Effects of spontaneous curvature on interfacial adsorption and collapse of phospholipid monolayers.

Abstract

To function effectively, pulmonary surfactant must adsorb rapidly to the alveolar air/water interface but avoid collapse from the surface when compressed to high interfacial densities. Prior studies show that phospholipids in the cylindrical monolayers of the inverse hexagonal (H_II) phase adsorb quickly. The monolayers have negative curvature, defined by the concave shape of the hydrophilic face. Formation of the H_II structures, however, involves significant disruption of chain-packing. Samples with significant spontaneous curvature, formed in the absence of applied force, may nonetheless have lamellar structures that optimize chain-packing. The experiments here tested whether planar lamellar bilayers formed by phospholipids with negative spontaneous curvature might adsorb rapidly but collapse slowly. Prior studies have shown that binary mixtures of dioleoyl phosphatidylcholine-dioleoyl phosphatidylethanolamine (DOPC-DOPE) with higher mol fractions of DOPE (X_PE) have more negative spontaneous curvature. Samples of DOPC-DOPE with higher X_PE studied here adsorbed more rapidly but also collapsed more quickly. Over that range of X_PE, small-angle X-ray scattering showed only lamellar structures. The H_II phase was undetectable. The results suggest that the innate tendency of the phospholipids to form curvature has primary importance for adsorption rather than the presence of the H_II phase. Planar structures are insufficient to minimize the tendency of spontaneous curvature to promote collapse. These findings are consistent with adsorption and collapse that occur via rate-limiting transient structures with significant negative curvature.NEW & NOTEWORTHY Pulmonary surfactant must adsorb rapidly to the surface of the alveolar liquid but collapse slowly when compressed. Prior studies show that cylindrical monolayers of the inverse hexagonal phase adsorb rapidly. These structures have negative curvature; the hydrophilic face of the phospholipid leaflet is concave. Our studies tested whether planar lamellar structures with a greater tendency to form negative curvature would adsorb rapidly but collapse slowly. Compositional change accelerated adsorption but also yielded faster collapse.