Structure of poly(γ-benzyl-L-glutamate) monolayers at the gas–water interface: A Brewster angle microscopy and x-ray scattering study

Abstract

This paper reports Brewster angle microscopy (BAM), x-ray specular reflectivity (XR), grazing incidence diffraction (GID) and off-specular diffuse scattering (XOSDS) measurements of Langmuir monolayers formed on water by both mono- and polydisperse samples of α-helical poly(γ-benzyl L-glutamate) (PBLG) as a function of area/monomer A. The microscopic behavior does not exhibit any discernible effects due to differing dispersity. At low surface densities (A>∼21 Å2/monomer, surface pressure Π=0), BAM images reveal partial surface coverage by solidlike monolayer islands. GID measurements show an interhelix peak corresponding to a local parallel alignment of rodlike PBLG molecules, indicating their tendency to aggregate laterally without external pressure. Compression to A<21 Å2/monomer first leads to full and uniform surface coverage by the monolayer, followed by a steep rise in Π that is accompanied by a decrease in the interhelix distance. Further compression results in a plateau of constant Π in the Π-A isotherm (∼11.5<A<∼18.5 Å2/monomer, Π∼9 dyn/cm), which has previously been attributed to a first-order monolayer–bilayer transition. The interfacial electron density profiles determined by the XR measurements on both sides of the coexistence plateau provide direct evidence for this transition. On the basis of x-ray scattering results, the film on the high-density side of the plateau is shown to consist of a newly formed incomplete and incommensurate second layer that sits on top of and has lower average density than a homogeneous first layer. GID measurements indicate that the second layer can be characterized by larger interhelix d-spacing than the first layer, while XOSDS measurements on the bilayer suggest that the second layer is microscopically inhomogeneous. For both mono- and bilayers, the analysis of observed GID peak widths indicates that the extent of lateral positional correlations between parallel PBLG rods ranges from a few to no more than ∼15 interhelix distances, implying short-range order.