Grating-induced plasmon mode in gold nanoparticle arrays

We study the dipolar coupling of gold nanoparticles arranged in regular two-dimensional arrays by extinction micro-spectroscopy. When the interparticle spacing approaches the plasmon resonance wavelength of the individual particles, an additional band of very narrow width emerges in the extinction spectrum. By systematically changing the particles dielectric environment, the particles shape, the grating constant and angle of incidence, we show how this band associated to a grating induced-resonance can be influenced in strength and spectral position. The spectral position can be qualitatively understood by considering the conditions for grazing grating orders whereas the strength can be related to the strength of dipolar scattering from the individual particles.     

Monitoring gold nanorod synthesis by localized surface plasmon resonance

Surfactants can direct the growth of gold nanoparticles to create anisotropic structures in high yield by simple means, yet the exact roles of surfactants and other reactants are not entirely understood. Here we show that one can exploit the geometrical dependence of the localized surface plasmon resonant extinction spectrum of gold nanorods to monitor their synthesis kinetics. By using quantitative measurements of nanorod extinction cross sections, Gans' theory for the spectral extinction of prolate spheroids can be normalized to provide values for the nanorod length and diameter from extinction spectra measured during growth. The nanorod length growth rate was first observed at 0.15 nm/s and decayed during the growth reaction. The rate dependence on nanorod size did not correspond to any simple reaction-limited or diffusion-limited growth mechanisms.     

Nanosensors based on responsive polymer brushes and gold nanoparticle enhanced transmission surface plasmon resonance spectroscopy

Swelling (and shrinking) of poly(2-vinylpyridine), P2VP, polymer brushes, caused by pH changes, could be readily monitored by transmission surface plasmon resonance, T-SPR, spectroscopy. Gold nanoparticles attached to the P2VP polymer brushes dramatically enhanced the pH-induced shift in the T-SPR absorption spectra. (A 50 nm shift of the absorption maximum of the T-SPR spectrum of the supporting gold nanoislands was observed upon changing the pH from 5.0 to 2.0, corresponding to a swelling of the polymer brushes from 8.1 +/- 0.7 to 24.0 +/- 2.0 nm. Same shift in the opposite direction was observed upon changing the pH from 2.0 to 5.0.)     

Efficient synthesis of single gold nanoparticle hybrid amphiphilic triblock copolymers and their controlled self-assembly

We report on a robust approach to the size-selective and template-free synthesis of asymmetrically functionalized ultrasmall (<4 nm) gold nanoparticles (AuNPs) stably anchored with a single amphiphilic triblock copolymer chain per NP. Directed NP self-assembly in aqueous solution can be facilely accomplished to afford organic/inorganic hybrid micelles, vesicles, rods, and large compound micelles by taking advantage of the rich microphase separation behavior of the as-synthesized AuNP hybrid amphiphilic triblock copolymers, PEO-AuNP-PS, which act as the polymer-metal-polymer analogue of conventional amphiphilic triblock copolymers. Factors affecting the size-selective fabrication and self-assembly characteristics and the time-dependent morphological evolution of NP assemblies were thoroughly explored.     

In situ synthesis of oligonucleotide arrays by using surface tension

This work describes the in situ synthesis of oligonucleotide arrays on glass surfaces. These arrays are composed of features defined and separated by differential surface tension (surface tension arrays). Specifically, photolithographic methods were used to create a series of spatially addressable, circular features containing an amino-terminated organosilane coupled to the glass through a siloxane linkage. Each feature is bounded by a perfluorosilanated surface. The differences in surface energies between the features and surrounding zones allow for chemical reactions to be readily localized within a defined site. The aminosilanation process was analyzed using contact angle, X-ray photoelectron spectroscopy (XPS), and time-of-flight/secondary ion mass spectroscopy (TOF-SIMS). The efficiency of phosphoramidite-based oligonucleotide synthesis on these surface tension arrays was measured by two methods. One method, termed step-yields-by-hybridization, indicates an average synthesis efficiency for all four (A,G,C,T) bases of 99.9 +/- 1.1%. Step yields measured for the individual amidite bases showed efficiencies of 98.8% (dT), 98.0% (dA), 97.0% (dC), and 97.6% (dG). The second method for determining the amidite coupling efficiencies was by capillary electrophoresis (CE) analysis. Homopolymers of dT (40- and 60mer), dA (40mer), and dC (40mer) were synthesized on an NH(4)OH labile linkage. After cleavage, the products were analyzed by CE. Synthesis efficiencies were calculated by comparison of the full-length product peak with the failure peaks. The calculated coupling efficiencies were 98.8% (dT), 96.8% (dA), and 96.7% (dC).     

