Nanoscale Structure of the Oil-Water Interface.

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. The XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

In situ x-ray reflectivity studies on the formation of substrate-supported phospholipid bilayers and monolayers.

We conducted time-dependent, in situ x-ray reflectivity measurements on the formation of substrate-supported lipid monolayers and bilayers at solid-liquid interfaces, buried under an aqueous buffer with various concentrations (5, 10, 20, 40, and 50 microg/ml ) of lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The DOPC bilayer is formed on the hydrophilic surface of a bare Si substrate, while the DOPC monolayer is formed on a hydrophobic octadecylthricholorsilane (OTS) monolayer-coated Si substrate. The evolution of the reflectivity curves from the lipid bilayers is well described by lateral growth of bilayer islands, consistent with the rupture and fusion model for the adsorption of lipid vesicles to solid-liquid interfaces. By contrast, the formation of the lipid monolayer on OTS-coated Si occurs through a relatively fast coverage of the entire interfacial area, followed by an increase in the monolayer thickness. For both monolayers and bilayers, the rate of lipid layer growth increases with increasing lipid concentration in the buffer solution.

Thin-thick coexistence behavior of 8CB liquid crystalline films on silicon.

The wetting behavior of thin films of 4-n-octyl-4'-cyanobiphenyl (8CB) on Si is investigated via optical and x-ray reflectivity measurement. An experimental phase diagram is obtained showing a broad thick-thin coexistence region spanning the bulk isotropic-to-nematic (T(IN)) and the nematic-to-smectic-A (T(NA)) temperatures. For Si surfaces with coverages between 47 and 72 +/- 3 nm, reentrant wetting behavior is observed twice as we increase the temperature, with separate coexistence behaviors near T(IN) and T(NA). For coverages less than 47 nm, however, the two coexistence behaviors merge into a single coexistence region. The observed thin-thick coexistence near the second-order NA transition is not anticipated by any previous theory or experiment. Nevertheless, the behavior of the thin and thick phases within the coexistence regions is consistent with this being an equilibrium phenomenon.

Confinement-induced order of tethered alkyl chains at the water/vapor interface.

Packing of tethered alkyl chains in Langmuir monolayers of a hairy-rod polypeptide poly[gamma-4-(n-hexadecyloxy)benzyl alpha,L-glutamate] on water has been studied by x-ray scattering measurements at room temperature. The rods lie parallel to the surface while the alkyl side chains segregate toward the vapor. Results indicate that the herringbone order of the alkyl chains is established initially by one-dimensionally confined chains between aligned rods and grows laterally with compression.