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We present a simple and intuitive picture, an electromagnetic analog of molecular orbital theory, that describes the plasmon response of complex nanostructures of arbitrary shape. Our model can be understood as the interaction or \"hybridization\" of elementary plasmons supported by nanostructures of elementary geometries. As an example, the approach is applied to the important case of a four-layer concentric nanoshell, where the hybridization of the plasmons of the inner and outer nanoshells determines the resonant frequencies of the multilayer nanostructure.

Au and Ag nanoshells are investigated as substrates for surface-enhanced Raman scattering (SERS). We find that SERS enhancements on nanoshell films are dramatically different from those observed on colloidal aggregates, specifically that the Raman enhancement follows the plasmon resonance of the individual nanoparticles. Comparative finite difference time domain calculations of fields at the surface of smooth and roughened nanoshells reveal that surface roughness contributes only slightly to the total enhancement. SERS enhancements as large as 2.5× 1010 on Ag nanoshell films for the nonresonant molecule p-mercaptoaniline are measured.

Metal nanoshells are a class of nanoparticles with tunable optical resonances. In this article, an application of this technology to thermal ablative therapy for cancer is described. By tuning the nanoshells to strongly absorb light in the near infrared, where optical transmission through tissue is optimal, a distribution of nanoshells at depth in tissue can be used to deliver a therapeutic dose of heat by using moderately low exposures of extracorporeally applied near-infrared (NIR) light. Human breast carcinoma cells incubated with nanoshells in vitro were found to have undergone photothermally induced morbidity on exposure to NIR light (820 nm, 35 W/cm2), as determined by using a fluorescent viability stain. Cells without nanoshells displayed no loss in viability after the same periods and conditions of NIR illumination. Likewise, in vivo studies under magnetic resonance guidance revealed that exposure to low doses of NIR light (820 nm, 4 W/cm2) in solid tumors treated with metal nanoshells reached average maximum temperatures capable of inducing irreversible tissue damage (ΔT = 37.4 ± 6.6° C) within 4-6 min. Controls treated without nanoshells demonstrated significantly lower average temperatures on exposure to NIR light (ΔT < 10° C). These findings demonstrated good correlation with histological findings. Tissues heated above the thermal damage threshold displayed coagulation, cell shrinkage, and loss of nuclear staining, which are indicators of irreversible thermal damage. Control tissues appeared undamaged.

The nature of light as an electromagnetic wave with transverse components has been confirmed using optical polarizers, which are sensitive to the orientation of the electric field. Recent advances in nanoscale optical technologies demand their magnetic counterpart, which can sense the orientation of the optical magnetic field. Here we report that subwavelength metallic apertures on infinite plane predominantly sense the magnetic field of light, establishing the orientation of the magnetic component of light as a separate entity from its electric counterpart. A subwavelength aperture combined with a tapered optical fibre probe can also serve as a nanoscale polarization analyser for the optical magnetic field, analogous to a nanoparticle sensing the local electric polarization. As proof of its functionality, we demonstrate the measurement of a magnetic field orientation that is parallel to the electric field, as well as a circularly polarized magnetic field in the presence of a linearly polarized electric field. Determining the direction of the magnetic field of light is important for optical applications. Here, scattering of light from a subwavelength aperture in a metal plane is shown to be governed by its magnetic vector, providing the magnetic field orientation independently of the electric field.

Metal nanoshells are a new class of nanoparticles with highly tunable optical properties. Metal nanoshells consist of a dielectric core nanoparticle such as silica surrounded by an ultrathin metal shell, often composed of gold for biomedical applications. Depending on the size and composition of each layer of the nanoshell, particles can be designed to either absorb or scatter light over much of the visible and infrared regions of the electromagnetic spectrum, including the near infrared region where penetration of light through tissue is maximal. These particles are also effective substrates for surface-enhanced Raman scattering (SERS) and are easily conjugated to antibodies and other biomolecules. One can envision a myriad of potential applications of such tunable particles. Several potential biomedical applications are under development, including immunoassays, modulated drug delivery, photothermal cancer therapy, and imaging contrast agents.

The scanning tunneling microscope (STM) has been used to observe threefold symmetric electron scattering from point defects on a graphite surface. These theoretically predicted electronic perturbations could not be observed with a bare metal tip but could only be imaged when a fullerene ([C.sub.60]) molecule was adsorbed onto the tunneling region (apex) of an STM tip. Functionalizing an STM tip with an appropriate molecular adsorbate alters the density of states near the Fermi level of the tip and changes its imaging characteristics.

The scanning tunneling microscope (STM) has been used to observe threefold symmetric electron scattering from point defects on a graphite surface. These theoretically predicted electronic perturbations could not be observed with a bare metal tip but could only be imaged when a fullerene (C 60 ) molecule was adsorbed onto the tunneling region (apex) of an STM tip. Functionalizing an STM tip with an appropriate molecular adsorbate alters the density of states near the Fermi level of the tip and changes its imaging characteristics.

Au and Ag nanoshells are investigated as substrates for surface-enhanced Raman scattering (SERS). We find that SERS enhancements on nanoshell films are dramatically different from those observed on colloidal aggregates, specifically that the Raman enhancement follows the plasmon resonance of the individual nanoparticles. Comparative finite difference time domain calculations of fields at the surface of smooth and roughened nanoshells reveal that surface roughness contributes only slightly to the total enhancement. SERS enhancements as large as 2.5 × 1010 on Ag nanoshell films for the nonresonant molecule p-mercaptoaniline are measured.

We present a simple and intuitive picture, an electromagnetic analog of molecular orbital theory, that describes the plasmon response of complex nanostructures of arbitrary shape. Our model can be understood as the interaction or \"hybridization\" of elementary plasmons supported by nanostructures of elementary geometries. As an example, the approach is applied to the important case of a four-layer concentric nanoshell, where the hybridization of the plasmons of the inner and outer nanoshells determines the resonant frequencies of the multilayer nanostructure.

Electromigrated nanoscale junctions have proven very useful for studying electronic transport at the single-molecule scale. However, confirming that conduction is through precisely the molecule of interest and not some contaminant or metal nanoparticle has remained a persistent challenge, typically requiring a statistical analysis of many devices. We review how transport mechanisms in both purely electronic and optical measurements can be used to infer information about the nanoscale junction configuration. The electronic response to optical excitation is particularly revealing. We briefly discuss surface-enhanced Raman spectroscopy on such junctions, and present new results showing that currents due to optical rectification can provide a means of estimating the local electric field at the junction due to illumination.