Plasmonic focusing in symmetry broken nanocorrals

Plasmonic focusing was investigated in symmetry broken nanocorrals under linearly polarized illumination. Near-field optical measurements of the perpendicular electric field show that a single subwavelength spot size of 320 nm can be generated. The interference pattern within the corral can be controlled by changing the polarization of optical excitation and the degree of symmetry breaking. The intensity enhancement factor was investigated using finite-difference time-domain simulations and confirmed by analytical calculations taking into account the plasmon damping and multiple reflections against the corral wall.     

Au/Ag芯-壳复合结构纳米颗粒的制备和表征

利用二步液相还原法制备了 Au/Ag 芯 壳复合结构的纳米颗粒。用 TEM对反应液中金离子和银离子的摩尔比分别为1∶2和1∶1时所制备的 Au/Ag芯 壳复合结构的纳米颗粒的尺寸和形貌进行了表征。其紫外 可见吸收光谱具有 2 个可区分的吸收带,与纯金和纯银纳米颗粒的光学吸收特性对比后认为:随着反应液中银离子摩尔份数的增加,等离子体共振吸收峰始终位于 410nm附近的吸收带为银纳米颗粒的等离子体吸收带;另一个将随之产生蓝移的吸收带为Au/Ag芯 壳复合结构纳米颗粒的等离子体吸收带,蓝移是由于银壳厚度的增加而引起的。     

Reversible shape transition: Plasmonic nanorods in elastic nanocontainers

We demonstrate the reversible rod-to-sphere shape transition of gold/mesoporous silica core/shell nanorods, where the shell acts as an elastic nanocontainer during the shape change. It is shown, that elongated core/shell nanorods are transformed into spherical core/shell particles at 300 °C. The anisometric shape of the composite particles can be recovered upon in-situ seeded growth of the gold core. The mesoporous silica shell acts as a nanoscale confinement, enabling control over the growth procedure during the chemical reaction. The shell of the particles was found to be elastic; it shows conformal shape-change with the core material during the heating and the subsequent seeded growth process. The effect of the reaction conditions during the seeded growth on the resulting particle morphology was also investigated. It is demonstrated, that depending on the growth conditions, core/shell nanorods or larger core/shell nanospheres can be obtained. The shape transformation cycle can be repeated for the same system several times, where the break-up of the confining shell represents the physical limit of the process.     

Multiplex biosensor using gold nanorods

Gold nanorods (GNRs) with different aspect ratios were fabricated through seed-mediated growth and surface activation by alkanethiols for the attachment of antibodies to yield gold nanorod molecular probes (GNrMPs). Multiplex sensing was demonstrated by the distinct response of the plasmon spectra of the GNrMPs to binding events of three targets (goat anti-human IgG1 Fab, rabbit anti-mouse IgG1 Fab, rabbit anti-sheep IgG (H+L)). Plasmonic sensors are highly specific and sensitive and can be used to monitor refractive index changes caused by molecular interactions in their immediate vicinity with potential to achieve single-particle biosensing. This technique can play a key role in developing novel optical biosensors for both in vivo and in vitro detection and single-receptor kinetics.     

Self-assembly of small gold colloids with functionalized gold nanorods

We present a general strategy to stabilize gold nanorod suspensions with mono- and bifunctional polyethylene glycol (PEG) and to attach a controlled number of nanoparticles or biomolecules. Characterization by gel electrophoresis, transmission electron microscopy (TEM), and optical dark-field microscopy show the specific binding of functionalized nanorods to their target while avoiding nonspecific binding to substrates, matrices, and other particles. Such nanorods are well suited for self-assembly of nanostructures and single-molecule labeling.     

