Improvements in Gold Nanorod Biocompatibility with Sodium Dodecyl Sulfate Stabilization

Due to their well-defined plasmonic properties, gold nanorods (GNRs) can be fabricated with optimal light absorption in the near-infrared region of the electromagnetic spectrum, which make them suitable for cancer-related theranostic applications. However, their controversial safety profile, as a result of surfactant stabilization during synthesis, limits their clinical translation. We report a facile method to improve GNR biocompatibility through the presence of sodium dodecyl sulfate (SDS). GNRs (120 × 40 nm) were synthesized through a seed-mediated approach, using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant to direct the growth of nanorods and stabilize the particles. Post-synthesis, SDS was used as an exchange ligand to modify the net surface charge of the particles from positive to negative while maintaining rod stability in an aqueous environment. GNR cytotoxic effects, as well as the mechanisms of their cellular uptake, were examined in two different cancer cell lines, Lewis lung carcinoma (LLC) and HeLa cells. We not only found a significant dose-dependent effect of GNR treatment on cell viability but also a time-dependent effect of GNR surfactant charge on cytotoxicity over the two cell lines. Our results promote a better understanding of how we can mediate the undesired consequences of GNR synthesis byproducts when exposed to a living organism, which so far has limited GNR use in cancer theranostics

Surface-Enhanced Infrared Absorption of Self-Aligned Nanogap Structures

Plasmonic nanostructures are often used in surface-enhanced infrared absorption (SEIRA) spectroscopy to probe surface assembled molecules or the dielectric environment surrounding the metallic nanostructures. Here we fabricate metallic nanogap structures using self-aligned techniques on an intrinsic silicon substrate and correlate resulting SEIRA spectra with the choice of metal nanostructure geometry. A motivation is to compare the enhancement from hybridization of bright plasmon modes with the effect of hybridization between bright and dark plasmon modes. These structures provide a gap size below 10 nm and support strong field enhancements. The structures demonstrate their sensitivity through the enhanced absorption signature of the Si–O stretch in the native silicon oxide layer of nanometer thickness beneath the metal. Simulations reveal this thin layer plays a critical role in determining the plasmon modes of the nanostructures. Numerical simulations of the optical properties are consistent with the observations that stronger Si–O stretch signals are detected on self-aligned nanogap structures than nanorod arrays, highlighting the enhanced electromagnetic fields in the underlying native oxide