Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.     

Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica-gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed ( approximately 40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from approximately 520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the effectiveness of nanoparticles of different sizes for real biomedical applications, size-normalized optical cross-sections or per micron coefficients are calculated. Gold nanorods show per micron absorption and scattering coefficients that are an order of magnitude higher than those for nanoshells and nanospheres. While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorods of high aspect ratio with a larger effective radius.     

Analysis of immunoreaction with localized surface plasmon resonance biosensor

The localized surface plasmon resonance (LSPR)-based optical biosensor was used as a potential tool for label-free detection of immunoreaction. The glass substrate covered with the self-assembled monolayer (SAM) of gold colloids was used widely in the sensors. Here, the glass substrate was modified by chemical hydroxylation first, and then gold colloids were immobilized on the substrate by electrostatic adsorption. The LSPR spectra were obtained on UV–vis absorption spectrometer. The specificity was examined by extensive nonspecific binding tests. The resonance condition on the local dielectric environment enables a simple form of molecular sensing. The binding of analyte to the biosensor surface causes a change in the absorbance which was responsive to the concentration of human IgG. So, the LSPR sensing yields similar results to the SPR technique, yet with much simpler instrument.     

Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles

We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface.     

Influence of particle size on the binding activity of proteins adsorbed onto gold nanoparticles

We used optical extinction spectroscopy to study the structure of proteins adsorbed onto gold nanoparticles of sizes 5-60 nm and their resulting biological binding activity. For these studies, proteins differing in size and shape, with well-characterized and specific interactions-rabbit immunoglobulin G (IgG), goat anti-rabbit IgG (anti-IgG), Staphylococcal protein A, streptavidin, and biotin-were used as model systems. Protein interaction with gold nanoparticles was probed by optical extinction measurements of localized surface plasmon resonance (LSPR) of the gold nanoparticles. Binding of the ligands in solution to protein molecules already immobilized on the surface of gold causes a small but detectable shift in the LSPR peak of the gold nanoparticles. This shift can be used to probe the binding activity of the adsorbed protein. Within the context of Mie theory calculations, the thickness of the adsorbed protein layer as well as its apparent refractive index is shown to depend on the size of the gold nanoparticle. The results suggest that proteins can adopt different orientations that depend on the size of the gold nanospheres. These different orientations, in turn, can result in different levels of biological activity. For example, we find that IgG adsorbed on spheres with diameter ≥20 nm does not bind to protein A. This study illustrates the principle that the size of nanoparticles can strongly influence the binding activity of adsorbed proteins. In addition to the importance of this in cases of direct exposure of proteins to nanoparticles, the results have implications for proteins adsorbed to materials with nanometer scale surface roughness.     

A spherical harmonic transform spectral analysis of a localized surface plasmon on a gold nano shell

We perform a study of the localized surface plasmon (LSP) modes of a gold nano shell having a silica core by means of discrete dipole approximation (DDA) and spherical harmonics transform for selected wavelengths. We demonstrate an efficient solution for the near and intermediate field terms by the dyadic Green function approach and determine the optical extinction efficiency by the far field term. Using this approach, we combine the advantages of a spectral analysis along with a DDA flexibility to solve an arbitrary shaped model and demonstrate the LSP dominant mode wavelength dependency. Our approach provides a metric which may be used to quantify the effects of minor changes in the model structure, or the external dielectric environment, in optical experiments. © 2014 Wiley Periodicals, Inc.     

Measurement of antibody binding to protein immobilized on gold nanoparticles by localized surface plasmon spectroscopy

Antibody binding to bovine serum albumin (BSA) and human serum albumin (HSA) immobilized onto gold nanoparticles was studied by means of localized surface plasmon resonance (LSPR) spectroscopy. Amine-modified glass was prepared by self-assembly of amine-terminated silane on substrate, and gold (Au) nanoparticles were deposited on the amine-modified glass substrate. Au nanoparticles deposited on the glass surface were functionalized by BSA and HSA. BSA immobilization was confirmed by LSPR spectroscopy in conjunction with surface-enhanced Raman scattering spectroscopy. Then, LSPR response attributable to the binding of anti-BSA and anti-HSA to BSA- and HSA-functionalized Au nanoparticles, respectively, was examined. Anti-HSA at levels larger than ∼10 nM could be detected by HSA-immobilized chips with LSPR optical response, which was saturated at concentrations greater than ∼650 nM of anti-HSA. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible to authorized users.     

