Plasmonic couplings in Ag-Au heterodimers.

The plasmonic coupling between silver (Ag) and gold (Au) nanoparticles (NPs) under four polarization modes was examined: a longitudinal mode (L-mode), where the electric field of a linearly polarized incident light parallels the dimer axis, and three transverse modes (T-modes), where the electric field of the light is perpendicular to the dimer axis. The coupling was studied using the discrete dipole approximation followed by an in-house postprocessing code that determines the extinction (Qext), absorption (Qabs), and near-field (Qnf) spectra from the individual NPs as well as the whole system. In agreement with the literature results, the extinction/absorption spectra of the whole dimer have two peaks, one near the Ag localized surface plasmon resonance (LSPR) region and the other at the Au LSPR region, with the peak at Ag LSPR being reduced in all modes and the peak at Au LSPR being red-shifted and increased in the L-mode but not in the T-modes. It is further shown that the scattering at the Ag LSPR region is reduced and becomes less than the isolated Ag NPs, but the absorption at the Ag LSPR is increased and becomes greater than the isolated Ag NPs for the 50 nm Ag-Au heterodimer. This suggests that the scattering from Ag NPs is being reabsorbed by the neighboring Au NPs due to the interband electronic transition in Au at that wavelength range. The Qext from the individual NP in the heterodimer shows the presence of the Fano profile on the Au NP but not on the Ag NP. This phenomenon was further investigated by using a dielectric particle (DP) placed near the Ag or Au NPs. The Fano profile appears in the absorbing DP spectra placed near either Ag or Au NPs. However, the Fano profile is masked upon further increases in the refractive index value of the DP particle. This explains the absence of a Fano profile on the Ag NPs in the Ag-Au heterodimer. The large near-field enhancement on both Ag and Au NPs at the Au plasmonic wavelength in the L-mode for large NPs was investigated through a DP-Au system. The large enhancement was shown to arise from a large imaginary component of the DP refractive index and a small real component. Through examination of both the near- and far-field properties of the individual NPs as well as the whole system and examinations of DP-Ag and DP-Au systems, our study provides a new understanding of the couplings between Ag and Au NPs.

An Investigation on the Use of Au@SiO2@Au Nanomatryoshkas as Gap-Enhanced Raman Tags.

Gap-enhanced Raman tags are a new type of optical probe that have wide applications in sensing and detection. A gap-enhanced Raman tag is prepared by embedding Raman molecules inside a gap between two plasmonic metals such as an Au core and Au shell. Even though placing Raman molecules beneath an Au shell seems counter-intuitive, it has been shown that such systems produce a stronger surface-enhanced Raman scattering response due to the strong electric field inside the gap. While the theoretical support of the stronger electric field inside the gap was provided in the literature, a comprehensive understanding of how the electric field inside the gap compares with that of the outer surface of the particle was not readily available. We investigated Au@SiO2@Au nanoparticles with diameters ranging from 35 nm to 70 nm with varying shell (2.5-10 nm) and gap (2.5-15 nm) thicknesses and obtained both far-field and near-field spectra. The extinction spectra from these particles always have two peaks. The low-energy peak redshifts with the decreasing shell thickness. However, when the gap thickness decreases, the low-energy peaks first blueshift and then redshift, producing a C-shape in the peak position. For every system we investigated, the near-field enhancement spectra were stronger inside the gap than on the outer surface of the nanoparticle. We find that a thin shell combined with a thin gap will produce the greatest near-field enhancement inside the gap. Our work fills the knowledge gap between the exciting potential applications of gap-enhanced Raman tags and the fundamental knowledge of enhancement provided by the gap.

Insight on the Coupling of Plasmonic Nanoparticles from Near-Field Spectra Determined via Discrete Dipole Approximations.

