Silver Nanocube- and Nanowire-Based SERS Substrates for Ultra-low Detection of PATP and Thiram Molecules

Plasmonics - The shape-anisotropic metal nanoparticles support large surface plasmon resonance (SPR) wavelength tuning and higher intrinsic electromagnetic hot spots for excellent surface-enhanced...     

Nanostructuring of Continuous Gold Film by Laser Radiation Under Surface Plasmon Polariton Resonance Conditions

The physical mechanisms of metallic nanoparticles formation by laser technology were studied. The system air/Au film/glass was irradiated by laser at the conditions of surface plasmon resonance. A surface electromagnetic wave was excited in Kretchmann configuration by the fundamental and second harmonics of the Q-switched YAG/Nd⁺³ laser with pulse power density close to the threshold of melting. Nanostructuring of Au film was observed only for the second harmonic (λ = 0.532 μm) irradiation at the surface plasmon polariton resonance (SPR) conditions. Estimations were done using the interference model of the differently directed plasmon polariton waves excited by a surface electromagnetic wave on the metal surface. It was shown that a regular pattern of locally heated spots can be formed in a metallic film by pulsed laser irradiation. The spatial distribution of this pattern is close to the period of interference. The observed effect of laser nanofragmentation is explained by the self-organization of plasmon polariton subsystem in the process of Au nanoparticles formation at high laser intensity levels. These methods open new possibilities for nanostructured surfaces formation utilizing simple self-organization processes.     

Sensitivity enhancement of surface plasmon resonance biosensor with colloidal gold

We enhanced the sensitivity of surface plasmon resonance biosensor by the conversion of the real-time direct binding immunoassay into the sandwich immunoassay, in which colloidal gold particles coated with anti-mouse IgG was used. By the immobilization of anti-mouse IgG onto the carboxymethyl dextran surface of thin gold film, the direct binding of analyte (mouse IgG) onto the sensor chip, and the injection of colloidal gold particles coated with antimouse IgG, about 100 times of sensitivity enhancement was obtained. This result suggests that nanoparticles, which has a high refractive index, homogeneous ultrafine structure and capability of size control, would be applicable for the detection of very small quantity of biomaterial.     

Experimental Study on Localized Surface Plasmon Mode Hybridization in the Near and Mid Infrared

We investigate plasmon excitations within a regular grating of double-layered gold/insulator nanoparticles in the infrared and visible spectral region. Provided a flat gold film as substrate, strong coupling between the localized surface plasmon modes and their image-like excitations in the metal is observed. The interaction results in a strong red shift of the plasmon mode as well as the splitting of the modes into levels of different angular momenta, often referred to as plasmon hybridization. The diameters of the nanoparticles are designed in a way that the splitting of the resonances occurs in the spectral region between 0.1 and 1 eV, thus being accessible using an infrared microscope. Moreover, we investigated the infrared absorption signal of gratings that contain two differently sized nanoparticles. The interaction between two autonomous localized surface plasmon excitations is investigated by analyzing their crossing behavior. In contrast to the interaction between localized surface plasmons and propagating plasmon excitations which results in pronounced anticrossing, the presented structures show no interaction between two autonomous localized surface plasmons. Finally, plasmon excitations of the nanostructured surfaces in the visible spectral region are demonstrated through photographs acquired at three different illumination angles. The change in color of the gratings demonstrates the complex interaction between propagating and localized surface plasmon modes.     

Aptamer–Au NPs conjugates-enhanced SPR sensing for the ultrasensitive sandwich immunoassay

The goal of this work is to explore the amplification effect of aptamer–gold nanoparticles (Au NPs) conjugates for ultrasensitive detection of large biomolecules by surface plasmon resonance (SPR). A novel sandwich immunoassay is designed to demonstrate the amplification effect of aptamer–Au NPs conjugates by using human immunoglobulin E (IgE) as model analyte. Human IgE, captured by immobilized goat anti-human IgE on SPR gold film, is sensitively detected by SPR spectroscopy with a lowest detection limit of 1 ng/ml after anti-human IgE aptamer–Au NPs conjugates is used as amplification reagent. Meanwhile, the non-specific adsorption of aptamer–Au NPs conjugates on goat anti-human IgE is confirmed by SPR spectroscopy and then it is minimized by treating aptamer–Au NPs conjugates with 6-mercaptohexan-1-ol (MCH). These results confirm that aptamer–Au NPs conjugates is a powerful sandwich element and an excellent amplification reagent for SPR-based sandwich immunoassay.     

