Publications

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The biocompatibility and possible toxicological consequences of engineered nanomaterials, including quantum dots (QDs) due to their unique suitability for biomedical applications, remain intense areas of interest. We utilized advanced imaging approaches to characterize the interactions of CdSe QDs of various sizes and shapes with live immune cells. Particle diffusion and partitioning within the plasma membrane, cellular uptake kinetics, and sorting of particles into lysosomes were all independantly characterized. Using high-speed total internal reflectance fluorescence (TIRF) microscopy, we show that QDs with an average aspect ratio of 2.0 (i.e., rod-shaped) diffuse nearly an order of magnitude slower in the plasma membrane than more spherical particles with aspect ratios of 1.2 and 1.6, respectively. Moreover, more rod-shaped QDs were shown to be internalized into the cell 2-3 fold more slowly. Hyperspectral confocal fluorescence microscopy demonstrates that QDs tend to partition within the cell membrane into regions containing a single particle type. Furthermore, data examining QD sorting mechanisms indicate that endocytosis and lysosomal sorting increases with particle size. Together, these observations suggest that both size and aspect ratio of a nanoparticle are important characteristics that significantly impact interactions with the plasma membrane, uptake into the cell, and localization within intracellular vesicles. Thus, rather than simply characterizing nanoparticle uptake into cells, we show that utilization of advanced imaging approaches permits a more nuanced and complete examination of the multiple aspects of cell-nanoparticle interactions that can ultimately aid understanding possible mechanisms of toxicity, resulting in safer nanomaterial designs. Using hyperspectral confocal fluorescence (HCF) microscopy, it is shown that quantum dots of various sizes and shapes partition themselves into distinct regions within the cell membrane of RBL-2H3 rat mast cells. HCF microscopy allows for deconvolving the signal from multiple, overlapping fluorophores in the sample in order to reveal precise concentrations and distributions of nanoparticles in the cell. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Subsurface containment of CO2 is predicated on effective caprock sealing. Many previous studies have relied on macroscopic measurements of capillary breakthrough pressure and other petrophysical properties without direct examination of solid phases that line pore networks and directly contact fluids. However, pore-lining phases strongly contribute to sealing behavior through interfacial interactions among CO2, brine, and the mineral or non-mineral phases. Our high resolution (i.e., sub-micron) examination of the composition of pore-lining phases of several continental and marine mudstones indicates that sealing efficiency (i.e., breakthrough pressure) is governed by pore shapes and pore-lining phases that are not identifiable except through direct characterization of pores. Bulk X-ray diffraction data does not indicate which phases line the pores and may be especially lacking for mudstones with organic material. Organics can line pores and may represent once-mobile phases that modify the wettability of an originally clay-lined pore network. For shallow formations (i.e., < {approx}800 m depth), interfacial tension and contact angles result in breakthrough pressures that may be as high as those needed to fracture the rock - thus, in the absence of fractures, capillary sealing efficiency is indicated. Deeper seals have poorer capillary sealing if mica-like wetting dominates the wettability. We thank the U.S. Department of Energy's National Energy Technology Laboratory and the Office of Basic Energy Sciences, and the Southeast and Southwest Carbon Sequestration Partnerships for supporting this work.

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Metallic materials in sliding contact typically undergo dislocation-mediated plasticity, which results in stick-slip frictional behavior associated with high coefficients of friction ({mu} > 0.8). Our recent work on two electroplated nanocrystalline Ni alloys reveal that under combined conditions of low stress and low sliding velocity, these metals have very low friction ({mu} < 0.3). The observed frictional behavior is consistent with the transition from dislocation-mediated plasticity to an alternative mechanism such as grain boundary sliding. Focused ion beam cross-sections viewed in the TEM reveal the formation of a subsurface tribological bilayer at the contact surface, where the parent nanocrystalline material has evolved in structure to accommodate the frictional contact. Grain growth at a critical distance below the contact surface appears to promote a shear-accomodation layer. We will discuss these results in the context of a grain-size dependent transition from conventional microcrystalline wear behavior to this unusual wear behavior in nanocrystalline FCC metals.

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We will present a study of the structure-property relations in Reststrahlen materials that possess a band of negative permittivities in the infrared. It will be shown that sub-micron defects strongly affect the optical response, resulting in significantly diminished permittivities. This work has implications on the use of ionic materials in IR-metamaterials.

Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.

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Subsurface containment of CO2 is predicated on effective caprock sealing. Many previous studies have relied on macroscopic measurements of capillary breakthrough pressure and other petrophysical properties without direct examination of solid phases that line pore networks and directly contact fluids. However, pore-lining phases strongly contribute to sealing behavior through interfacial interactions among CO2, brine, and the mineral or non-mineral phases. Our high resolution (i.e., sub-micron) examination of the composition of pore-lining phases of several continental and marine mudstones indicates that sealing efficiency (i.e., breakthrough pressure) is governed by pore shapes and pore-lining phases that are not identifiable except through direct characterization of pores. Bulk X-ray diffraction data does not indicate which phases line the pores and may be especially lacking for mudstones with organic material. Organics can line pores and may represent once-mobile phases that modify the wettability of an originally clay-lined pore network. For shallow formations (i.e., < {approx}800 m depth), interfacial tension and contact angles result in breakthrough pressures that may be as high as those needed to fracture the rock - thus, in the absence of fractures, capillary sealing efficiency is indicated. Deeper seals have poorer capillary sealing if mica-like wetting dominates the wettability.

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The role of crystal coherence length on the infrared optical response of MgO thin films was investigated with regard to Reststrahlen band photon-phonon coupling. Preferentially (001)-oriented sputtered and evaporated ion-beam assisted deposited thin films were prepared on silicon and annealed to vary film microstructure. Film crystalline coherence was characterized by x-ray diffraction line broadening and transmission electron microscopy. The infrared dielectric response revealed a strong dependence of dielectric resonance magnitude on crystalline coherence. Shifts to lower transverse optical phonon frequencies were observed with increased crystalline coherence. Increased optical phonon damping is attributed to increasing granularity and intergrain misorientation.

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