The most effective gold nanorod size for plasmonic photothermal therapy: theory and in vitro experiments.

The development of new and improved photothermal contrast agents for the successful treatment of cancer (or other diseases) via plasmonic photothermal therapy (PPTT) is a crucial part of the application of nanotechnology in medicine. Gold nanorods (AuNRs) have been found to be the most effective photothermal contrast agents, both in vitro and in vivo. Therefore, determining the optimum AuNR size needed for applications in PPTT is of great interest. In the present work, we utilized theoretical calculations as well as experimental techniques in vitro to determine this optimum AuNR size by comparing plasmonic properties and the efficacy as photothermal contrast agents of three different sizes of AuNRs. Our theoretical calculations showed that the contribution of absorbance to the total extinction, the electric field, and the distance at which this field extends away from the nanoparticle surface all govern the effectiveness of the amount of heat these particles generate upon NIR laser irradiation. Comparing between three different AuNRs (38 × 11, 28 × 8, and 17 × 5 nm), we determined that the 28 × 8 nm AuNR is the most effective in plasmonic photothermal heat generation. These results encouraged us to carry out in vitro experiments to compare the PPTT efficacy of the different sized AuNRs. The 28 × 8 nm AuNR was found to be the most effective photothermal contrast agent for PPTT of human oral squamous cell carcinoma. This size AuNR has the best compromise between the total amount of light absorbed and the fraction of which is converted to heat. In addition, the distance at which the electric field extends from the particle surface is most ideal for this size AuNR, as it is sufficient to allow for coupling between the fields of adjacent particles in solution (i.e., particle aggregates), resulting in effective heating in solution.

Hollow gold nanorectangles: the roles of polarization and substrate.

Dimers of hollow gold nanorectangles ((197 ± 4) × (134 ± 6) nm outside and (109 ± 5) × (53 ± 3) nm inside) were fabricated via electron beam lithography with interparticle separations ranging from 27 ± 2 nm to 596 ± 8 nm. Spectroscopic investigation of these arrays showed multiple peaks under illumination polarized both parallel and perpendicular to the interparticle axis. Discrete dipole approximation theoretical calculations were used to investigate the nature of these multiple peaks. These calculations demonstrate that the multiple peaks arise due to a combination of multiple plasmon modes and interactions with the substrate. The substrate effects are more pronounced for the parallel polarization because parallel polarization (along the long axis) of the nanorectangles results in a much stronger dipole mode than for the perpendicular polarization (along the short axis). Next, we show how these peaks change, as the hollow nanorectangles are brought within coupling range of one another. In this endeavor, we make use of our previously reported method to directly convert scanning electron microscope images of the nanoparticles into the shape files for the theoretical calculations.

Surface assembly and plasmonic properties in strongly coupled segmented gold nanorods.

An assembly strategy is reported such that segmented nanorods fabricated through template-assisted methods can be robustly transferred and tethered to a pre-functionalized substrate with excellent uniformity over large surface areas. After embedding the rods, sacrificial nickel segments were selectively etched leaving behind strongly coupled segmented gold nanorods with gaps between rods below 40 nm and as small as 2 nm. Hyper-spectral imaging is utilized to measure Rayleigh scattering spectra from individual and coupled nanorod elements in contrast to common bulk measurements. This approach discerns the effects of not only changing segment and gap size but also the presence of characteristic defects on the plasmonic coupling between closely spaced nanorods. Polarized hyper-spectral measurements are conducted to provide direct observation of the anisotropic plasmonic resonance modes in individual and coupled nanorods, which are close to those predicted by computer simulations for nanorods with ideal shapes. Some common deviations from ideal shape such as non-flat facets and asymmetric tails are demonstrated to result in the appearance of characteristic plasmon resonances, which have not been considered before. The large-scale assembly of coupled noble nanostructures with fine control over geometry and high uniformity provides means to strongly tune the scattering, absorption, and near-field plasmonic properties through the geometric arrangement of precisely controlled nanorod segments.

Pronounced effects of anisotropy on plasmonic properties of nanorings fabricated by electron beam lithography.

Gold nanoring dimers were fabricated via EBL with dimensions of 127.6 ± 2.5 and 57.8 ± 2.3 nm for the outer and inner diameters, respectively, with interparticle separations ranging from 17.8 ± 3.4 to 239.2 ± 3.7 nm. The coupling between the inner and outer surfaces of a single nanoring renders it very sensitive to any anisotropy. We found that anisotropy in the particle geometry and anisotropy introduced by the substrate combine to create very unique spectral features in this system.