Plasmonic circular dichroism of Peptide-functionalized gold nanoparticles

Nature is remarkable at tailoring the chirality of different biomolecules to suit specific functions. Chiral molecules can impart optical activity to achiral materials in the form of the particle's electronic transition frequency. Herein, we used peptides of differing secondary structures (random coil and α-helix) to artificially create optically active chiral gold nanoparticles through peptide-nanoparticle interactions as observed by circular dichroism (CD) spectroscopy. This interaction produces a CD signal at the plasmon resonance frequency (～520 nm) of the chiral peptide-nanoparticle complex. Aggregation of the peptide-coated nanoparticles using metal ions results in a red-shifted plasmonic CD response. Our results suggest that chiroptical properties of nanomaterials can be engineered using peptides.     

Zero-phonon linewidth in CdSe/ZnS core/shell nanorods

High-resolution spectral hole-burning studies of CdSe/ZnS core/shell nanorods reveal a sharp zero-phonon line, with a line width dependent on the measurement time scale. The zero-phonon line width is attributed to contributions from radiative decay, spectral diffusion induced by surface electric field fluctuations, and phonon-assisted migration of excitons localized in the nanorods. A decoherence rate as small as 4.5 GHz has been observed, when the effects of spectral diffusion are suppressed in the spectral hole-burning measurement. Comparison between zero-phonon line widths in nanorods and spherical nanocrystals also elucidates important differences in the decoherence process between the one- and zero-dimensional nanostructures.     

Surface-driven bulk reorganization of gold nanorods

Molecular dynamic simulations are used to study the structural stability of gold nanorods upon heating. We show that the global stability of the rod is governed by the free energetics of its surface. In particular, an instability of surface facets nucleates a bulk instability that leads to both surface and bulk reorganization of the rod. The surface reorganizes to form new, more stable, {111} facets, while the underlying fcc lattice completely reorients to align with this new surface structure. Rods with predominantly {111} facets remain stable until melting.     

Synthesis of gold nanorods in organic media

A seed mediated approach for the synthesis of anisotropic rod shaped gold nanoparticles in organic media (toluene) is demonstrated. Pre-formed gold nanoparticles stabilized in toluene by 4-hexadecylaniline (HDA) are used as seeds. These when reacted with 1-octadecylamine (ODA) hydrophobised chloroaurate ions in toluene lead to the formation of gold nanorods. ODA or alkylamines of different chain lengths which are the chloroaurate ion phase transfer agent have been found to play a key role in the formation of the nanorods. The gold nanorods that have a five-fold symmetry evolve from multiply twinned particles and are bound at the tips by [1 11] faces and at the sides by [100] faces. The gold nanorods have been shown to grow under the shape directing effect of the alkylamines which stabilize the high energy [100] faces. The concentration of the alkylamines has been found to play a critical role in the formation of the gold nanorods. Higher concentrations of the alkylamines lead to formation of spherical particles, at times of narrow size distribution.     

Luminescence quantum yield of single gold nanorods

We study the luminescence quantum yield (QY) of single gold nanorods with different aspect ratios and volumes. Compared to gold nanospheres, we observe an increase of QY by about an order of magnitude for particles with a plasmon resonance >650 nm. The observed trend in QY is further confirmed by controlled reshaping of a single gold nanorod to a spherelike shape. Moreover, we identify two spectral components, one around 500 nm originating from a combination of interband transitions and the transverse plasmon and one coinciding with the longitudinal plasmon band. These components are analyzed by correlating scattering and luminescence spectra of single nanorods and performing polarization sensitive measurements. Our study contributes to the understanding of luminescence from gold nanorods. The enhanced QY we report can benefit applications in biological and soft matter studies.     

Three-dimensional morphology and crystallography of gold nanorods

We determine the three-dimensional shape, to within 1 nm resolution, of single-crystal gold nanorods grown in the presence of silver ions using electron tomography and thickness profile measurements. We find that, contrary to the current literature, the octagonal side-facets are sparsely packed atomic planes all belonging to the same symmetry-equivalent family, {0 5 12}. Furthermore, the rod ends terminate in a pyramid with slightly different facets, and each pyramid is connected to the sides by four small {0 5 12} "bridging" facets.     