Multiple Surface Plasmon Resonances in Compound Structure with Metallic Nanoparticle and Nanohole Arrays

The optical properties of a compound structure with metallic nanoparticle and nanohole arrays are numerically investigated by the means of finite-difference time domain method. We report on the observation of multi-valleys in the reflection spectra due to the excitation of surface plasmon (SP) resonant modes of the compound structure. Simulation results show that multiple SP resonances consist of surface plasmon polaritons on the gold film, localized surface plasmons on the nanoparticles, and coupling mode between them. These findings are important for applications utilizing multiple surface plasmon resonances.     

α,ω-Aliphatic Diamines as Molecular Linkers for Engineering Ag Nanoparticle Clusters: Tuning of the Interparticle Distance and Sensing Application

The controlled tuning of interparticle distance at the nanoscale level is a major challenge for nanofabrication of surface-enhanced Raman scattering (SERS) active clusters and their application to molecular sensing. In fact, the geometrical properties of the narrow gaps between nanoparticles play a key role in determining the local field enhancement (and therefore, the SERS enhancement factor) and the spatial enhancement distribution in the gap region. Besides, very short interparticle distances may block the access of the analyte to the hot zone. In this paper, we report the synthesis of silver colloid NP clusters with interparticle distances fine tuned in the ≤2 nm range, by exploiting the chemical properties of linear α,ω-aliphatic diamines as molecular linkers with varying chain length. The bifunctional diamines also form intermolecular cavities within their self-assembled monolayers, suitable to host molecular analytes for nanosensing applications, as evidenced by SERS detection of organochlorine insecticides at the trace level. In this regard, the extension of the aliphatic chain played a crucial role in determining the SAM conformation and thus the final sensitivity of the functionalized SERS substrate.     

Iridium Oxide‐Assisted Plasmon‐Induced Hot Carriers: Improvement on Kinetics and Thermodynamics of Hot Carriers

Plasmonic nanostructures are capable of driving photocatalysis through absorbing photons in the visible region of the solar spectrum. Unfortunately, the short lifetime of plasmon‐induced hot carriers and sluggish surface chemical reactions significantly limit their photocatalytic efficiencies. Moreover, the thermodynamically favored excitation mechanism of plasmonic photocatalytic reactions is unclear. The mechanism of how the plasmonic catalyst could enhance the performance of chemical reaction and the limitation of localized surface plasmon resonance devices is proposed. In addition, a design is demonstrated through co‐catalyst decorated plasmonic nanoparticles Au/IrO_X upon a semiconductor nanowire‐array TiO₂ electrode that are able to considerably improve the lifetime of plasmon‐induced charge‐carriers and further facilitate the kinetics of chemical reaction. A thermodynamically favored excitation with improved kinetics of hot carriers is revealed through electrochemical studies and characterization of X‐ray absorption spectrum. This discovery provides an opportunity to efficiently manage hot carriers that are generated from metal nanostructures through surface plasmon effects for photocatalysis applications.     

Shell Thickness-Dependent Plasmon Coupling and Creation of SERS Hot Spots in Au@Ag Core-Shell Nanostructures

The main objective of the present study is to investigate the shell thickness-dependent Raman enhancement activity of silver-coated gold nanoparticles (Au@Ag NPs) when bound to a model analyte 2-mercaptobenzoic acid (2-MBA). With an optimized Ag:Au ratio, dimeric and trimeric Au@Ag nanostructures were prepared in the presence of 2-MBA and are characterized by spectroscopic and microscopic techniques. These dimeric junctions act as hot spots and the molecules trapped at these junctions showed higher Raman signal enhancements due to the presence of amplified electric field.     

Speckled SiO2@Au Core–Shell Particles as Surface Enhanced Raman Scattering Probes

Silica particles of ~800 nm size were functionalized using 3-amino propyl triethoxysilane molecules on which gold particles (~20 nm size) were deposited. The resulting particles appeared to form speckled SiO₂@Au core–shell particles. The surface roughness, along with hot spots, due to nanogaps between the gold nanoparticles was responsible for the enhancement of the Raman signal of crystal violet molecules by ~3.2?×?10⁷ and by ~1.42?×?10⁸ of single-wall carbon nanotubes. It has also been observed that the electromagnetic excitation near surface plasmon resonance (SPR) of core–shell particles is more effective than off resonance SPR excitation.     

