Nanorod Solution Research Articles

Extraction of Hexadecyltrimethylammonium Bromide from Gold Nanorod Solutions: Adsorption of Gold Nanorods on Anionic Glass Surfaces

Gold nanorods dispersed in hexadecyltrimethylammonium bromide (CTAB) solutions were extracted with chloroform containing phosphatidylcholine (PC). Triple extractions decreased CTAB concentrations and gave PC-modified nanorods which adsorbed on an anionic glass surface. When more than 8.1 mM CTAB was retained in the nanorod solutions after the extractions, the nanorods dispersed stably without agglomeration. In order to have adsorption of the nanorods on an anionic glass surface, the residual CTAB after extraction should be less than 13.8 mM. Controllable adsorption was obtained between these concentrations.

Determination of the aspect ratio statistical distribution of gold nanorods in solution from a theoretical fit of the observed inhomogeneously broadened longitudinal plasmon resonance absorption spectrum

The determination of the statistical distribution of aspect ratios of a nanorod solution is desirable for experimentally synthesized solutions. The traditional method of using transmission electron microscopy (TEM) images for size determination gives statistically incorrect values due to distortions introduced by TEM sample preparation and by difficulties in counting a sufficiently large number of rods. In the present work, we propose a method to obtain the aspect ratio distribution using the observed longitudinal surface plasmon resonance absorption spectrum of gold nanorods in solution. The observed inhomogeneously broadened spectrum is fitted with a collection of homogeneously broadened spectra of nanorods each with a specific aspect ratio and population contribution using Gans extension [Ann. Phys. 47, 270 (1915)] of Mie theory. The fit generates an aspect ratio distribution for the rods in solution from which the median value and the statistical distribution are determined. This method is statistically more accurate, more convenient, and less expensive than the traditional method of TEM analysis on a solid substrate.

Spatio-selective surface modification of glass assisted by laser-induced deposition of gold nanoparticles

Using pulsed laser irradiation (532 nm), dodecanethiol-capped gold nanoparticles (DT-Au) were deposited on the laser-irradiated region of a hydrophobic glass substrate modified with dimethyloctadecylchlorosilane (DMOS). After removal of deposited DT-Au, the laser-deposited region on the substrate was hydrophilic, as verified by static water contact angles. X-ray photoelectron spectroscopy suggested that the naked glass surface was not exposed at the hydrophilic region. Immersion of the substrate into gold nanorod (NR) solution selectively immobilized NRs on the hydrophilic surface via electrostatic interactions, indicating that the hydrophilic region was an anionic surface. From these results, it is expected that some immobilized DMOS groups on the laser-irradiated region of the substrate were oxidized during DT-Au deposition and fragmentation of the deposited DT-Au.

Surface-Functionalized CdSe Nanorods for Assembly in Diblock Copolymer Templates

Poly(ethylene oxide)-covered CdSe nanorods were prepared and assembled in diblock copolymer templates by floating the block copolymer templates onto aqueous nanorod solutions. The assembly was enabled by consideration of the surface ligand coverage of the nanorods. Alkane-covered CdSe nanorods prepared by state-of-the-art techniques are not compatible with this assembly process. However, poly(ethylene oxide) (PEO)-functionalized CdSe nanorods were successfully used to assemble the nanorods into the channels and pores of diblock copolymer templates. Other water-dispersible CdSe nanorods, such as those covered with 11-mercaptoundecanoic acid (MUA), did not give the desired assemblies. These results are understood by considering the surface energies of the PEO-covered CdSe nanorods in this interfacial assembly process.

Pushing the Limits of Mercury Sensors with Gold Nanorods

The method presented here provides a direct way to determine mercury in tap water samples at the parts-per-trillion level. Its outstanding selectivity and sensitivity results from the well-known amalgamation process that occurs between mercury and gold. The entire procedure takes less than 10 min. No sample separation or sample preconcentration is required. The only step prior to mercury determination consists of mixing the water sample with a gold nanorod solution in sodium borohydride. The analytical figures of merit demonstrate precise and accurate analysis at the parts-per-trillion level. The limit of detection (6.6 x 10(-13) g x L(-1)) shows excellent potential for monitoring ultralow levels of mercury in water samples.

Fast and slow deposition of silver nanorods on planar surfaces: application to metal-enhanced fluorescence.

Two methods have been considered for the deposition of silver nanorods onto conventional glass substrates. In the first method, silver nanorods were deposited onto 3-(aminopropyl)triethoxysilane-coated glass substrates simply by immersing the substrates into the silver nanorod solution. In the second method, spherical silver seeds that were chemically attached to the surface were subsequently converted and grown into silver nanorods in the presence of a cationic surfactant and silver ions. The size of the silver nanorods was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration of immersion, ranging from tens of nanometers to a few micrometers. Atomic force microscopy and optical density measurements were used to characterize the silver nanorods deposited onto the surface of the glass substrates. The application of these new surfaces is for metal-enhanced fluorescence (MEF), whereby the close proximity of silver nanostructures can alter the radiative decay rate of fluorophores, producing enhanced signal intensities and an increased fluorophore photostability. In this paper, it is indeed shown that irregularly shaped silver nanorod-coated surfaces are much better MEF surfaces as compared to traditional silver island or colloid films. Subsequently, these new silver nanorod preparation procedures are likely to find a common place in MEF, as they are a quicker and much cheaper alternative as compared to surfaces fabricated by traditional nanolithographic techniques.

