Tammy Y. Olson

Synthesis of Graphene Aerogel with High Electrical Conductivity

We report the synthesis of ultra-low-density three-dimensional macroassemblies of graphene sheets that exhibit high electrical conductivities and large internal surface areas. These materials are prepared as monolithic solids from suspensions of single-layer graphene oxide in which organic sol-gel chemistry is used to cross-link the individual sheets. The resulting gels are supercritically dried and then thermally reduced to yield graphene aerogels with densities approaching 10 mg/cm(3). In contrast to methods that utilize physical cross-links between GO, this approach provides covalent carbon bonding between the graphene sheets. These graphene aerogels exhibit an improvement in bulk electrical conductivity of more than 2 orders of magnitude (∼1 × 10(2) S/m) compared to graphene assemblies with physical cross-links alone (∼5 × 10(-1) S/m). The graphene aerogels also possess large surface areas (584 m(2)/g) and pore volumes (2.96 cm(3)/g), making these materials viable candidates for use in energy storage, catalysis, and sensing applications.

In vitro and in vivo targeting of hollow gold nanoshells directed at epidermal growth factor receptor for photothermal ablation therapy

Laser-induced phototherapy is a new therapeutic use of electromagnetic radiation for cancer treatment. The use of targeted plasmonic gold nanoparticles can reduce the laser energy necessary for selective tumor cell destruction. However, the ability for targeted delivery of the currently used gold nanoparticles to tumor cells is limited. Here, we describe a new class of molecular specific photothermal coupling agents based on hollow gold nanoshells (HAuNS; average diameter, ∼30 nm) covalently attached to monoclonal antibody directed at epidermal growth factor receptor (EGFR). The resulting anti-EGFR-HAuNS exhibited excellent colloidal stability and efficient photothermal effect in the near-infrared region. EGFR-mediated selective uptake of anti-EGFR-HAuNS in EGFR-positive A431 tumor cells but not IgG-HAuNS control was shown in vitro by imaging scattered light from the nanoshells. Irradiation of A431 cells treated with anti-EGFR-HAuNS with near-infrared laser resulted in selective destruction of these cells. In contrast, cells treated with anti-EGFR-HAuNS alone, laser alone, or IgG-HAuNS plus laser did not show observable effect on cell viability. Using 111In-labeled HAuNS, we showed that anti-EGFR-HAuNS could be delivered to EGFR-positive tumors at 6.8% ID/g, and the microscopic image of excised tumor with scattering signal from nanoshells confirmed preferential delivery to A431 tumor of anti-EGFR-HAuNS compared with IgG-HAuNS. The absence of silica core, the relatively small particle size and high tumor uptake, and the absence of cytotoxic surfactant required to stabilize other gold nanoparticles suggest that immuno-HAuNS have the potential to extend to in vivo molecular therapy. [Mol Cancer Ther 2008;7(6):1730–9]

High Surface Area, sp2-Cross-Linked Three-Dimensional Graphene Monoliths

Developing three-dimensional (3D) graphene assemblies with properties similar to those individual graphene sheets is a promising strategy for graphene-based electrodes. Typically, the synthesis of 3D graphene assemblies relies on van der Waals forces for holding the graphene sheets together, resulting in bulk properties that do not reflect those reported for individual graphene sheets. Here, we report the use of sol-gel chemistry to introduce chemical bonding between the graphene sheets and control the bulk properties of graphene-based aerogels. Adjusting synthetic parameters allows a wide range of control over surface area, pore volume, and pore size, as well as the nature of the chemical cross-links (sp(2) vs sp(3)). The bulk properties of the graphene-based aerogels represent a significant step toward realizing the properties of individual graphene sheets in a 3D assembly with surface areas approaching the theoretical value of an individual sheet.

Shape control synthesis of fluorapatite structures based on supersaturation: prismatic nanowires, ellipsoids, star, and aggregate formation

Fluorapatite nanostructures of various shapes (prismatic, ellipsoidal, star, and aggregate) were synthesized and their structures correlated with the supersaturation of the system. Reagent concentration and pH were adjusted and the change in supersaturation was simulated by the Geochemists Workbench® software and the MINTEQ database. A higher pH caused changes to the FAP surface charge and was shown to be the dominant force behind aggregate formation. This led to nanorod aggregates and when combined with an increase in reagent concentration, FAP stars were generated. Increasing reaction temperature (room temperature to 100 °C) allowed release of calcium by the chelating agent, EDTA, which steadily increased the supersaturation as demonstrated by simulation. This condition led to ellipsoidal nanorods. As the crystal growth continued with an increasing reaction temperature of up to 150 °C, ellipsoidal nanorods transformed to prismatic nanowires. This transformation was explained by the decreasing supersaturation of the system as the growth nutrients were consumed. Microwave irradiation, the role of fluorite, and control of monodispersity for the FAP synthesis are also discussed.

