Fluorescent (Au@SiO2)SiC Nanohybrids: Influence of Gold Nanoparticle Diameter and SiC Nanoparticle Surface Density

Gold@silica core–shell nanoparticles were prepared with various gold core diameters (ranging from 20 to 150 nm) and silica thicknesses (ranging from 10 to 30 nm). When the gold diameter is increased, the size dispersion became larger, leading to a broader plasmon band. Then, silicon carbide (SiC) nanoparticles were covalently immobilized onto silica to obtain hybrid (Au@SiO₂) SiC nanoparticles. The absorption properties of these hybrid nanoparticles showed that an excess of SiC nanoparticles in the dispersion can be identified by a strong absorption in the UV region. Compared to SiC reference samples, a blue shift of the fluorescence emission, from 582 to 523 nm, was observed, which was previously attributed to the strong surface modification of SiC when immobilized onto silica. Finally, the influence of several elaboration parameters (gold diameter, silica thickness, SiC concentration) on fluorescence enhancement was investigated. It showed that the highest enhancements were obtained with 10 nm silica thickness, low concentration of SiC nanoparticles, and surprisingly, with a 20-nm gold core diameter. This last result could be attributed to the broad plasmon band of big gold colloids. In this case, SiC emission strongly overlapped gold absorption, leading to possible quenching of SiC fluorescence by energy transfer.     

Tailoring LSPR-Based Absorption and Scattering Efficiencies of Semiconductor-Coated Au nanoshells

Absorption and scattering efficiencies of semiconductor-coated Au nanoshell have been studied by the extended Mie theory for their possible solar cell, optical imaging, and photothermal applications, etc. The effect of Au shell layer thickness, core size, and surrounding medium on the absorption and scattering efficiencies at the localized surface plasmon resonance (LSPR) wavelengths has been reported. It has been found that both the absorption and scattering efficiencies get blue-shifted with an increase in Au shell layer thickness from 2 to 10 nm and with an increase in surrounding refractive index whereas the corresponding LSPR peaks shift towards red. It has also been found that the spectra are red-shifted with an increase in the core radius from 20 to 40 nm while keeping the shell thickness same. The effect of shell thickness on the absorption peak position and absorption linewidth has also been studied. Hence, the optical response of both CdSe- and CdTe-coated Au nanoshells can be tuned and controlled from the visible to the near-infrared (NIR) region of the electromagnetic (EM) spectrum. Finally, the CdSe-coated Au nanoshell exhibits high scattering and absorption efficiencies in comparison to the CdTe-coated nanoshell.     

Tuning Plasmonic Properties of Truncated Gold Nanospheres by Coating

The influence of TiO₂ coating on resonant properties of gold nanoisland films deposited on silica substrates was studied numerically and in experiments. The model describing plasmonic properties of a metal truncated nanosphere placed on a substrate and covered by a thin dielectric layer has been developed. The model allows calculating a particle polarizability spectrum and, respectively, its surface plasmon resonance (SPR) wavelength for any given cover thickness, particle radius and truncation parameter, and dielectric functions of the particle, the substrate, the coating layer, and the surrounding medium. Dependence of the SPR position calculated for truncated gold nanospheres has coincided with the measured one for the gold nanoisland films covered with titania of different thicknesses. In the experiments, gold films with thickness of 5 nm were deposited on a silica glass substrate, annealed at 500 °C to form nanoislands of 20 nm in diameter, and covered with amorphous titania layers using atomic layer deposition technique. The resulting structures were characterized with scanning electron microscopy and optical absorption spectroscopy. The measured dependence of the SPR position on titania film thickness corresponded to the one calculated for truncated sphere-shaped nanoparticles with the truncation angle of ~50°. We demonstrated the possibility of tuning the SPR position within ~100 nm range by depositing to 30 nm thick titania layer.