Quantitative optical trapping of single gold nanorods

We report a quantitative analysis of the forces acting on optically trapped single gold nanorods. Individual nanorods with diameters between 8 and 44 nm and aspect ratios between 1.7 and 5.6 were stably trapped in three dimensions using a laser wavelength exceeding their plasmon resonance wavelengths. The interaction between the electromagnetic field of an optical trap and a single gold nanorod correlated with particle polarizability, which is a function of both particle volume and aspect ratio.     

Plasmonic detection of mercury via amalgam formation on surface-immobilized single Au nanorods

Abstract

Au nanorods were used as plasmonic transducers for investigation of mercury detection through a mechanism of amalgam formation at the nanorod surfaces. Marked scattering color transitions and associated blue shifts of the surface plasmon resonance peak wavelengths (λ_max) were measured in individual nanorods by darkfield microscopy upon chemical reduction of Hg(II). Such changes were related to compositional changes occurring as a result of Hg–Au amalgam formation as well as morphological changes in the nanorods’ aspect ratios. The plot of λ_max shifts vs. Hg(II) concentration showed a linear response in the 10–100 nM concentration range. The sensitivity of the system was ascribed to the narrow width of single nanorod scattering spectra, which allowed accurate determination of peak shifts. The system displayed good selectivity as the optical response obtained for mercury was one order of magnitude higher than the response obtained with competitor ions. Analysis of mercury content in river and tap water were also performed and highlighted both the potential and limitation of the developed method for real sensing applications.     

Silica-coated gold nanorods as photoacoustic signal nanoamplifiers

Photoacoustic signal generation by metal nanoparticles relies on the efficient conversion of light to heat, its transfer to the environment, and the production of pressure transients. In this study we demonstrate that a dielectric shell has a strong influence on the amplitude of the generated photoacoustic signal and that silica-coated gold nanorods of the same optical density are capable of producing about 3-fold higher photoacoustic signals than nanorods without silica coating. Spectrophotometry measurements and finite difference time domain (FDTD) analysis of gold nanorods before and after silica coating showed only an insignificant change of the extinction and absorption cross sections, hence indicating that the enhancement is not attributable to changes in absorption cross section resulting from the silica coating. Several factors including the silica thickness, the gold/silica interface, and the surrounding solvent were varied to investigate their effect on the photoacoustic signal produced from silica-coated gold nanorods. The results suggest that the enhancement is caused by the reduction of the gold interfacial thermal resistance with the solvent due to the silica coating. The strong contrast enhancement in photoacoustic imaging, demonstrated using phantoms with silica-coated nanorods, shows that these hybrid particles acting as "photoacoustic nanoamplifiers" are high efficiency contrast agents for photoacoustic imaging or photoacoustic image-guided therapy.     

Multiple surface plasmon modes for a colloidal solution of nanoporous gold nanorods and their comparison to smooth gold nanorods

The paper represents a novel approach to investigating localized surface plasmon (LSP) resonance modes of nanoporous Au nanorods (NRs) in a solution phase with control over surface morphology. Au NRs, which have distinctive features such as nanopores and ligaments, showed interesting LSP resonance modes depending on the surface morphology and the total length of the structure. Compared with the analogous smooth surface NRs, the LSP modes of nanoporous NRs are red-shifted, which can be interpreted as a longer effective rod length and larger amplitude of plasmon oscillation.     

Plasmonic planet-satellite analogues: hierarchical self-assembly of gold nanostructures

In the past few years, a remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures, known as plasmonic molecules. However, realization of such plasmonic molecules using nonlithographic approaches remains challenging largely due to the lack of facile and robust assembly methods. Previous attempts to achieve plasmonic nanoassemblies using molecular ligands were limited to dipolar assembly of nanostructures, which typically results in polydisperse linear and branched chains. Here, we demonstrate that core-satellite structures comprised of shape-controlled plasmonic nanostructures can be achieved through self-assembly using simple molecular cross-linkers. Prevention of self-conjugation and promotion of cross-conjugation among cores and satellites plays a key role in the formation of core-satellite heteroassemblies. The in-built electromagnetic hot-spots and Raman reporters of core-satellite structures make them excellent candidates for surface-enhanced Raman scattering probes.     