Coupling between plasmonic nanoparticles (NPs) in nanoparticle assemblies has been investigated extensively via far-field properties, such as absorption and scattering, but very rarely via near-field properties, and a quantitative investigation of near-field properties should provide great insight into the nature of the coupling. We report a numerical procedure to obtain reliable near-field spectra (Q NF) around spherical gold nanoparticles (Au NPs) using Discrete Dipole Approximation (DDA). The reliability of the method was tested by comparing Q NF from DDA calculations with exact results from the Mie theory. We then applied the method to examine Au NPs assembled in dimer, trimer, and up to pentamer in a linear arrangement. For the well-studied dimer system, we show that the Q NF enhancement, due to coupling in longitudinal mode, is much greater than the enhancement in Q ext. There is a linear correlation between the Q NF and Q ext peak positions, with the Q NF peak redshifted from the Q ext peak by an average of approximately 12 nm. In the case of the multimers, Q NF spectra from individual spheres were not always identical and become dependent on the sphere location. In the longitudinal model, the center sphere has the strongest Q NF spectra. For the transverse mode, we differentiate two different scenario, transverse-Y where both electric field (E) and light propagation vector (k) are perpendicular the chain axis, and transverse-X where k is parallel to the chain axis. In transverse-Y mode, coupling leads to reduced Q NF spectra and the center sphere has the lowest Q NF intensity. In transverse-X mode, there is retardation effect from the front sphere to the back sphere. The Q NF from the front sphere is stronger than from the back sphere. In addition, due to the phase lag in k-direction, the Q NF in transverse-X can differ quite significantly from transverse-Y for large particles. All these results could be understood when one considers how electric field from induced dipoles on neighboring NPs add on or subtract from the incident E-field. These results provide new insight into the coupling properties of Au NPs.

Synthesis and Properties of Magnetic-Optical Core-Shell Nanoparticles.

Due to their high integrity, facile surface chemistry, excellent stability, and dual properties from the core and shell materials, magnetic-plasmonic core-shell nanoparticles are of great interest across a number of science, engineering and biomedical disciplines. They are promising for applications in a broad range of areas including catalysis, energy conversion, biological separation, medical imaging, disease detection and treatment. The technological applications have driven the need for high quality nanoparticles with well controlled magnetic and optical properties. Tremendous progress has been made during past few decades in synthesizing and characterizing magnetic-plasmonic core-shell nanoparticles, mainly iron oxide-gold core-shell nanoparticles. This review introduces various approaches for the synthesis of spherical and anisotropic magnetic-plasmonic core-shell nanoparticles focusing on iron oxide-gold core-shell nanoparticles. Growth mechanisms are discussed to provide understanding of the key factors controlling shape-controlled synthesis. Magnetic and optical properties are summarized from both computational and experimental studies.

Dependence of SERS enhancement on the chemical composition and structure of Ag/Au hybrid nanoparticles.

Noble metal nanoparticles (NPs) such as silver (Ag) and gold (Au) have unique plasmonic properties that give rise to surface enhanced Raman scattering (SERS). Generally, Ag NPs have much stronger plasmonic properties and, hence, provide stronger SERS signals than Au NPs. However, Ag NPs lack the chemical stability and biocompatibility of comparable Au NPs and typically exhibit the most intense plasmonic resonance at wavelengths much shorter than the optimal spectral region for many biomedical applications. To overcome these issues, various experimental efforts have been devoted to the synthesis of Ag/Au hybrid NPs for the purpose of SERS detections. However, a complete understanding on how the SERS enhancement depends on the chemical composition and structure of these nanoparticles has not been achieved. In this study, Mie theory and the discrete dipole approximation have been used to calculate the plasmonic spectra and near-field electromagnetic enhancements of Ag/Au hybrid NPs. In particular, we discuss how the electromagnetic enhancement depends on the mole fraction of Au in Ag/Au alloy NPs and how one may use extinction spectra to distinguish between Ag/Au alloyed NPs and Ag-Au core-shell NPs. We also show that for incident laser wavelengths between ∼410 nm and 520 nm, Ag/Au alloyed NPs provide better electromagnetic enhancement than pure Ag, pure Au, or Ag-Au core-shell structured NPs. Finally, we show that silica-core Ag/Au alloy shelled NPs provide even better performance than pure Ag/Au alloy or pure solid Ag and pure solid Au NPs. The theoretical results presented will be beneficial to the experimental efforts in optimizing the design of Ag/Au hybrid NPs for SERS-based detection methods.