     

The Study of Surface Plasmon in Au/Ag Core/Shell Compound Nanoparticles

Au/Ag core/shell nanoparticles are fabricated by laser-ablating Ag plates in Au colloid solution. The absorption band is found to blue shift with increasing ablation time. Mie theory calculations show that the shift is caused by the increase of the Ag shell thickness. The average Ag shell thickness can be determined from the measured absorption peak. Using the plasmon hybridization approach, we show that the absorption band around 510 nm originates from an anti-bonding mode ω _?+ caused by the interaction between a bonding Ag shell mode ω _?? and Au sphere mode ω _S-Au. The blue shift of the ω _?+ mode with the increase of Ag shell thickness is also well predicted by the hybridization theory.     

Fluorescence Quenching of CdTe Nanocrystals by Bound Gold Nanoparticles in Aqueous Solution

Water-soluble gold nanoparticles with an average diameter of 5 nm were prepared with carboxylic acid terminated thiol ligands. These ligands contain zero to eight methylene moieties. CdTe nanocrystals with an average diameter of 5 nm were synthesized with aminoethanethiol capping. These nanocrystals displayed characteristic absorption and emission spectra of quantum dots. The amine terminated CdTe nanocrystals and carboxylic-acid-terminated gold nanoparticles were conjugated in aqueous solution at pH 5.0 by electrostatic interaction, and the conjugation was monitored with fluorescence spectroscopy. The CdTe nanocrystals were significantly quenched upon binding with gold nanoparticles. The quenching efficiency was affected by both the concentration of gold nanoparticles in the complex and the length of spacer between the CdTe nanocrystal and Au nanoparticle. The observed quenching was explained using Förster resonance energy transfer (FRET) mechanism, and the Förster distance was estimated to be 3.8 nm between the donor–acceptor pair.     

Optical and Thermal Enhancement of Plasmonic Nanofluid Based on Core/Shell Nanoparticles

The plasmonic effect is introduced in solar thermal areas to enhance light harvest and absorption. The optical properties of plasmonic nanofluid are simulated by finite difference time domain (FDTD) method. Due to the excitation of localized surface plasmon resonance (LSPR) effect, an intensive absorption peak is observed at 0.5 μm. The absorption characteristics are sensitive to particle size and concentration. As the particle size increases, the absorption peak is broadened and shifted to longer wavelength. The absorption of SiO₂/Ag plasmonic nanofluid is improved gradually as the volume concentration increases, especially in the UV region. The absorption edge is shifted from 0.6 to 1.0 μm as the volume concentration increases from 0.001 to 0.01. The thermal simulation of suspended SiO₂/Ag nanoparticle shows a uniform temperature rise of 17.91 K under solar irradiation (AM 1.5), while under the same condition, the temperature rises in Ag nanoparticle and Al nanoparticle are 11.12 and 5.39 K, respectively. The core/shell plasmonic nanofluid exhibits a higher photothermal performance, which has a potential application in photothermal areas. A higher temperature rise can be obtained by improving the incident light intensity or optical absorption properties of nanoparticles.     

Decorated Core-Shell Architectures: Influence of the Dimensional Properties on Hybrid Resonances

Emerging nanoplasmonics utilizing asymmetric core-shell architectures present opportunities to precisely control the plasmon position and signal amplification within a single particle. In particular, asymmetric gold nanorods, assembled into a “matryoshka” structure (gold nanorod core, silica spacer shell, and outer gold shell) have the unique ability to enhance and precisely manipulate the plasmonic signature when compared to single gold nanorods via the generation of hybridized plasmonic modes. Currently, the fundamental understanding of the impact of the gold nanorod matryoshka dimensional parameters on the subsequent resonance behavior is incomplete. In this work, we elucidate the structural-hybridized resonance relationship of gold nanorod nanomatryoshka designs by experimentally varying the key geometrical properties; including silica spacer thickness, gold nanorod core size, and gold shell thickness/continuity.     