Waveguide surface plasmon resonance studies of surface reactions on gold electrodes

We describe the fabrication and characterisation of gold-coated graded index channel waveguide sensors designed for simultaneous electrochemical and surface plasmon resonance studies. The active sensing electrode area is a thin gold film between 0.5 and 5 mm in length and 200 microm wide deposited on top of a 3 microm wide waveguide which forms one arm of a Y-junction while the other arm of the Y-junction serves as a reference. Using these devices we have measured simultaneously the changes in transmittance through the device whilst carrying out cyclic voltammetry in either sulfuric or perchloric acid solution or during the deposition of an UPD layer of copper at the gold surface. In all cases we obtain stable and reproducible results which demonstrate the very high sensitivity of the devices to sub-monolayer changes occurring at the gold electrode surface. The response of these integrated optoelectrochemical devices is discussed in terms of a numerical model for the propagation of light within the waveguide structure.     

Reversible pH-driven conformational switching of tethered superoxide dismutase with gold nanoparticle enhanced surface plasmon resonance spectroscopy

A new class of surface-immobilized protein nanomachines can be reversibly actuated by cycling the solution pH between 2.5 and 12.3, which induces a conformational change, thereby modulating the thickness of superoxide dismutase (SOD1) tethered to the Au thin film. By placing Au nanoparticles (AuNP) atop the immobilized SOD1 by means of a gold-thiol assembly, the nanoscale motion of SOD1 at the interface produces mechanical work to lift and then lower the AuNP from the Au substrate by a distance of ca. 3 nm and transduces this motion into an easily measurable reflectivity change in the surface plasmon resonance (SPR) spectrum. As-made supported conjugate consisting of SOD1 and AuNP is quite robust and stable, and its operation in response to pH variations, which mirrors the conformational changes of responsive SOD1 at the interface, is found to be highly reversible and reproducible. This is the first demonstration of the development of novel solid-state sensors and/or switching devices based on substrate-bound protein conformational changes and AuNP enhanced SPR spectroscopy.     

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.     

Patterned arrays of au rings for localized surface plasmon resonance

In this paper, we examined the characteristic behavior of localized surface plasmon resonances (LSPR) of Au dot and ring arrays in response to the selective binding of biomolecules. To do this, patterned arrays of Au rings and dots with various feature scales were fabricated over large areas by an imprint lithography technique. Our results showed that the LSPR spectra of the Au nanorings exhibited a blue shift with increase in the ring widths and asymptotically converged to those for Au nanodots. This clearly implies that the LSPR spectra can be tuned over an extended wavelength range by varying the ring width. For an illustrative purpose, the patterned Au structures were used to detect the binding of streptavidin to biotin. In doing this, the Au patterns were chemically modified with G4 dendrimers of amine terminated poly(amidoamine), which facilitated the tethering of biotin onto the Au pattern. Exposure of the biotinylated Au nanorings to aqueous streptavidin solution induced both red-shifts of the LSPR spectra and changes in the peak intensities. The sensitivity of the LSPR spectra to the binding of the biomolecules was enhanced as the ring width of Au rings was decreased.     

In situ sensing of metal ion adsorption to a thiolated surface using surface plasmon resonance spectroscopy

The kinetics of the adsorption of metal ions onto a thiolated surface and the selective and quantitative sensing of metal ions were explored using surface plasmon resonance (SPR) spectroscopy. The target metal ion was an aqueous solution of Pt2+ and a thin-gold-film-coated glass substrate was modified with 1,6-hexanedithiol (HDT) as a selective sensing layer. SPR spectroscopy was used to examine the kinetics of metal ion adsorption by means of the change in SPR angle. The selectivity of the thiolated surface for Pt2+ over other divalent metal ions such as Cu2+, Ni2+, and Cd2+ was evident by the time-resolved SPR measurement. SPR angle shift, deltatheta(SPR), was found to increase logarithmically with increasing concentration of Pt2+ in the range of 1.0 x 10(-5)-1.0 mM. The rate of Pt2+ adsorption on HDT observed at both 0.1 and 1 mM Pt2+ accelerates until the surface coverage reaches approximately 17%, after which the adsorption profile follows Langmuirian behavior with the surface coverage. The experimental data indicated that heavy metal ions were adsorbed to the hydrophobic thiolated surface by a cooperative mechanism. A mixed self-assembled monolayer (SAM) composed of HDT and 11-mercaptoundecanoic acid was used to reduce the hydrophobicity of the thiol-functionalized surface. The addition of hydrophilic groups to the surface enhanced the rate of adsorption of Pt2+ onto the surface. The findings show that the adsorption of metal ions is strongly dependent upon the hydrophilicity/hydrophobicity of the surface and that the technique represents an easy method for analyzing the adsorption of metal ions to a functionalized surface by combining SPR spectroscopy with a SAM modification.     

Carbon-on-metal films for surface plasmon resonance detection of DNA arrays

Surface plasmon resonance (SPR) imaging affords label-free monitoring of biomolecule interactions in an array format. A surface plasmon conducting metal thin film is required for SPR measurements. Gold thin films are traditionally used in SPR experiments as they are readily functionalized with thiol-containing molecules through formation of a gold-sulfur bond. The lability of this gold-thiol linkage upon exposure to oxidizing conditions and ultraviolet light renders these surfaces incompatible with light-directed synthetic methods for fabricating DNA arrays. It is shown here that applying a thin carbon overlayer to the gold surface yields a chemically robust substrate that permits light-directed synthesis and also supports surface plasmons. DNA arrays fabricated on these carbon-metal substrates are used to analyze two classes of biomolecular interactions: DNA-DNA and DNA-protein. This new strategy allows the combinatorial study of binding interactions directly from native, unmodified biomolecules of interest and offers the possibility of discovering new ligands in complex mixtures such as cell lysates.     

