Analysis of Phospholipid Bilayers on Gold Nanorods by Plasmon Resonance Sensing and Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) and localized surface plasmon resonance sensing (LSPR) have been applied for a detailed analysis of lipid bilayers at the surface of gold nanorods. The spatial dependence of surface enhancement and the optical effects of the lipid phase transition confirm the presence of a bilayer membrane structure. Deuterated lipids exchanged rapidly between the nanorod surface and lipid vesicles in solution, suggesting a loosely bound, natural membrane structure. However, at a low solution concentration of lipid vesicles, the lipids on the gold nanorod surface convert to a nonbilayer structure, which could impact biological applications of these nanomaterials.

Gold nanobelts as high confinement plasmonic waveguides.

Plasmon propagation in thin plasmonic waveguides is strongly damped, making it difficult to study with diffraction-limited optics. Here we directly characterize plasmon propagation in gold nanobelts with incoherent light. The data indicate a short average propagation length of 0.94 µm but also reveal a weakly excited antisymmetric mode that has a propagation length greater than 10 µm with strong confinement of 2400 nm(2). These results demonstrate that high confinement and long propagation length can be achieved with thin plasmonic structures.

A tunable plasmon resonance in gold nanobelts.

Plasmonic nanowires with sub-100-nm rectangular cross sections were found to exhibit a strong transverse plasmon peak at visible wavelengths. By correlating atomic force microscopy measurements of individual nanobelts with their dark-field scattering spectra, it is seen that the transverse peak tunes with cross-sectional aspect ratio. Simulations revealed that the scattering plasmonic modes are transverse antisymmetric excitations across the nanobelt width. Unlike larger diameter silver nanowires, these nanobelts exhibit sharp, tunable plasmon resonances similar to those of nanoparticles.

Structural transition in the surfactant layer that surrounds gold nanorods as observed by analytical surface-enhanced Raman spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) of gold nanorods in cetyltrimethylammonium bromide solution has been used to analyze the interfacial surfactant structure based on the distance-dependent electromagnetic enhancement. The spectra were consistent with a surfactant bilayer oriented normal to the surface. As the surfactant concentration was reduced, a structural transition in the surfactant layer was observed through a sudden increase in the signal from the alkane chains. The structural transition was shown to influence the displacement of the surfactant layer by thiolated poly(ethylene glycol). The monodisperse and thoroughly characterized gold nanorod samples yield consistent enhancement factors that were compared to electromagnetic simulations.

The stabilization and targeting of surfactant-synthesized gold nanorods.

The strong cetyltrimethylammonium bromide (CTAB) surfactant responsible for the synthesis and stability of gold nanorod solutions complicates their biomedical applications. The critical parameter to maintain nanorod stability is the ratio of CTAB to nanorod concentration. The ratio is approximately 740,000 as determined by chloroform extraction of the CTAB from a nanorod solution. A comparison of nanorod stabilization by thiol-terminal PEG and by anionic polymers reveals that PEGylation results in higher yields and less aggregation upon removal of CTAB. A heterobifunctional PEG yields nanorods with exposed carboxyl groups for covalent conjugation to antibodies with the zero-length carbodiimide linker EDC. This conjugation strategy leads to approximately two functional antibodies per nanorod according to fluorimetry and ELISA assays. The nanorods specifically targeted cells in vitro and were visible with both two-photon and confocal reflectance microscopies. This covalent strategy should be generally applicable to other biomedical applications of gold nanorods as well as other gold nanoparticles synthesized with CTAB.

Synthesis and Crystal Structure of Gold Nanobelts.

Gold nanobelts were synthesized by the reduction of tetrachloroauric acid with ascorbic acid in the presence of the surfactants cetyltrimethylammonium bromide and sodium dodecylsulfate. The resulting structures have rectangular cross sectional dimensions that are tens of nanometers and lengths that are tens to hundreds of micrometers. We find that the nanobelt yield and resulting structures are very sensitive to temperature which is likely due to the transition of the surfactant solution from wormlike micelles to spherical micelles. The nanobelt crystal structure contains a mixture of face centered cubic and hexagonally close packed lattice phases that can be isolated and examined individually due to the unique nanobelt size and shape.