Gold nanoparticles of different shapes and sizes, including nanospheres, nanocubes, nanobranches, nanorods, and nanobipyramids, were dispersed into water-glycerol mixtures of varying volume ratios to investigate the response of their surface plasmon peaks to the refractive index of the surrounding medium. The refractive index sensitivities and figures of merit were found to be dependent on both the shape and the size of the Au nanoparticles. The index sensitivities generally increase as Au nanoparticles become elongated and their apexes become sharper. Au nanospheres exhibit the smallest refractive index sensitivity of 44 nm/RIU and Au nanobranches exhibit the largest index sensitivity of 703 nm/RIU. Au nanobipyramids possess the largest figures of merit, which increase from 1.7 to 4.5 as the aspect ratio is increased from 1.5 to 4.7.

Tailoring the longitudinal surface plasmon wavelengths (LSPWs), scattering, and absorption cross sections of gold nanorods has been demonstrated by combining anisotropic shortening and transverse overgrowth and judiciously choosing starting Au nanorods. Shortening yields Au nanorods with decreasing lengths but a fixed diameter, while overgrowth produces nanorods with increasing diameters but a nearly unchanged length. Two series of Au nanorods with LSPWs varying in the same spectral range but distinct extinction coefficients are thus obtained. The systematic changes in the LSPW and extinction for the two series of Au nanorods are found to be in good agreement with those obtained from Gans theory. Dark-field imaging performed on two representative nanorod samples with similar LSPWs shows that the scattering intensities of the overgrown nanorods are much larger than those of the shortened nanorods. The experimental results are found to be in very good agreement with those obtained from finite-difference time-domain (FDTD) calculations. FDTD calculations further reveal that the scattering-to-extinction ratio increases linearly as a function of the diameter for Au nanorods with a fixed aspect ratio.

Gold nanorods (NRs) have received much attention due to their size-dependent surface plasmon-related optical properties. A seed-mediated approach has recently been developed for the synthesis of Au NRs with varying length-to-diameter aspect ratios. With the introduction of silver ions in the growth solution, Au NRs of narrow size distributions can be produced in high yields. Herein we describe an approach for the continuous and selective shortening of Au NRs synthesized by the silver ion-assisted seed-mediated method through oxidation with environmentally benign oxygen at slightly elevated temperatures. UV-visible extinction measurements indicate that the longitudinal surface plasmon band of Au NRs decreases in intensity and blue-shifts as a function of the oxidation time. Transmission electron microscopy (TEM) imaging shows that the length of Au NRs decreases with oxidation and their diameter stays almost constant, which suggests that oxidation starts at the ends of Au NRs. The size distributions of shortened Au NRs are similar to those of starting NRs. Further oxidation transforms Au NRs into nanospheres, which become smaller in diameter and finally completely disappear. It has been found that the oxidation rate of Au NRs can be controlled by temperature and acid concentration. Furthermore, high-resolution TEM studies reveal that Au NRs synthesized by the silver ion-assisted seed-mediated method are single crystalline and they stay single crystalline during oxidation. It is expected that Au NRs of any aspect ratio with narrow size distributions within the limit of that possessed by starting NRs can be produced by this mild oxidation approach.

Gold nanorods exhibit rich surface-plasmon-resonance (SPR)derived properties, which have made discrete nanorods useful for many interesting applications such as optical data storage, [1] submicrometer metallic barcodes, [2] sensing, [3] biological imaging, [4] and controlled gene delivery. [5] Future scientific and technological applications of Au nanorods require the capability to assemble into complex one-, two-, or even three-dimensional (3D) functional architectures. The assembly of Au nanorods also allows for the utilization of their collective properties that result from the coupling of the optical and electronic properties between neighboring individual nanorods. Several approaches have been developed for the assembly of Au nanorods in either end-to-end (EE) or side-by-side (SS) orientations. They include i) assembly through electrostatic interactions, hydrogen bonding, or covalent bonding, [6] ii) antibody/antigen and streptavidin/biotin biorecognitions, [7] iii) use of carbon nanotubes and silica nanofibers as templates, [8] and iv) interactions between functionalized polymers in selective solvents. [9] Au nanorods assembled by these approaches are generally difficult to disassemble. Even though significant progress has been made in the organization of nanomaterials, reversible assembly and disassembly of Au nanorods in either EE or SS orientations has remained a big challenge. So far, reversible aggregation of spherical Au nanoparticles has been demonstrated by functionalizing them with thiol-modified DNA oligomers. [10] Here, we report on a robust strategy for the reversible assembly and disassembly of Au nanorods in both EE and SS fashion. Thiol-containing bifunctional molecules are selectively bound to the end or side surface of individual Au nanorods. The bound molecules induce the assembly of Au nanorods if the pH of the nanorod solution is adjusted within an optimal range. Outside the optimal pH range, Au nanorods are disassembled. This pH-controlled assembly and disassembly is reversible and can be repeated many times. Moreover, the distances between assembled nanorods are estimated to vary from 0.080 to 1.8 nm for different assembling molecules and assembly orientations.As-prepared Au nanorods are stabilized in 0.1 M aqueous cetyltrimethylammonium bromide (CTAB) solutions with pH ¼ 3.5. Their ensemble transverse and longitudinal plasmon wavelengths are 515 and 780 nm, respectively. The ensemble extinction values at the two plasmon peaks are 1.0 and 3.7, respectively, suggesting a high yield of Au nanorods. The nanorod concentration is estimated to be %0.8 nM according to previously determined molar extinction coefficients. [11] The average length, diameter, and aspect ratio, determined from %500 nanorods on transmission electron microscopy (TEM) images, are 38 AE 4 nm, 11 AE 1 nm, and 3.6 AE 0.5 nm, respectively. The used bifunctional molecules include 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA), glutathione (GSH), and cysteine (CYS). Their concentrations in nanorod so...