Immobilization of gold nanorods onto acid-terminated self-assembled monolayers via electrostatic interactions.

We report the immobilization of gold nanorods onto self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid (16-MHA). The simple two step protocol involves formation of a SAM of 16-MHA molecules onto gold-coated glass slides and subsequent immersion of these slides into the gold nanorod solution. The nanorods, formed by a seed-mediated, surfactant-assisted synthesis protocol, are stabilized in solution due to surface modification by the surfactant cetyltrimethylammonium bromide (CTAB). Attractive electrostatic interactions between the carboxylic acid group on the SAM and the positively charged CTAB molecules are likely responsible for the nanorod immobilization. UV-vis spectroscopy has been used to follow the kinetics of the nanorod immobilization. The nature of interaction between the gold nanorods and the 16-MHA SAM has been probed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the immobilized rods is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. SEM was also used to determine the density of the immobilized nanorods as a function of the pH of immobilization. Control over the surface coverage of the immobilized gold nanorods has been demonstrated by simple pH variation. Such well-dispersed immobilized gold nanorods with control over the surface coverage could be interesting substrates for applications such as surface-enhanced Raman spectroscopy (SERS).

Hyper-Rayleigh scattering of gold nanorods and their relationship with linear assemblies of gold nanospheres.

The surface plasmon enhanced hyper-Rayleigh scattering light collected from an aqueous solution of gold nanorods is reported. A non negligible part of the signal is attributed to a photoluminescence background attributed to the electron hole recombination following multiphoton excitation of d-valence band electrons into the sp-conduction band. This radiative relaxation process is likely favored by the presence of the organic species adsorbed at the surface of the nanorods. The absolute value for the hyperpolarisability of nanorods is also compared by the external reference method to that of para-nitroaniline and found to be rather large although an absolute value cannot be given because the exact number density of the gold nanorods is unaccessible. This value is however compared with values reported for linear assemblies of gold spherical nanoparticles and further support the simple model of gold metal ellipsoids to describe the hyper-Rayleigh light intensities. The polarisation analysis of the hyper-Rayleigh scattering light is also determined for gold nanorods and compared to the expected one for gold nanospheres. For the latter spheres, the weakness of the signal intensities precludes a definite comparison with the model. On the opposite, for the nanorods, the polarisation dependence of the hyper-Rayleigh scattered light clearly deviates from the one expected for nanospheres.

Origin and Scaling of the Permanent Dipole Moment in CdSe Nanorods

Transient electric birefringence measurements were performed on dilute solutions of CdSe nanorods. The results confirm the existence of a permanent dipole along the c-crystallographic axis. Measurements on nanorods with different widths and lengths show that the longitudinal permanent dipole moment scales linearly with volume, suggesting it arise from the noncentrosymmetric crystallographic lattice.

Room temperature optical gain in CdSe nanorod solutions

We have performed femtosecond transient absorption measurements on CdSe nanorods in hexane solution as a function of pump wavelength and pump intensity. We found that although it is not possible to achieve optical gain when pumping at energies (400 nm) high above the band-gap energy, this problem can be circumvented by pumping the CdSe nanorods directly at the lowest 1S transition. We attribute the difference to alternative relaxation pathways and possibly trapping, resulting in a competing induced absorption below the band-gap energy when excitation is carried out at high energies. Our results suggest that it is possible to achieve stimulated emission from CdSe nanoparticles in solution at ambient temperature if the excitation wavelength is chosen properly.

Synthesis of Cobalt Nanoparticles, Nanorods and Nanowires assisted by Oleic Acid and Oleylamine based Mixtures.

ABSTRACTIn this paper we report on the synthesis in solution of cobalt nanoparticles, nanorods and nanowires achieved through the decomposition of an organometallic precursor Co(η3-C8H13)(η4-C8H12) and stabilized by carboxylic acid / amine based mixtures. Through decomposition of the precursor in the presence of a 1/1 mixture of oleylamine / oleic acid during 3 hours, the formation of 3 nm spherical nanoparticles is observed while hcp-cobalt nanorods are obtained if the reaction is pursued for 48 hours. Increasing the amount of oleic acid to 2 equivalents with respect to the amine results in the formation of hcp-cobalt nanowires, micrometers in length and 6 nm mean diameter‥ By using amines with various chain lengths we have observed a modification of the aspect ratio of the cobalt nanorods1. For example, the decomposition of Co(η3-C8H13)(η4-C8H12) in the presence of octadecyl-, hexadecyl-, dodecyl- and octylamine in association with oleic acid allows to selectively produce nanorods of varying aspect ratio.Physical characterization using TEM and HRTEM, shows that the nanoparticles, nanorods and nanowires are all hcp single crystals. The magnetic properties reveal a saturation magnetization similar to that of bulk and a ferromagnetic behavior at room temperature for the nanorods and nanowires while the 3 nm nanoparticles remain super-paramagnetic.