Investigation of Gold and Silver Nanoparticles on Absorption Heating and Scattering Imaging

Efficient conversion of absorbed light to heat energy and strong scattering by gold and silver nanoparticles suggest these nanoparticles as the agents of heating and imaging. Absorption efficiency and scattering efficiency of gold and silver nanoparticles were studied through numerical simulation using the discrete dipole approximation method. This study shows that the size of gold and silver nanoparticles can effect gold and silver nanoparticles’ absorption efficiency and scattering efficiency. The gold nanoparticle is found to possess the maximum absorption efficiency when the size of gold nanoparticle is 50 nm and the incident wavelength is 540 nm, and the increasing scattering efficiency with the increasing size of gold nanoparticle in the medium, and refractive index of the medium is around 1.33. However, the silver nanoparticle owns the maximum absorption efficiency when the size of silver nanoparticle is 20 nm and the incident wavelength is 396 nm, and the maximum scattering efficiency when the size of silver nanoparticle is 30 nm and the incident wavelength is 410 nm in the same medium. The conditions for achieving the maximum adsorption efficiency and scattering efficiency of gold and silver nanoparticle can be used for heating and imaging using visible and near-infrared light.     

Antiviral Activity of Gold/Copper Sulfide Core/Shell Nanoparticles against Human Norovirus Virus-Like Particles

Human norovirus is a leading cause of acute gastroenteritis worldwide in a plethora of residential and commercial settings, including restaurants, schools, and hospitals. Methods for easily detecting the virus and for treating and preventing infection are critical to stopping norovirus outbreaks, and inactivation via nanoparticles (NPs) is a more universal and attractive alternative to other physical and chemical approaches. Using norovirus GI.1 (Norwalk) virus-like particles (VLPs) as a model viral system, this study characterized the antiviral activity of Au/CuS core/shell nanoparticles (NPs) against GI.1 VLPs for the rapid inactivation of HuNoV. Inactivation of VLPs (GI.1) by Au/CuS NPs evaluated using an absorbance-based ELISA indicated that treatment with 0.083 μM NPs for 10 min inactivated ~50% VLPs in a 0.37 μg/ml VLP solution and 0.83 μM NPs for 10 min completely inactivated the VLPs. Increasing nanoparticle concentration and/or VLP-NP contact time significantly increased the virucidal efficacy of Au/CuS NPs. Changes to the VLP particle morphology, size, and capsid protein were characterized using dynamic light scattering, transmission electron microscopy, and Western blot analysis. The strategy reported here provides the first reported proof-of-concept Au/CuS NPs-based virucide for rapidly inactivating human norovirus.     

Preparation and Optical Characterization of Core–Shell Bimetal Nanoparticles

Chemical approaches allow for the synthesis of highly defined metal heteronanostructures, such as core–shell nanospheres. Because the material in the metal nanoparticles determines the plasmon resonance-induced absorption band, control of particle composition results in control of the position of the absorption band. Metal deposition on gold or silver nanoparticles yielded core–shell particles with modified optical properties. UV–vis spectroscopy on solution-grown, as well as surface-grown, particles was conducted and provided ensemble measurements in solution. Increasing the layers of a second metal leads to a shift in the absorption band. A shell diameter comparable to the original particle diameter leads to a predominant influence by the shell material. Extent of shell growth could be controlled by reaction time or the concentration of metal salt or reducing agent. Besides optical characterization, the utilization of atomic force microscopy, scanning electron microscopy, and transmission electron microscopy yielded important information about the ultrastructure of nanoparticle complexes. Surface-grown core–shell particles were superior in terms of achievable shell thickness, because of difficulties encountered with solution-grown particles due to salt-induced aggregation.     