Effects of chromophore orientation and molecule conformation on surface-enhanced Raman scattering studied with alkanoic acids and colloidal silver nanoparticles

Experimental studies have been carried out to gain a better understanding of the effects of chromophore orientation and molecular conformation on surface-enhanced Raman scattering (SERS) based on metal nanostructures. A series of alkanoic acids that contain a phenyl ring separated by methylene groups from the carboxylic acid, including phenylacetic acid, 3-phenylpropionic acid, 4-phenylbutyric acid, 5-phenylvaleric acid, and 6-phenylhexanoic acid, was investigated as model molecules with colloidal silver nanoparticles as SERS substrates. As the number of methylene groups increases, the molecules display an interesting zigzag intensity pattern of the phenyl ring bending mode around 1000 cm(-1) as well as a trend of appearance and disappearance of either the degenerate ring breathing mode or C[Double Bond]O vibrational mode near 1585 and 1630 cm(-1), respectively. Molecules containing an odd number of methylene units display a higher ring bending intensity and degenerate ring breathing mode and are suggested to have a trans conformation on the particle surface. Molecules with an even number of methylene units show a C[Double Bond]O vibrational mode and weaker ring bending in their SERS spectra and are suggested to have a gauche conformation on the silver nanoparticle surface. The different conformation is attributed to the varying interactions of the carboxylic group or the phenyl ring pi electrons with the silver surface. The SERS intensity was found to change little as the length between the phenyl ring and the carboxylic group was increased by adding CH(2) spacers. This is possibly because the effective distance between the phenyl ring and the silver surface does not change much with increasing number of CH(2) spacers as a result of changes in molecular conformation and variations in the phenyl ring orientation with CH(2) addition. The insight gained from this study is important for understanding SERS of complex molecules for which chromophore orientation and molecular conformation must be taken into careful consideration.

Raman and Surface-Enhanced Raman Detection of Domoic Acid and Saxitoxin

The use of surface-enhanced Raman scattering (SERS) for detecting domoic acid and saxitoxin was demonstrated and vibrational modes have been assigned based on the current literature. Silver nanoparticles were used to obtain the SERS spectra of domoic acid for the first time, which displayed enhancement of nearly 70 times the normal Raman spectra. Unique features in the SERS spectrum of domoic acid allowed the binding effect and orientation of the domoic acid to the metal surface to be analyzed. Saxitoxin exhibited an undetectable normal Raman signal but revealed very prominent SERS peaks. SERS peak positions closely matched published experimental and theoretical values, but with different peak ratios, indicating variance in molecule–nanoparticle interaction depending on the SERS substrate utilized. SERS is demonstrated as a powerful analytical tool for detecting toxins at low concentration with molecular specificity and shows immense potential for fast and remote sensing of toxins in various applications.

Laser damage mechanisms in conductive widegap semiconductor films

Laser damage mechanisms of two conductive wide-bandgap semiconductor films - indium tin oxide (ITO) and silicon doped GaN (Si:GaN) were studied via microscopy, spectroscopy, photoluminescence (PL), and elemental analysis. Nanosecond laser pulse exposures with a laser photon energy (1.03 eV, 1064 nm) smaller than the conductive films bandgaps were applied and radically different film damage morphologies were produced. The laser damaged ITO film exhibited deterministic features of thermal degradation. In contrast, laser damage in the Si:GaN film resulted in highly localized eruptions originating at interfaces. For ITO, thermally driven damage was related to free carrier absorption and, for GaN, carbon complexes were proposed as potential damage precursors or markers.

Multiphase separation of copper nanowires

This communication reports a new method to purify copper nanowires with nearly 100% yield from undesired copper nanoparticle side-products formed during batch processes of copper nanowire synthesis. This simple separation method can yield large quantities of long, uniform, high-purity copper nanowires to meet the requirements of nanoelectronics applications as well as provide an avenue for purifying copper nanowires in the industrial scale synthesis of copper nanowires, a key step for commercialization and application of nanowires.

Nanosecond laser-induced damage of transparent conducting ITO film at 1064nm

Transparent conducting films with superior laser damage performance have drawn intense interests toward optoelectronic applications under high energy density environment. In order to make optoelectronic applications with high laser damage performance, a fundamental understanding of damage mechanisms of conducting films is crucial. In this study, we performed laser damage experiments on tin-doped indium oxide films (ITO, Bandgap = 4.0 eV) using a nanosecond (ns) pulse laser (1064 nm) and investigated the underlying physical damage mechanisms. Single ns laser pulse irradiation on ITO films resulted in common thermal degradation features such as melting and evaporation although the laser photon energy (1.03 eV, 1064 nm) was smaller than the bandgap. Dominant laser energy absorption of the ITO film is attributed to free carriers due to degenerate doping. Upon multi-pulse irradiation on the film, damage initiation and growth were observed at lower laser influences, where no apparent damage was formed upon single pulse, suggesting a laser-induced incubation effect.