Size and Temperature Effects on the Surface Plasmon Resonance in Silver Nanoparticles

The surface plasmon energy in spherical silver nanoparticles embedded in silica host matrix depends on the size and temperature of the nanoparticles. The dependences of the surface plasmon energy were studied for silver nanoparticles in the size range 11?C30?nm and in the temperature interval 293?C650?K. As the size of the nanoparticles decreases or the temperature increases, the surface plasmon resonance shifts to red. When the size of the nanoparticles decreases, the scattering rate of the conduction electrons increases, which results in the nonlinear red shift of the surface plasmon resonance. The red shift with temperature is linear for larger nanoparticles and becomes nonlinear for smaller ones. As the temperature of the nanoparticles increases, the volume thermal expansion of the nanoparticles leads to the red shift of the surface plasmon resonance. The thermal volume expansion coefficient depends on the size and temperature. It increases with a decrease of the nanoparticle size and an increase of the temperature.     

Remote Excitation Surface Plasmon and Consequent Enhancement of Surface-Enhanced Raman Scattering Using Evanescent Wave Propagating in Quasi-One-Dimensional MoO3 Ribbon Dielectric Waveguide

We report experimentally the remote excitation surface plasmon and consequent enhancement of surface-enhanced Raman scattering (SERS) using evanescent wave propagating in quasi-one-dimensional (Q1D) MoO₃ ribbon dielectric waveguide. The propagating dielectric waveguide along Q1D MoO₃ ribbon is realized experimentally, when the 632.8 nm laser radiates on the one side edge of Q1D MoO₃ ribbon. The remote excitation SERS spectra-enhanced by chemical and electromagnetic field mechanisms are measured, respectively, where silver (Ag) nanoparticles are excited by electromagnetic field after propagating 7.3 μm in the ribbon. The chemical mechanism for the remote excitation SERS is contributed from the charge transfer between the analyte molecule and MoO₃ ribbon. The electromagnetic field mechanism for the remote excitation SERS arises from the energy conversion from the propagating dielectric waveguide to the surface plasmon of Ag nanoparticles on the Q1D MoO₃ ribbon. It is important to reveal the mechanism of energy conversion from the propagating dielectric waveguide to the surface plasmon for potential applications in micro- and nanoscale devices.     

A Surface Design for Enhancement of Light Trapping Efficiencies in Thin Film Silicon Solar Cells

We report on a surface design of thin film silicon solar cells based on silver nanoparticle arrays and blazed grating arrays. The light transmittance is increased at the front surface of the cells, utilizing the surface plasmon resonance effect induced by silver nanoparticle arrays. As a reflection layer structure, blazed gratings are placed at the rear surface to increase the light reflectance at bottom of the thin film cells. With the combination of the silver nanoparticle arrays and the blazed gratings, the light trapping efficiency of the thin film solar cell is characterized by its light absorptance, which is determined from the transmittance at front surface and the reflectance at bottom, via the finite-difference time-domain (FDTD) numerical simulation method. The results reveal that the light trapping efficiency is enhanced as the structural parameters are optimized. This work also shows that the surface plasmon resonance effect induced by the silver nanoparticles and the grating characteristics of the blazed gratings play crucial roles in the design of the thin film silicon solar cells.     

Compensation for loss of ligand activity in surface plasmon resonance experiments

The determination of equilibrium binding constants is an important aspect of the analysis of protein-protein interactions. In recent years surface plasmon resonance experiments (e.g., with a BIAcore instrument) have provided a valuable experimental approach to determining such constants. The standard method is based on measuring amounts of analyte bound at equilibrium for different analyte concentrations. During the course of a typical surface plasmon resonance experiment the measured equilibrium levels for a given analyte concentration often decrease. This appears to be due to a loss of activity of the protein coupled to the sensor chip or other phenomena. The loss in signal can lead to an erroneous determination of the equilibrium constant. A data analysis approach is introduced that aims to compensate for the loss of activity so that its influence on the results of the experiments is reduced.     

Fruit extract capped colloidal silver nanoparticles and their application in reduction of methylene blue dye

Green synthesis of silver nanoparticles (AgNPs) has become a promising environmentally benign synthetic route in nanoscience and nanotechnology during recent years. In the present work, we have developed an environment-friendly and low-cost method for synthesis of silver nanoparticles from silver nitrate using aqueous fruit extract of Dillenia indica. The as-synthesized nanoparticles were characterized by UV-Vis spectrophotometer, transmission electron microscopy (TEM) and X-ray diffraction (XRD). FTIR study was performed to know the interaction of bio-molecules present in the fruit extract with AgNPs. The catalytic application of the as-synthesized AgNPs was demonstrated against degradation of methylene blue (MB) in aqueous system. The absorption spectra of colloidal suspension of AgNPs showed characteristic surface plasmon resonance (SPR) band centred at a wavelength of 416?nm. TEM image showed that the AgNPs were almost spherical in shape having an average diameter of 10.78?±?.48?nm. XRD pattern and selected area electron diffraction (SAED) pattern with bright spots signify the crystalline nature of nanoparticles. The fruit extract-capped AgNPs was highly stable and have showed the effective catalytic activity in reduction of MB dye.     