Simulation Studies of Photoacoustic Response from Gold-Silica Core-Shell Nanoparticles

Metal nanoparticles especially of noble metals are used as an exogenous contrast agent for biomedical photoacoustic (PA) imaging in the tissue transmission window extending from visible to near infrared 700–1100 nm band. Different geometrical configurations of gold and silver nanoparticles like spherical core-shell, nanorod, and nanocages are promising candidates for thermoplasmonics, photothermal therapy, photothermal imaging, and photoacoustic imaging. In the current study, we simulated the photoacoustic response of gold and silica core-shell nanoparticle in water medium. Finite element simulations were carried out to study the spectral absorption response and effect of nanosecond laser pulse excitation on the spatial/temporal temperature as well as photoacoustic pressure variations of different core-shell geometry of nanoparticle. We have optimized the dimensions of gold nanosphere, gold-silica, and silica-gold core-shell geometries for optimum photoacoustic conversion efficiency. Further, the effect of shell thickness on the pulse photoacoustic signals for core-shell gold-silica and silica-gold nanoparticle has been studied. We concluded that silica-gold core-shell nanoparticles possess better photoacoustic conversion efficiency in comparison to gold nanosphere and gold-silica core-shell geometries. The prime aim of this study is to design efficient nano-probes for photoacoustic imaging, photoacoustic tomography, photothermal therapy, and drug delivery.     

Nonlinear Dependences of Optical Properties of Spherical Core–Shell Silver–Gold and Gold–Silver Nanoparticles on Their Parameters

Modeling of nonlinear optical properties of spherical core–shell gold–silver and silver–gold nanoparticles (NPs) placed in water was carried out on the base of extended Mie theory. Efficiency cross sections of absorption σ _abs, scattering σ _sca, and extinction σ _ext of radiation with wavelengths λ?=?400 and 532 nm for core–shell NPs with constant core radii r ₀₀?=?5, 10, 20, and 40 nm and in the range of relative radii r ₁/r ₀₀?=?1–8 were calculated (r ₁ is the radius of shell). Dependences of optical properties of gold–silver and silver–gold NPs on increasing of core radius r ₀ in the range 0???r ₁ under condition r ₁?=?const and increasing of r ₀ under r ₁???r ₀?=?const were investigated. Results show the nonlinear behavior of optical properties of core–shell gold–silver and silver–gold NPs on radiation wavelengths (optical indexes of metals), different core and shell radii, and their correlation, on relative NP radii r ₁/r ₀₀. An increase and decrease of absorption, scattering, and extinction efficiency cross sections of core–shell NPs with changing of wavelengths, core and shell radii, and relative NP radii r ₁/r ₀₀ are established. These dependences can be used for experimental investigation of the interesting first stages of shell formation on core and optical determination of core–shell NP parameters.     

Optimization of immunolabeled plasmonic nanoparticles for cell surface receptor analysis

Noble metal nanoparticles hold great potential as optical contrast agents due to a unique feature, known as the plasmon resonance, which produces enhanced scattering and absorption at specific frequencies. The plasmon resonance also provides a spectral tunability that is not often found in organic fluorophores or other labeling methods. The ability to functionalize these nanoparticles with antibodies has led to their development as contrast agents for molecular optical imaging. In this review article, we present methods for optimizing the spectral agility of these labels. We discuss synthesis of gold nanorods, a plasmonic nanoparticle in which the plasmonic resonance can be tuned during synthesis to provide imaging within the spectral window commonly utilized in biomedical applications. We describe recent advances in our group to functionalize gold and silver nanoparticles using distinct antibodies, including EGFR, HER-2 and IGF-1, selected for their relevance to tumor imaging. Finally, we present characterization of these nanoparticle labels to verify their spectral properties and molecular specificity.     

Resonance Rayleigh-scattering method for the determination of proteins with gold nanoparticle probe