Improving surface plasmon resonance imaging of DNA by creating new gold and silver based surface nanostructures

The use of nanoparticles (NPs) can substantially improve the analytical performance of surface plasmon resonance imaging (SPRi) in general, and in DNA sensing in particular. In this work, we report on the modification of the gold surface of commercial biochips with gold nanospheres, silica-coated gold nanoshells, and silver nanoprisms, respectively. The NPs were tethered onto the surface of the chip and functionalized with a DNA probe. The effects of tethering conditions and varying nanostructures on the SPRi signals were evaluated via hybridization assays. The results showed that coupling between planar surface plasmons and electric fields, generated by localized surface plasmons of the NPs, is mandatory for signal enhancement. Silver nanoprisms gave the best results in improving the signal change at a target DNA concentration of <50 nM by +50 % (compared to a conventional SPRi chip). The limit of detection for the target DNA was 0.5 nM which is 5 times less than in conventional SPRi.

High-sensitivity biosensors fabricated by tailoring the localized surface plasmon resonance property of core-shell gold nanorods

An enhanced sensitive biosensor has been developed to detect biological targets by tailoring the localized surface plasmon resonance property of core–shell gold nanorods. In this new concept, a shell layer is produced on gold nanorods by generating a layer of chalcogenide on the gold nanorod surface after attachment of the recognition reagent, namely, goat IgG and antigen of schistosomiasis japonica. The bioactivity of these attached biomolecules is retained and the sensitivity of this biosensor is thus enhanced significantly. The plasmonic properties of the gold nanorods attached with the biomolecules can be adjusted and the plasmon resonance wavelength can be red-shifted up to several hundred nanometers in the visible or near infrared (NIR) region, which is extremely important to biosensing applications. This leads to a lager red-shift in the localized surface plasmon resonance absorption compared to the original gold nanorod-based sensor and hence offers greatly enhanced sensitivity in the detection of schistosomiasis japonica. The human serum infected with schistosomiasis japonica diluted to 1:50,000 (volume ratio, serum/buffer solution) can be detected readily. The technique offers enhanced sensitivity and can be easily extended to other sensing applications based on not only immuno-recognition but also other types of specific reactions.     

Seed‐Mediated Synthesis of Single‐Crystal Gold Nanospheres with Controlled Diameters in the Range 5–30 nm and their Self‐Assembly upon Dilution

Single‐crystal gold nanospheres with controlled diameters in the range 5–30 nm were synthesized by using a facile approach that was based on successive seed‐mediated growth. The key to the success of this synthesis was the use of hexadecyltrimethylammonium chloride (CTAC) as a capping agent and a large excess of ascorbic acid as a reductant to ensure fast reduction and, thus, single crystallinity and a spherical shape of the resultant nanoparticles. The diameters of the gold nanospheres could be readily controlled by varying the amount of seeds that were introduced into the reaction system. The gold nanospheres could be produced with uniform diameters of up to 30 nm; thus, their localized surface plasmon resonance properties could be directly compared with the results that were obtained from theoretical calculations. Interestingly, we also found that these gold nanospheres self‐assembled into dimers, larger aggregates, and wavy nanowires when they were collected by centrifugation, dispersed in deionized water, and then diluted to different volumes with deionized water.     

Surface-enhanced Raman scattering of EDOT and PEDOT on silver and gold nanoparticles

Surface-enhanced Raman scattering (SERS) spectra of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and its monomer 3,4-ethylenedioxythiophene (EDOT) on Ag and Au nanoparticles presenting different morphologies and stabilizing agents have been obtained using the excitation radiation at 633 nm. The SERS spectra of the monomer and polymer are strongly dependent both on the metal and capping agent of the substrate. SERS spectra of EDOT on Au nanospheres indicates that adsorption occurs with the thiophene ring perpendicular to the metal surface. In contrast, polymerization takes place on the silver surface of Ag nanospheres. EDOT adsorption on Ag nanoprisms with polyvinylpyrrolidone (PVP) as capping agent occurs similarly to that observed on gold. Surface-enhanced resonance Raman scattering (SERRS) spectra of PEDOT on gold nanostars that present a thick layer of PVP show no chemical interaction of PEDOT with the metal surface; however, when PEDOT is adsorbed on citrate stabilized gold nanospheres, the SERRS spectra suggest that thiophene rings are perpendicular to the surface. Oxidation of PEDOT also is observed on Ag nanospheres. The investigation of the interface between PEDOT and metal surface is crucial for the development in polymer-based optoelectronic devices since this interface plays a crucial role in their stability and performance.     

