Surface rheology of monolayers of phospholipids and cholesterol measured with axisymmetric drop shape analysis

Surface rheology of monolayers of a saturated phospholipid (dipalmitoylphosphatidylcholine, DPPC), an unsaturated phospholipid (dioleoylphosphatidylcholine, DOPC) and cholesterol is studied with axisymmetric drop shape analysis at the argon/water interface. Measurement techniques for lipids are described in detail. Profile analysis tensiometry (PAT) is used to determine the film pressure Π, surface elasticity and surface dilational viscosity of monolayers upon sinusoidal oscillations of the drop surface for various amplitudes a and frequencies f to assess their dependence on these dynamic parameters. It is shown that surface dilational viscosity strongly depends on the frequency and decreases by a factor 2–5 with increasing f in the considered range. Dilational viscosity is higher the more the monolayer approaches a relaxed state. Thus, the molecular interactions are stronger in the relaxed than in the stressed state. Surface elasticity is much less dependent on dynamic conditions. For DPPC a minimum of the dynamic surface elasticity is found for f = 12.5 mHz (at Π = 17.5 mN m−1) which coincides well with the relaxation frequencies measured in stress relaxation experiments. The dynamic surface elasticity of DPPC exhibits a plateau in the range 13.5 mN m−1 ≤ Π ≤ 27 mN m−1 in good coincidence with the phase boundaries of the coexistence region of micron-sized liquid crystalline domains surrounded by a fluid monolayer phase. In equilibrium measurements (Π/A-isotherms) a plateau of the film pressure is seen at the lower bound and a break at the upper bound of the coexistence region. Film pressure/area isotherms produced by PAT and a Langmuir film balance closely coincide as is shown in a comparison to literature values. However, the surface elasticities measured dynamically with oscillating surfaces widely deviate from those derived from isotherms in the case of DPPC and cholesterol, whereas for DOPC very good agreement can be found.