Effects of surface pressure on the structure of distearoylphosphatidylcholine monolayers formed at the air/water interface.

The structure of the monolayer formed at an air/water interface by the phospholipid distearoylphosphatidylcholine (DSPC) has been determined as a function of the monolayer surface pressure (pi) using Brewster angle microscopy and neutron reflectivity. The microscopy studies demonstrate that the DSPC molecules form an extremely homogeneous monolayer on the water surface with no evidence of any domain formation. The neutron reflectivity measurements provide information on the thickness of the DSPC alkyl chains, head groups, and associated solvent distributions, along with the separations between these distributions and the interfacial area per molecule. Partial structure factor analyses of the reflectivity data show that the area occupied by each DSPC molecule decreases from 49 A2 at pi = 20 mN/m to 44 A2 at pi = 50 mN/m. There are concomitant increases in the widths of the lipids' alkyl chains and headgroup distributions (modeled as Gaussians), with the former rising from 18 A (at pi = 20 mN/m) to 20 A (at pi = 50 mN/m) and the latter rising from 14 A (at pi = 20 mN/m) to 18 A (at pi = 50 mN/m). The compression of the monolayer is also shown to give rise to an increased surface roughness, the principal component of which is found to be the thermal roughness caused by capillary waves. At all surface pressures studied (covering the range from 20 to 50 mN/m), the alkyl chains and head groups of the DSPC are found to have roughly the same orientations, with the alkyl chains tilted with respect to the surface normal by about 34 degrees and the head groups lying parallel to the interface normal, projecting vertically down into the aqueous subphase. Given the various trends noted on how the structure of the DSPC monolayer changes as a function of pi, we extrapolate to consider the structure of the monolayer immediately before its collapse.