Gold nanostructures: engineering their plasmonic properties for biomedical applications

The surface plasmon resonance peaks of gold nanostructures can be tuned from the visible to the near infrared region by controlling the shape and structure (solid vs. hollow). In this tutorial review we highlight this concept by comparing four typical examples: nanospheres, nanorods, nanoshells, and nanocages. A combination of this optical tunability with the inertness of gold makes gold nanostructures well suited for various biomedical applications.     

Nanoscale actuation of thermoreversible polymer brushes coupled with localized surface plasmon resonance of gold nanoparticles

This paper describes the fabrication of hybrid nanoassemblies with polymer brushes and gold nanoparticles enabling detection of nanoscale optical changes based on localized surface plasmon resonance. The reversible and thermosensitive nanoscale actuation is achieved by combining stimuli-responsive polymer brushes and gold nanoparticles independently and selectively assembled on substrates. These hybrid nanoassemblies are assembled on numerous substrates and will be applicable for optoelectronics, nanoactuator, and nanosensor applications.     

静电组装金纳米粒子制备局域表面等离子体共振传感膜

采用聚电解质自组装技术制备局域表面等离子体共振(LSPR)传感膜的方法, 在玻璃基片上依次沉积聚电解质PDDA, PSS和PVTC, 并通过静电吸附构建胶体金纳米粒子自组装膜形成LSPR传感膜. 利用扫描电镜对LSPR传感膜表面形貌以及膜中金纳米粒子的粒径进行了表征, 同时通过紫外-可见消光光谱对其灵敏度和渗透深度等重要参数进行检测. 研究结果表明, 所制备的LSPR传感膜粒子分布均匀、单分散性好、稳定性高、重现性好; 消光峰位对样品溶液折射率的检测灵敏度为71 nm/RIU, 相应的峰强检测灵敏度为0.21 AU/RIU, 对表面吸附层的渗透深度约为16 nm.     

A novel C-shaped, gold nanoparticle coated, embedded polymer waveguide for localized surface plasmon resonance based detection

In this study, a novel embedded optical waveguide based sensor which utilizes localized surface plasmon resonance of gold nanoparticles coated on a C-shaped polymer waveguide is being reported. The sensor, as designed, can be used as an analysis chip for detection of minor variations in the refractive index of its microenvironment, which makes it suitable for wide scale use as an affinity biosensor. The C-shaped waveguide coupled with microfluidic channel was fabricated by single step patterning of SU8 on an oxidized silicon wafer. The absorbance due to the localized surface plasmon resonance (LSPR) of SU8 waveguide bound gold nano particle (GNP) was found to be linear with refractive index changes between 1.33 and 1.37. A GNP coated C-bent waveguide of 200 μ width with a bend radius of 1 mm gave rise to a sensitivity of ~5 ΔA/RIU at 530 nm as compared to the ~2.5 ΔA/RIU (refractive index units) of the same dimension bare C-bend SU8 waveguide. The resolution of the sensor probe was ~2 × 10(-4) RIU.     

Enhancement of the sensitivity of surface plasmon resonance biosensor with colloidal gold labeling technique

In our experiment colloidal gold was used to enhance the signal obtained from the surface-plasmonresonance biosensor. Fab′ fragments of human IgG molecules were immobilized on the gold surface and reacted with the sheep-anti-human IgG(SAH-IgG) molecules in solution. It was found that when the colloidal gold labeling technique was introduced the sensitivity of surface plasmon resonance instruments increased by a factor of about 300.     