Separation of gold nanorods using density gradient ultracentrifugation

High quality gold nanorods (NRs) with a monodisperse size and aspect ratio are essential for many applications. Here, we describe how nearly monodisperse gold NRs can be separated from polydisperse samples using density gradient ultracentrifugation. Size and dimension analysis by transmission electron microscopy (TEM) and absorption spectroscopy revealed that the Au NRs were separated mainly as a function of their aspect ratio. The surface-enhanced Raman scattering (SERS) activity of Au NRs with lower aspect ratio is notably stronger than that of NRs with higher aspect ratio under 633 nm laser excitation, due to the size-dependent absorption of the longitudinal plasmon band. The separation approach provides a method to improve the quality of NRs produced by large scale synthetic methods.      

Photoacoustic imaging of multiple targets using gold nanorods

Photoacoustic (PA) imaging has been used mainly for anatomical and functional imaging. Although functionalized nanoparticles also have been developed for PA molecular imaging, only single targeting has been demonstrated. In this study, PA imaging of multiple targets using gold nanorods is demonstrated experimentally using HER2 and CXCR4 as target molecules. The two corresponding monoclonal antibodies were conjugated to two types of gold nanorod with different aspect ratios. Gold nanorods with mean aspect ratios of 5.9 and 3.7 exhibited peak optical absorptions at 1000 and 785 nm, respectively. Appropriate selection of laser irradiation wavelength enhances PA signals by 7-12 dB and allows signals from gold nanorods corresponding to specific bindings to be distinguished. This approach potentially allows the expression levels of different oncogenes of cancer cells to be revealed simultaneously.     

Plasmonic properties of gold nanoparticles separated from a gold mirror by an ultrathin oxide

That a nanoparticle (NP) (for example of gold) residing above a gold mirror is almost as effective a surface enhanced Raman scattering (SERS) substrate (when illuminated with light of the correct polarization and wavelength) as two closely coupled gold nanoparticles has been known for some time. The NP-overmirror (NPOM) configuration has the valuable advantage that it is amenable to top-down fabrication. We have fabricated a series of Au-NPOM substrates with varying but thin atomic layer-deposited oxide spacer and measured the SERS enhancement as a function of spacer thickness and angle of incidence (AOI). These were compared with high-quality finite-difference time-domain calculations, which reproduce the observed spacer thickness and AOI dependences faithfully. The SERS intensity is expected to be strongly affected by the AOI on account for the fact that the hot spot formed in the space between the NP and the mirror is most efficiently excited with an electromagnetic field component that is normal to the surface of the mirror. Intriguingly we find that the SERS intensity maximizes at ~60° and show that this is due to the coherent superposition of the incident and the reflected field components. The observed SERS intensity is also shown to be very sensitive to the dielectric constant of the oxide spacer layer with the most intense signals obtained when using a low dielectric constant oxide layer (SiO(2)).     

Influence of stirring in the synthesis of gold nanorods

Gold nanorods have been prepared by the seed-mediated growth method, in order to find the effect of stirring during the synthesis to the final shape and optical properties. The presence or absence of stirring during each step of the preparation procedure was considered a parameter to control in order to adjust the optical absorption associated with the surface plasmon resonance of the nanorods. Results show that the longitudinal surface plasmon resonance band shifts to larger wavelengths in the absence of stirring of the growth solution. Width and intensity of the absorption band associated with the longitudinal surface plasmon is reduced upon stirring during the synthesis. On the contrary, the position of the transversal surface plasmon resonance band scarcely depends upon stirring. Theoretical calculations performed using the Gans model are coherent with experimental obtained results, showing that as the aspect ratio increases, longitudinal plasmons absorption shifts toward larger wavelengths and increases both intensity and bandwidth.