Shape-dependent plasmon-resonant gold nanoparticles.
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Biomedical subjects
Publications and source records attributed to Tapan K Sau.
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This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.
Fe3O4 nanoparticles with size approximately 13 nm have been prepared successfully in aqueous micellar medium at approximately 80 degrees C. To make Fe3O4 nanoparticles resistant to surface poisoning a new route is developed for coating Fe3O4 nanoparticles with noble metals such as gold or silver as shell. The shell thickness of the core-shell particles becomes tunable through the adjustment of the ratio of the constituents. Thus, the route yields well-defined core-shell structures of size from 18 to 30 nm with varying proportion of Fe3O4 to the noble metal precursor salts. These magnetic nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FTIR, differential scanning calorimetry (DSC), Raman and temperature-dependent magnetic studies.
Surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) self-assembled monolayers (SAMs) on gold substrates is presented for SAMs onto which gold nanoparticles of various shapes have been electrostatically immobilized. SERS spectra of 4-MBA SAMs are enhanced in the presence of immobilized gold nanocrystals by a factor of 10(7)-10(9) relative to 4-MBA in solution. Large enhancement factors are a likely result of plasmon coupling between the nanoparticles (localized surface plasmon) and the smooth gold substrate (surface plasmon polariton), creating large localized electromagnetic fields at their interface, where 4-MBA molecules reside in this sandwich architecture. Moreover, enhancement factors depend on nanoparticle shape and vary by a factor of 10(2). This SERS geometry offers large surface enhancements for molecules adsorbed onto planar substrates and could be quite useful for determining chemical information for poor Raman scatterers from assays on 2-D substrates.
Gold nanocrystals of various shapes, which were produced in high yield in the presence of cetyltrimethylammonium bromide (CTAB), showed a range of two-dimensional self-assembly patterns upon drying from aqueous solution. The interparticle spacings were independent of the size and shape of the gold nanocrystals. Energy-dispersive X-ray analysis (EDAX) and Fourier-transform infrared (FTIR) spectroscopic studies revealed that the CTAB molecules adsorb onto surfaces of the gold nanocrystals in a bilayer or multilayer fashion, consistent with other groups' results. Zeta potential measurements showed that CTAB-coated nanocrystals were positively charged and the zeta potential remained almost the same upon two centrifugations and redispersion of the nanocrystals in deionized water, confirming the high stability of the surfactant-nanoparticle interaction. The nanocrystal shape strongly influenced the nature of the self-assembly patterns, in some cases in accord with theoretical predictions. CTAB is proposed as the medium for self-assembly, via interdigitation of its hydrophobic chains from adjacent nanocrystals for close contact, or via sharing a layer of counterions for larger inter-nanocrystal spacings.
A seed-mediated growth method was used to control the morphology and dimensions of Au nanocrystals by the manipulation of the experimental parameters in aqueous solution at room temperature. This chemical route produces various structural architectures with rod-, rectangle-, hexagon-, cube-, triangle-, and starlike profiles and branched (such as bi-, tri-, tetra-, and multipod) Au nanocrystals of various dimensions in high yield in the presence of a single surfactant, cetyltrimethylammonium bromide.
Short gold nanorods of average lengths ranging between 20 and 100 nm (with corresponding aspect ratios of 2 and 4) were synthesized in excellent yield (approximately 97%). These nanorods were characterized by dark-field microscopy, UV-visible spectrophotometry, and transmission electron microscopy. Temporal evolution of rod shape had also been followed by UV-visible spectrophotometry and transmission electron microscopy and indicates that the nanorods briefly increase in length, then increase slightly in width, as they grow. The effect of the synthetic parameters on the rod dimension and yield was explored to find out suitable conditions to produce short nanorods; short nanorods have both plasmon bands in the visible region of the spectrum, which is a valuable property for sensor applications.
The evolution of sphere- and rod-shaped superparamagnetic Ni--Pd and Ni--Pt nanoparticles by wet chemical methods is reported. It has been shown that increased CTAB (cetyltrimethylammonium bromide) concentration at room temperature promotes the formation of a higher proportion of rod-shaped nanomagnets over spherical particles. Temperature-dependent magnetic properties, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and electron dispersive X-ray (EDX) studies reveal the superparamagnetic behavior, size distribution, and percentage composition of the alloyed structures.