Electrophoretic separation of gold nanoparticles according to bifunctional molecules‐induced charge and size

Gold nanospheres modified with bifunctional molecules have been separated and characterized by using agarose gel electrophoresis as well as optical spectroscopy and electron microscopy. The electrophoretic mobility of a gold nanosphere capped with 11‐mercaptoundecanoic acid (MUA) has been found to depend on the number of MUA molecules per gold nanosphere, indicating that it increases with the surface charge of the nanoparticle. The extinction spectrum of gold nanospheres capped with MUA at an MUA molecules per gold nanosphere value of 1000 and connected via 1,6‐hexanedithiol (HDT) decreases by 33% in magnitude and shifts to the red as largely as 22 nm with the increase of the molar ratio of HDT to MUA (R_HM). Gold nanospheres capped with MUA and connected via HDT have been separated successfully using gel electrophoresis and characterized by measuring reflectance spectra of discrete electrophoretic bands directly in the gel and by monitoring transmission electron microscope images of gold nanoparticles collected from the discrete bands. Electrophoretic mobility has been found to decrease substantially with the increment of HDT to MUA, indicating that the size of aggregated gold nanoparticles increases with the concentration of HDT.     

Surface-plasmon-resonance-enhanced cavity ring-down detection

The cavity ring-down technique is used to probe the absolute optical response of the localized surface plasmon resonance (SPR) of a gold nanoparticle distribution to adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) from the gas phase. Extended Mie theory for a coated sphere with a particle-size-dependent dielectric function is used to elucidate size-dispersion effects, the size-dependence of the SPR sensitivity to adsorption, and the kinetics of adsorption. An approximate Gaussian distribution of nanospheres with a mean diameter of 4.5 nm and a standard deviation of 1.1 nm, as determined by atomic force microscopy, is provided by the intrinsic granularity of an ultrathin, gold film, having a nominal thickness of approximately 0.18 nm. The cavity ring-down measurements employ a linear resonator with an intracavity flow cell, which is formed by a pair of ultrasmooth, fused-silica optical flats at Brewster's angle, where the Au film is present on a single flat. The total system intrinsic loss is dominated by the film extinction, while the angled flats alone contribute only approximately 5 x 10(-5)/flat to the total loss. Based on a relative ring-down time precision of 0.1% for ensembles averages of 25 laser shots from a pulsed optical parametric oscillator, the minimum detectable concentrations of PCE and TCE obtained by probing the SPR response are found to be 2 and 7 x 10(-8) mol/L, respectively, based on a 30 s integration time.     

Gold nanoshells on polystyrene cores for control of surface plasmon resonance

A method is presented for synthesizing core-shell structures consisting of monodisperse polystyrene latex nanospheres as cores and gold nanoparticles as shells. Use of polystyrene spheres as the core in these structures is advantageous because they are readily available commercially in a wide range of sizes, and with dyes or other molecules doped into them. Gold nanoparticles, ranging in size from 1 to 20 nm, are prepared by reduction of a gold precursor with sodium citrate or tetrakis(hydroxymethyl)phosphonium chloride (THPC). Carboxylate-terminated polystyrene spheres are functionalized with 2-aminoethanethiol hydrochloride (AET), which forms a peptide bond with carboxylic acid groups on their surface, resulting in a thiol-terminated surface. Gold nanoparticles then bind to the thiol groups to provide up to about 50% coverage of the surface. These nanoparticles serve as seeds for growth of a continuous gold shell by reduction of additional gold precursor. The shell thickness and roughness can be controlled by the size of the nanoparticle seeds as well as by the process of their growth into a continuous shell. By variation of the relative sizes of the latex core and the thickness of the gold overlayer, the plasmon resonance of the nanoshell can be tuned to specific wavelengths across the visible and infrared range of the electromagnetic spectrum, for applications ranging from the construction of photonic crystals to biophotonics. The position and width of the plasmon resonance extinction peak are well-predicted by extended Mie scattering theory.     

Photochemical and analytical applications of gold nanoparticles and nanorods utilizing surface plasmon resonance

In recent years, plasmonics has emerged as a promising tool in the fields of analytical chemistry and biochemistry. In particular, surface plasmon resonance at the surfaces of gold nanostructures has led to the development of widespread interest in gold nanoparticles. In this review, we describe some of the recent progress in the manufacture and use of gold nanoparticles, with particular emphasis on gold nanorods. Furthermore, the spectroscopic and photochemical applications of gold nanospheres and nanorods are described.