Fukumo, MasafumiHeilmann, Ralf K.Pershan, PeterYu, Seungju M.Griffiths, Jennifer A.Tirrell, David A.2013-02-281999Fukumo, Masafumi, Ralf K. Heilmann, Peter S. Pershan, Seungju M. Yu, Jennifer A. Griffiths, and David A. Tirrell. 1999. Structure of poly(\(\gamma\)-benzyl-L-glutamate) monolayers at the gas–water interface: A Brewster angle microscopy and x-ray scattering study. Journal of Chemical Physics 111(21): 9761-9777.0021-9606http://nrs.harvard.edu/urn-3:HUL.InstRepos:10356598This 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 \(\alpha\)-helical poly(\(\gamma\)-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 > \(\sim\) 21  Å\(^2\)/monomer, surface pressure \(\Pi\) = 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  Å\(^2\)/monomer first leads to full and uniform surface coverage by the monolayer, followed by a steep rise in \(\Pi\) that is accompanied by a decrease in the interhelix distance. Further compression results in a plateau of constant \(\Pi\) in the \(\Pi\)-A isotherm ( \(\sim\) 11.5 < A < \(\sim\) 18.5  Å\(^2\)/monomer, \(\Pi\) \(\sim\) 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 \(\sim\)15 interhelix distances, implying short-range order.en-USmonolayerspolymer structurex-ray scatteringoptical microscopyJournal Article2013-02-2810.1063/1.480312