An in situ electrochemical surface plasmon resonance immunosensor with polypyrrole propylic acid film: comparison between SPR and electrochemical responses from polymer formation to protein immunosensing

A novel in situ electrochemical surface plasmon resonance (EC-SPR) immunosensor is presented in this paper. The EC-SPR measurement can be used to in situ monitor the polymer formation, probe immobilization, antigen-antibody interaction and protein immunosensing process. A sandwich immunosensor based on permeable polypyrrole propylic acid (PPA) film is constructed using mouse IgG as a model analyte. The results show that the introduction of capture antibody conjugated enzyme not only enhances the current responses but also increases the SPR angle shift. The calibration curves of electrochemical (EC) and surface plasmon resonance (SPR) measurement exhibit a similar dependence on the bulk concentration of antigen. An approximate linear relationship can be obtained by plotting the data in semi-logarithmic reference frame. Compared with SPR, EC shows higher sensitivity with prolonged time. The in situ EC-SPR immunosensor described herein could have important potentials for diagnostics and medicine applications.     

Calibration-free concentration analysis for an analyte prone to self-association

Calibration-free concentration analysis (CFCA) based on surface plasmon resonance uses the diffusion coefficient of an analyte to determine the concentration of that analyte in a bulk solution. In general, CFCA is avoided when investigating analytes prone to self-association, as the heterogeneous diffusion coefficient results in a loss of precision. The derivation for self-association of the analyte was presented here. By using the diffusion coefficient for the monomeric state, CFCA provides the lowest possible concentration even though the analyte is self-associated.     

Enhanced Sensitivity of Surface Plasmon Resonance Phase-Interrogation Biosensor by Using Silver Nanoparticles

It is demonstrated that the sensitivity of surface plasmon resonance phase-interrogation biosensor can be enhanced by using silver nanoparticles. Silver nanoparticles were fabricated on silver films by using thermal evaporation. Sizes of silver nanoparticles on silver thin film can be tuned by controlling the deposition parameters of thermal evaporation. By using surface plasmon resonance heterodyne interferometey to measure the phase difference between the p and s polarization of incident light, we have demonstrated that sensitivity of glucose detection down to the order of 10⁻⁸ refractive index units can be obtained.     

Transmitive Spectral SPR Droplet Biosensing: Principle,Sensor Design,and Experimental Demonstration

Surface plasmons resonance (SPR) architectures based on grating coupler/disperser combination is an attractive alternative for spectral-based biochemical sensing. In this paper, we investigate theoretically and experimentally a new concept where the plasmon coupling occurs through a thin film grating and sensing occurs via the first evanescent diffraction order in transmitive mode. The surface plasmon wave excitation induces a peak in the wavelength as well as in the angular spectra of the detected first transmitted diffraction order. Accordingly, a change in SPR spectrum of the detected diffraction order can be used to quantify the amount of the target molecules immobilized on the sensor surface, and therefore, the concentration of these molecules in the analyte solution. The developed sensor architecture is dedicated to droplet biochemical sensing and appears to be especially suitable for biosensor integration and miniaturization. The presented sensor concept is perfectly suited for mass production of low-cost and reproducible SPR sensor chip for biochemical analysis. The implemented setup gives access to multichannel biosensing with the potential for efficient internal referencing essential to achieve sufficiently high reproducibility and accuracy of the measurements.     

Plasmon Hybridization in Silver Nanoislands as Semishells Arrays Coupled to a Thin Metallic Film

We obtained experimentally strong plasmon interactions between localized surface plasmon with delocalized surface plasmon polaritons in a new nanosystem of silver semishells island film arrays arranged as a closed-packing structure coupled to an adjacent thin silver film. We show that plasmon interactions for such a nanosystem exhibits two pronounced resonances and interpret the coupling in terms of Fano resonances. The higher energy resonance is identified as a symmetric hybridization mode between localized plasmon resonances in the island semishell array and surface plasmon polaritons in the metal film and while the lower energy resonance is identified as a corresponding anti-symmetric hybridization mode. Increasing the size of the particle arrays enhances and red shifts the resonances. We show that adding a dielectric spacer between the semishell island array and the metal film results in a red shifting of the resonances and introduce an additional high energy spectral peak. The effect of the spacer layer is interpreted as a reduced hybridization and the generation of additional localized surface plasmon resonances.