Gold nanoparticles with a 12-nm diameter were used as probes for the determination of proteins by resonance Rayleigh-scattering techniques. In weak acidic solution, large amounts of citrate anions will self-assemble on the surface of positively charged gold nanoparticles to form supermolecular compounds with negative charges. Below the isoelectric point, proteins with positive charges such as human serum albumin (HSA), bovine serum albumin (BSA), and ovalbumin (Ova) can bind gold nanoparticles to form larger volume products (the diameter of the binding product of gold nanoparticles with HSA is 23 nm.) through electrostatic force, hydrogen bonds, and hydrophobic effects, which can result in a red shift of the maximum absorption wavelength, the remarkable enhancement of the resonance Rayleigh-scattering intensity (RRS), and the appearance of the RRS spectra. At the same time, the second-order-scattering (SOS) and frequency-doubling-scattering (FDS) intensities are also enhanced. The binding products of gold nanoparticles with different proteins have similar spectral characteristics and the maximum wavelengths are located near 303 nm for RRS, 540 nm for SOS, and 390 for FDS, respectively. The scattering enhancement (DeltaI) is directly proportional to the concentration of proteins. Among them, the RRS method has the highest sensitivity and the detection limits are 0.38 ng/ml for HSA, 0.45 ng/ml for BSA, and 0.56 ng/ml for Ova, separately. The methods have good selectivity. A new RRS method for the determination of trace proteins using a gold nanoparticle probe has been developed. Because gold nanoparticle probes do not need to be modified chemically in advance, the method is very simple and fast.     

Polarization-Dependent Resonance Light Scattering of Biomolecular Layer Coated Gold Nanoshell

Polarization-dependent resonance light scattering (RLS) of biomolecular layer coated gold nanoshell are investigated theoretically by means of the quasistatic approximation. Both the intensity and wavelength of RLS are sensitive to the azimuth angle and can be tuned by altering the core dielectric constant and biomolecular layer thickness. In the direction parallel to the incident polarization, RLS could be enhanced by decreasing the core dielectric constant or increasing the layer thickness whereas, in the direction perpendicular to the incident polarization, the RLS is only sensitive to the core dielectric constant. The variation of RLS corresponding to the changing of biomolecular layer thickness also greatly depends on the polarization. The variation of RLS intensity always reaches its maximum when the azimuth angle is 0 and can be improved by increasing the gold shell thickness or decreasing the core dielectric constant. However, the variation of RLS wavelength always reaches its maximum when the azimuth angle is between 0 and π/2 and can be improved by decreasing the gold shell thickness or core dielectric constant. This optimization of polarization-dependent RLS response of gold nanoshell to the biocoating is potentially useful in biosensing applications.     

Tuning the Dipolar Plasmon Hybridization of Multishell Metal-Dielectric Nanostructure: Gold Nanosphere in a Gold Nanoshell

Because of the interaction between dipole resonances of the inner gold sphere and the outer gold shell, gold-dielectric-gold multishells with sub-50 nm diameter may at most have three hybridization modes of surface plasmon resonance (SPR). Theoretical calculations based on quasi-static theory indicate that there are blending and splitting of SPR bands in the absorption spectra, which makes the number of absorption peak tunable by changing the radius of inserted gold sphere, thickness of gold shell, dielectric constant of middle dielectric shell or outer environment. The two absorption peaks at longer wavelength, which correspond to the hybridization from the bonding shell plasmon and the sphere plasmon, are usually intense and well tunable. The absorption peak at shorter wavelength, which corresponds to the symmetric coupling between the anti-bonding shell plasmon and the sphere plasmon, is relative weak and only occurs with large dielectric constant of the middle shell, small dielectric constant of the outer surrounding, large inner radius of the gold shell, and small radius of the inner gold sphere. Furthermore, the physical origin of these plasmon hybridizations in gold-dielectric-gold multishells nanostructure has also been illuminated by analyzing the local electric field distributions.     

Scattering Efficiency and LSPR Tunability of Bimetallic Ag,Au, and Cu Nanoparticles

Scattering efficiencies of Ag–Cu, Ag–Au, and Au–Cu alloy nanoparticles are studied based on Mie theory for their possible applications in solar cells. The effect of size (radius), surrounding medium, and alloy composition on the scattering efficiency at the localized surface plasmon resonance (LSPR) wavelengths has been reported. In the alloy nanoparticles of Ag_1?x Cu _x , Au_1?x Cu _x and Ag_1?x Au _x ; the scattering efficiency gets red-shifted with increase in x. Moreover, the scattering efficiency enhancement can be tuned and controlled with both the alloy composition and the surrounding medium refractive index. A linear relationship which is in good agreement to the experimental observations between the scattering efficiency and metal composition in the alloys are found. The effect of nanoparticle size and LSPR wavelength (scattering peak position) on the full width half maxima and scattering efficiency has also been studied. Comparison of Au–Ag, Au–Cu, and Ag–Cu alloy nanoparticles with 50-nm radii shows the optical response of Ag–Cu alloy nanoparticle with wide bandwidth in the visible region of the electromagnetic spectrum making them suitable for plasmonic solar cells. Further, the comparison of Ag–Cu alloy and core@shell nanoparticles of similar size and surrounding medium shows that Cu@Ag nanoparticle exhibits high scattering efficiency with nearly the same bandwidth.     

