Kyungil Kim

Observation of surface layering in a nonmetallic liquid.

Oscillatory density profiles (layers) have previously been observed at the free surfaces of liquid metals but not in other isotropic liquids. We have used x-ray reflectivity to study a molecular liquid, tetrakis(2-ethylhexoxy)silane. When cooled to T/Tc approximately 0.25 (well above the freezing point for this liquid), density oscillations appear at the surface. Lateral order within the layers is liquidlike. Our results confirm theoretical predictions that a surface-layered state will appear even in dielectric liquids at sufficiently low temperatures, if not preempted by freezing.

Observation of an organic-inorganic lattice match during biomimetic growth of (001)-oriented calcite crystals under floating sulfate monolayers.

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.

Synchrotron X-ray studies of rapidly evolving morphology of self-assembled nanoparticle films under lateral compression.

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.

Reduced Water Density in a Poly(ethylene oxide) Brush.

A model poly(ethylene oxide) (PEO) brush system, prepared by spreading a poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PnBA) amphiphilic diblock copolymer onto an air-water interface, was investigated under various grafting density conditions by using the X-ray reflectivity (XR) technique. The overall electron density profiles of the PEO-PnBA monolayer in the direction normal to the air-water interface were determined from the XR data. From this analysis, it was found that inside of the PEO brush, the water density is significantly lower than that of bulk water, in particular, in the region close to the PnBA-water interface. Separate XR measurements with a PnBA homopolymer monolayer confirm that the reduced water density within the PEO-PnBA monolayer is not due to unfavorable contacts between the PnBA surface and water. The above result, therefore, lends support to the notion that PEO chains provide a hydrophobic environment for the surrounding water molecules when they exist as polymer brush chains.

Ultrastable-Stealth Large Gold Nanoparticles with DNA Directed Biological Functionality

The stability of gold nanoparticles (AuNPs) in biological samples is very important for their biomedical applications. Although various molecules such as polystyrenesulfonate (PSS), phosphine, DNA, and polyethylene glycol (PEG) have been used to stabilize AuNPs, it is still very difficult to stabilize large AuNPs. As a result, biomedical applications of large (30-100 nm) AuNPs are limited, even though they possess more favorable optical properties and are easier to be taken up by cells than smaller AuNPs. To overcome this limitation, we herein report a novel method of preparing large (30-100 nm) AuNPs with a high colloidal stability and facile chemical or biological functionality, via surface passivation with an amphiphilic polymer polyvinylpyrrolidone (PVP). This PVP passivation results in an extraordinary colloidal stability for 13, 30, 50, 70, and 100 nm AuNPs to be stabilized in PBS for at least 3 months. More importantly, the PVP capped AuNPs (AuNP-PVP) were also resistant to protein adsorption in the presence of serum containing media and exhibit a negligible cytotoxicity. The AuNP-PVPs functionalized with a DNA aptamer AS1411 remain biologically active, resulting in significant increase in the uptake of the AuNPs (∼12,200 AuNPs per cell) in comparison with AuNPs capped by a control DNA of the same length. The novel method developed in this study to stabilize large AuNPs with high colloidal stability and biological activity will allow much wider applications of these large AuNPs for biomedical applications, such as cellular imaging, molecular diagnosis, and targeted therapy.

A comparative study of Langmuir surfactant films: Grazing incidence x-ray off-specular scattering vs. x-ray specular reflectivity

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-ra...

Governing factors in stress response of nanoparticle films on water surface

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.

Aggregation-governed oriented growth of inorganic crystals at an organic template

X-ray studies performed during the growth of CdCO(3) and MnCO(3) crystals from supersaturated aqueous solutions, at fatty acid monolayer templates, reveal that the nucleates are nearly three-dimensional powders below a threshold supersaturation. However, at higher supersaturations, the crystals are preferentially oriented with the {0 1 2} direction vertical. Scanning electron microscope images of samples transferred to substrates show discrete crystals at low concentrations, while at higher concentrations the crystals self-aggregate to form linear chains and sheets. The authors speculate that preferential alignment at the organic-inorganic interface is enhanced as a consequence of oriented aggregation of crystals. The role of monolayer-ion interactions in governing the morphologies and the resulting orientation of the inorganic nucleate is discussed.

Epitaxy driven interactions at the organic-inorganic interface during biomimetic growth of calcium oxalate

During oriented biomimetic crystallization of calcium oxalate monohydrate under floating fatty acid monolayers, the (01) surface structure is initially compressed and epitaxial with the monolayer lattice. The surface subsequently relaxes to the bulk structure and the monolayer expands, reestablishing a lattice match. These interactions were observed in situ using synchrotron X-ray diffraction.

Effects of Chitosan on the Morphology and Alignment of Calcite Crystals Nucleating Under Langmuir Monolayers

The growth of calcium carbonate crystals under Langmuir monolayers was investigated in the presence of chitosan, a soluble derivative of chitin added to the subphase to better simulate the polyelectrolyte-containing in vivo environment. Chitosan causes distinct concentration-dependent changes in the orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.