Surface monolayers assembled on a liquid sub-phase represent a class of systems that is of great interest for studies of phase transitions in quasi-2D systems, chemical self-assembly, surfactant behavior, and biologically relevant monolayers and membranes. X-ray scattering is ideal for studying structural, dynamic, and mechanical properties of these surface monolayers at nanoscale due to the penetrating ability and short wavelength of x-rays. We show here that grazing incidence x-ray off-specular scattering (GIXOS) provides rapid access to in-plane and out-of-plane nanoscale structure, surface fluctuating modes, and potentially bending stiffness. We show that analysis of GIXOS data is highly sensitive to resolution effects. We further present detailed analysis of GIXOS from phospholipid 1,2-dipalmitoyl-phosphatidyl-choline C40H80NO8P (DPPC) and obtain quantitative, angstrom-resolution details of electron density profile normal to the surface that is comparable to those that are obtained from specular x-ray reflectivity measurements. We compare these GIXOS results to x-ray reflectivity measurements performed on the same samples. While electron density and main structural characteristics (such as monolayer thickness) obtained by GIXOS agree with x-ray reflectivity results, the interfaces of GIXOS-derived density profiles are found to be systematically sharper than those obtained with x-ray reflectivity. The possible reasons for these differences are discussed.
The mechanical properties of self-assembled silver nanoparticle (Ag-NP) films at the air-liquid interface are studied using both visible light optics and x-ray scattering techniques. The response of such films to compression is compared with results from previously studied gold nanoparticle (Au-NP) films, showing many similarities, along with significant differences. Possible factors governing the stress response of nanoparticle films are discussed.
Interfacial nanostructures represent a class of systems that are highly relevant to studies of quasi-2D phases, chemical self-assembly, surfactant behavior, and biologically relevant membranes. Previous studies have shown that under lateral compression a Langmuir film of gold (Au) nanoparticles assembled at the liquid-air interface exhibits rich mechanical behavior: it undergoes a rapid structural and morphological evolution from a monolayer to a trilayer via an intermediate hash-like phase. We report the results of studying this structural evolution using grazing incidence X-ray off-specular scattering (GIXOS). We utilize GIXOS to obtain a quantitative mapping of electron density profile normal to the liquid surface with a subnanometer resolution and follow the structural evolution of the Au nanoparticle film under lateral compression with a subminute temporal resolution. As the surface pressure is increased, the self-assembled nanoparticle monolayer first crinkles into a double-layer phase before forming a trilayer. This study reveals the existence of a transient bilayer phase and provides a microscopic picture of the particle-level crinkling phenomena of ultrathin films. These studies were previously impossible due to the relatively short time scales involved in crinkling formation of these transient phases and their intrinsically inhomogeneous nature.
Macromolecular layers rich in amino acids and with some sulfated polysaccharides appear to control oriented calcite growth in living organisms. Calcite crystals nucleating under floating acid monolayers have been found to be unoriented on average. We have now observed directly, using in situ grazing incidence X-ray diffraction, that there is a 1:1 match between the monolayer unit cell and the unit cell of the (001) plane of calcite. Thus, sulfate head groups appear to act as templates for the growth of (001)-oriented calcite crystals, which is the orientation commonly found in biominerals.
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