sulphate (SDDS) at concentrations <10^–4 M/dm³. The unfolding of the triple helix affected by pH and SDDS is reversible by rechilling the solution. The triple helical content of gelatin solutions decreases at SDDS concentrations higher than 10^–4 M/dm³. In all cases the decrease of the amount of triple helical structure is connected with an increase of the cis-configuration in single chains and leads to chain reversals. At sufficiently high SDDS concentrations-sheets are formed. These changes are thermally irreversible. Sodium decyl sulphate (SDS) has a more minor influence than SDDS except in the range of the c.m.c. of SDS. At sufficiently high SDS concentrations,-turns appear.     

Properties of mixed protein/surfactant adsorption layers

The adsorption isotherms, adsorption kinetics and surface rheological properties of β-lactoglobulin, β-casein, in the absence and presence of Tween 20 were measured. To study the adsorption process (isotherms and kinetics) at the water–air interface the pendant drop technique (axial drop shape analysis, ADSA), and ring tensiometry were used. The surface shear rheological parameters were measured with a torsion pendulum set-up. Also, data of the equilibrium film thickness and surface diffusion coefficients obtained from fluorescence recovery after photobleaching (FRAP) measurements are used to understand the competitive adsorption mechanism. The adsorption process and shear rheological behaviour of the studied systems show a rather complex behaviour which depends most of all on the system's composition. At high protein or surfactant content the behaviour is controlled by the main component while for the more mixed systems the adsorption process is complex and consists of partial adsorption, surfactant–protein interaction and protein rearrangement as a function of surface coverage. The results obtained illustrate that all these processes must be taken into account in future new theoretical models to be derived for such systems.     

Rheology of interfacial layers

The response of interfacial layers to deformations in size and shape depends on their composition. The corresponding main mechanical quantities are elasticity and viscosity of dilation and shear, respectively. Hence, the interfacial rheology represents a kind of two-dimensional equivalent to the traditional bulk rheology. Due to growing interest in the quantitative understanding of foams and emulsions, more works are dedicated to studies on interfacial rheology. This overview presents the theoretical basis for traditional and recently developed experimental tools and discusses their application to different interfacial systems. While dilational rheology provides information on the composition of mixed interfacial layers, the shear rheology gives answers essentially on structures formed at an interface. The most frequently used methods at present are the oscillating drop and bubble tensiometry methods for dilational deformations and oscillating ring/bicone rheometers for shear deformations.     

Zum Scherverhalten unzerstörter Grenzflächenstrukturen gespreitetern-Octadecansäuremonoschichten und adsorbierter Gelatineschichten an fluiden Phasengrenzen

Zusammenfassung Eine Apparatur zur Bestimmung grenzflächenrheologischer Kriechkurven wird beschrieben.In Übereinstimmung mit theoretischen Analysen über die Beanspruchung der Phasengrenze durch einen die Grenzfläche berührenden Ring können minimal Oberflächenscherviskositäten von 10^–3 mNs/m hinreichend genau bestimmt werden.Die Funktionsfähigkeit der Apparatur wurde an ausgewählten Meßbeispielen demonstriert. Gespreiteten-Octadecansäuremonoschichten zeigen im Bereich der untersuchten Oberflächenkonzentrationen typisch Newtonsches Grenzflächenfließverhalten. Die für diese Systeme ermittelten Oberflächenscherviskositäten stimmen gut mit Literaturdaten überein. Die Reproduzierbarkeit beträgt 5–8%.Adsorbierte Gelatineschichten zeigen bereits bei sehr geringen Konzentrationen typisch viskoelastisches Verhalten. Bei Einhaltung eines strengen Meßregimes können grenzflächenrheologische Parameter mit einer Reproduzierbarkeit von 15–20% ermittelt werden.

