Lateral Intermolecular Forces between Biomembrane Lipids in Two Dimensions: 1,2-Dipalmitin at the Heptane/Water Interface Compared with Phospholipids

Abstract

The lateral interaction forces between phospholipids in two-dimensional arrays are fundamental to understanding membrane biophysics. In previous studies the related thermodynamic functions have been measured for spread phospholipid monolayers at the oil/water interface over a range of temperatures and densities, and the two-dimensional virial coefficients obtained. These coefficients have been computed from a model that emphasizes the head group zwitterion interactions. In this study we examine the contribution of the diglyceride portion of phospholipid molecules to the lateral intermolecular forces. Measurements of the heptane/water interfacial tension as a function of the concentration of 1,2-dipalmitoyl glycerol (DP) in the heptane were made over a range of low surface pressures at 25 degrees C. Infrared measurements on the DP solutions show that the solutions are ideal. The results are interpreted to give two-dimensional virial coefficients for the adsorbed monolayer. The second virial coefficient B2(T) for DP is +0.31 nm2/molecule, in marked contrast to the much larger positive values found for the corresponding phospholipids at the same interface and temperature, and clearly indicating an attractive component to the lateral potentials of mean force between pairs of DP molecules. The contribution of the diglyceride moiety to the pair potentials of the phospholipids thus appears to be minor but not negligible. The differences in the second virial coefficients for DP and the phospholipids are interpreted primarily in terms of the orientation of the ester carbonyl dipoles, also drawing on spectroscopic and diffraction evidence from related structures.