On Optical Properties of Dilute Colloidal Gold

Wavelength-dependent complex effective refractive index of dilute colloidal gold, i.e., spherical gold nanoparticles in water was measured using a reflectometer and a spectrophotometer. The spectral data obtained was used for the calculation of the wavelength-dependent complex permittivity of the gold nanoparticle with the aid of the Maxwell Garnett effective medium model for the colloid. It is shown that the wavelength-dependent complex permittivity of gold nanoparticle is different from the complex permittivity of bulk gold. Furthermore, Smakula’s formula is introduced for the calculation of the relative concentration of gold nanoparticles embedded in liquid using absorption data of the colloid.     

Silica‐modified luminescent LaPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis,structural and luminescent properties

Monoclinic‐type tetragonal LaPO₄:Eu (core) and LaPO₄:Eu@LaPO₄ (core/shell) nanorods (NRs) were successfully prepared using a urea‐based co‐precipitation process under ambient conditions. An amorphous silica layer was coated around the luminescent core/shell NRs via the sol–gel process to improve their solubility and colloidal stability in aqueous and non‐aqueous media. The prepared nano‐products were systematically characterized by X‐ray diffraction pattern, transmission electron microscopy, energy dispersive X‐ray analysis, and FTIR, UV/Vis, and photoluminescence spectroscopy to examine their phase purity, crystal phase, surface chemistry, solubility and luminescence characteristics. The length and diameter of the nano‐products were in the range 80–120 nm and 10–15 nm, respectively. High solubility of the silica‐modified core/shell/Si NRs was found for the aqueous medium. The luminescent core NRs exhibited characteristic excitation and emission transitions in the visible region that were greatly affected by surface growth of insulating LaPO₄ and silica layers due to the multiphonon relaxation rate. Our luminescence spectral results clearly show a distinct difference in intensities for core, core/shell, and core/shell/Si NRs. Highly luminescent NRs with good solubility could be useful candidates for a variety of photonic‐based biomedical applications.     

Optical Absorption Modeling of Plasmonic Organic Solar Cells Embedding Silica-Coated Silver Nanospheres

We numerically study plasmonic solar cells in which a square periodic array of core–shell Ag@SiO₂ nanospheres (NSs) are placed on top of the indium tin oxide (ITO) layer using a 3D finite-difference time-domain (FDTD) method. We investigate the influence of various parameters such as the periodicity of the array, the Ag core diameter, the active layer thickness, the shell thickness, and the refractive index of the shell materials on the optical performance of the organic solar cells (OSC). Our results show that the optimal periodicity of the array of NSs is dependent on the size of Ag core NSs in order to maximize optical absorption in the active layer. A very thin active layer (<70 nm) and an ultrathin (<5 nm) SiO₂ shell are needed in order to obtain the highest optical absorption enhancement. Strong electric field localization is observed around the plasmonic core–shell nanoparticles as a result of localized surface plasmon resonance (LSPR) excited by Ag NSs with and without silica shell. Embedding 50 nm Ag NSs with 1-nm-thick SiO₂ shell thickness on top of ITO leads to an enhanced intrinsic optical absorption in a 40-nm-thick poly(3-hexylthiophene):phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) active layer by 24.7% relative to that without the NSs. The use of 1-nm-thick ZnO shell instead of SiO₂ leads to an enhanced intrinsic absorption in a 40-nm-thick P3HT:PCBM active layer by 27%.