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Summary An equipment for the measurement of interfacional rheologic creep curves is described. Minimal surface shear viscosities of 10^–3 mNs/m can be detected with sufficient accuracy in agreement with the theoretical analysis on the treatment of the interface with an interface-touching ring.Results are reported for different systems. Insoluble monolayers ofn-octadecanoic acid show a typical Newton surface flow in the interval of surface concentrations measured. The results are in good agreement with those of other equipments. The reproducibility is about 5–8%.Adsorbed gelatin-layers show typical viscoelastic behaviour at low concentrations. Surface theological parameters are determined with a reproducibility of about 15–20% by following a definite procedure of preparing the gelatinsolutions.

     

Consistency of surface mechanical properties of spread protein layers at the liquid–air interface at different spreading conditions

Π/A isotherms of spread β-lactoglobulin and β-casein at the air–water interface are measured under different spreading conditions. While the isotherms do not show drastic effects of the spreading concentration and the compression rate the interfacial shear rheological behaviour is significantly influenced. In particular, the shear viscosity of β-lactoglobulin layers depend directly on the spreading concentration. Significant viscosity increase is obtained at larger surface pressures when the spreading concentration is increased. In contrast the shear rheology of the spread β-casein layers can be normalised by plotting the viscosities as a function of the surface pressure Π. The different behaviour is discussed in terms of denaturation of the β-lactoglobulin during the monolayer formation process by adsorption from the spread thin protein solution layer.     

Stress relaxation behaviour of dipalmitoyl phosphatidylcholine monolayers spread on the surface of a pendant drop

Dipalmitoyl phosphatidylcholine (DPPC) monolayers were characterised by surface pressure/area isotherms (π/A) and surface dilational rheological parameters at temperatures 20–40°C. The methods used were the Langmuir trough and the pendant drop micro-film balance. The latter allows accurate measurements at higher temperatures and transient drop deformation. Stable DPPC monolayers were found only for low surface pressures, π<15 mN m⁻¹. At higher monolayer compression π decreases over a long time, mainly caused by molecular rearrangement processes in the monolayer starting in the coexisting region. At π>25 mN m⁻¹ and 20°C relaxation experiments give evident of rupturing, brittle monolayer structures. At higher temperatures the monolayers became more fluid-like. π/A-isotherms determined by using both methods principally agree with each other, but show also remarkable differences, which cannot be explained so far satisfactory. Transient drop relaxation experiments were analysed for the short time range (600 s). At 20°C the dilational modulus (_r) and the surface dilational viscosity (ξ_r) passes a stationary maximum at 0.54 nm² molecule⁻¹ and increase strongly at higher surface coverage, thus indicating crystalline monolayer structure. Increasing temperature from 20 to 30°C causes a rapid decrease of _r and ξ_r and a shift of the stationary maximum to lower surface coverage. No evidence for crystalline structure is found. Further increase of temperature causes _r and ξ_r increase again. This increase is caused by a rising relaxation time, while the elasticity does not change in the same manner. Such intermediate decrease of _r and ξ_r in the range 30–40°C appears to be unusual and can be interpreted as a consequence of strong DPPC interactions and strongly pronounced retardation of monolayer deformation. The study is discussed in connection to the physiology of breathing. For pulmonary surfactants the observed behaviour seems to be understandable. It is however interesting that such complex behaviour is observed for monolayers consisting of DPPC only.     

Gd<Superscript>3+</Superscript> binding of carboxylated polyglycidyl methacrylate latices and their colloidal stability

The binding of Gd³⁺ to two carboxylated polyglycidyl methacrylate latices was investigated. The latices differed in size (60 and 140 nm for CL6 and CL3, respectively) and surface charge density. The Gd³⁺ concentration in aqueous suspension was determined using an arsenazo (III) assay. Using ¹⁵³Gd³⁺, the bound amount was determined directly. Because of the high binding affinity, ligand depletion became evident. The binding was pH dependent, investigated in buffer solutions not influencing the arsenazo (III) assay. Optimal binding occurs by formation of sodium salts of the carboxylic groups and replacement of Na⁺ and H⁺ by Gd³⁺. The dissociation constants of the particles were k _D ≈ 5 × 10⁻⁵ mol/L (CL3) and 10⁻⁴ mol/L (CL6), without cooperativity (Hill plot). Colloidal stability was investigated. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.