Size- and Shape-Controlled Synthesis and Properties of Magnetic-Plasmonic Core-Shell Nanoparticles.

Magnetic-plasmonic core-shell nanomaterials offer a wide range of applications across science, engineering and biomedical disciplines. However, the ability to synthesize and understand magnetic-plasmonic core-shell nanoparticles with tunable sizes and shapes remains very limited. This work reports experimental and computational studies on the synthesis and properties of iron oxide-gold core-shell nanoparticles of three different shapes (sphere, popcorn and star) with controllable sizes (70 to 250 nm). The nanoparticles were synthesized via a seed-mediated growth method in which newly formed gold atoms were added onto gold-seeded iron oxide octahedrons to form gold shell. The evolution of the shell into different shapes was found to occur after the coalescence of gold seeds, which was achieved by controlling the amount of additive (silver nitrate) and reducing agent (ascorbic acid) in the growth solution. First principles calculation, together with experimental results, elucidated the intimate roles of thermodynamic and kinetic parameters in the shape-controlled synthesis. Both discrete dipole approximation calculation and experimental results showed that the nanopopcorns and nanostars exhibited red-shifted plasmon resonance compared with the nanospheres, with the nanostars giving multispectral feature. This research has made a great step further in manipulating and understanding magnetic-plasmonic hybrid nanostructures and will make important impact in many different fields.

Impact of core dielectric properties on the localized surface plasmonic spectra of gold-coated magnetic core-shell nanoparticles.

Gold-coated iron oxide core-shell nanoparticles (IO-Au NPs) are of interest for use in numerous biomedical applications because of their unique combined magnetic-plasmonic properties. Although the effects of the core-dielectric constant on the localized surface plasmon resonance (LSPR) peak position of Au-shell particles have been previously investigated, the impact that light-absorbing core materials with complex dielectric functions have on the LSPR peak is not well established. In this study, we use extended Mie theory for multilayer particles to examine the individual effects of the real and imaginary components of core refractive indices on Au-shell NP plasmonic peaks. We find that the imaginary component dampens the intensity of the cavity plasmon and results in a decrease of surface plasmon coupling. For core materials with large imaginary refractive indices, the coupled mode LSPR peak disappears, and only the anticoupled mode remains. Our findings show that the addition of a nonabsorbing polymer layer to the core surface decreases the dampening of the cavity plasmon and increases LSPR spectral intensity. Additionally, we address apparent discrepancies in the literature regarding the effects of Au-shell thickness on LSPR peak shifts.

Capture and detection of cancer cells in whole blood with magnetic-optical nanoovals.

AIM: To develop a simple assay for the capture and detection of rare cancer cells in whole blood using iron oxide-gold (IO-Au) nanoparticles. MATERIALS & METHODS: IO-Au nanoovals (NOVs) were synthesized, coated with Raman tags and linked with antibodies targeting breast cancer. An integrated system was constructed for on-line magnetic cell capture and surface-enhanced Raman scattering (SERS) detection. The capabilities of IO-Au SERS NOVs to capture and detect rare cancer cells in blood were investigated in the integrated system using circulating tumor cell-mimic SK-BR-3 cells. RESULTS: SK-BR-3 cells in whole blood were magnetically captured under a flow condition using IO-Au SERS NOVs, followed by on-line SERS detection with a limit of detection of 1-2 cells/ml blood. CONCLUSION: We developed a sensitive method that can capture and detect cancer cells in whole blood with a single nanoconstruct, which is highly promising for the detection of circulating tumor cells in the clinic.