Coating sulfonated polystyrene microspheres with highly dense gold nanoparticle shell for SERS application

The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH₃)₂]⁺ ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS.

DNA-templated self-assembly of protein and nanoparticle linear arrays

Self-assembling DNA tiling lattices represent a versatile system for nanoscale construction. Self-assembled DNA arrays provide an excellent template for spatially positioning other molecules with increased relative precision and programmability. Here we report an experiment using a linear array of DNA triple crossover tiles to controllably template the self-assembly of single-layer or double-layer linear arrays of streptavidin molecules and streptavidin-conjugated nanogold particles through biotin-streptavidin interaction. The organization of streptavidin and its conjugated gold nanoparticles into periodic arrays was visualized by atomic force microscopy and scanning electron microscopy.     

Sensitivity of metal nanoparticle surface plasmon resonance to the dielectric environment

Electrodynamic simulations of gold nanoparticle spectra were used to investigate the sensitivity of localized surface plasmon band position to the refractive index, n, of the medium for nanoparticles of various shapes and nanoshells of various structures. Among single-component nanoparticles less than 130 nm in size, sensitivities of dipole resonance positions to bulk refractive index are found to depend only upon the wavelength of the resonance and the dielectric properties of the metal and the medium. Among particle plasmons that peak in the frequency range where the real part of the metal dielectric function varies linearly with wavelength and the imaginary part is small and slowly varying, the sensitivity of the peak wavelength, lambda, to refractive index, n, is found to be a linearly increasing function of lambda, regardless of the structural features of the particle that determine lambda. Quasistatic theory is used to derive an analytical expression for the refractive index sensitivity of small particle plasmon peaks. Through this analysis, the dependence of sensitivity on band position is found to be determined by the wavelength dependence of the real part, epsilon', of the particle dielectric function, and the sensitivity results are found to extend to all particles with resonance conditions of the form, epsilon' = -2chin(2), where chi is a function of geometric parameters and other constants. The sensitivity results observed using accurate computational methods for dipolar plasmon bands of gold nanodisks, nanorods, and hollow nanoshells extend, therefore, to particles of other shapes (such as hexagonal and chopped tetrahedral), composed of other metals, and to higher-order modes. The bulk refractive index sensitivity yielded by the theory serves as an upper bound to sensitivities of nanoparticles on dielectric substrates and sensitivities of nanoparticles to local refractive index changes, such as those associated with biomolecule sensing.     

A gold nanoparticle labeling strategy for the sensitive kinetic assay of the carbamate-acetylcholinesterase interaction by surface plasmon resonance

The article presents a novel strategy for a sensitive investigation of the interaction between acetylcholinesterase (AChE) and its small molecular carbamate inhibitors. Two carbamate inhibitors with different ether linkages and the terminal lipoate were synthesized and labeled with gold nanoparticles (AuNPs). With the signal amplification of AuNPs, the specific interactions between the AuNPs labeled carbamate inhibitors (ALC1 and ALC2) and the immobilized AChE on sensor chip surface were readily examined. The detection sensitivities of ALC1 and ALC2 were 176 and 121 m°/nM, respectively, with the detection limits of 7.0 and 12 pM at a signal-to-noise ratio of 3. The association/dissociation constants for the binding interaction between carbamate inhibitors and AChE were reported for the first time. The affinity constants were estimated to be 3.13 × 10⁶ and 6.39 × 10⁵ M⁻¹ for ALC1 and ALC2 respectively. This AuNPs labeling strategy is versatile and may be applicable for the direct or competitive SPR kinetic assay of the interaction between small molecule inhibitors and their target proteins with a high sensitivity.     

In situ surface plasmon resonance measurements of self-assembled monolayers of ferrocenylalkylthiols under constant potentials.

A commercial system for surface plasmon resonance (SPR) possessing a batch-type flow channel has been simply modified so as to conduct in situ SPR measurements under polarization of an Au sensor chip at constant potentials. The modified instrument can monitor electrochemical reactions of monolayer materials with high stability and high reproducibility. The redox reaction of a self-assembled monolayer (SAM) of 6-ferrocenyl-1-hexanethiol (FcHT) induced the resonance angle shifts, the magnitudes of which accorded with the Nernst equation. The measurements in electrolyte solutions containing different electrolyte anions revealed that the SPR measurements detected ion pairing of electrolyte anions with oxidized FcHT. In cases of measurements in alkylsulfonic acid solution, simulation of the results based on the N-layer model has clarified that alkylsulfonate anions make an assembled layer on the FcHT SAM.     

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.     

A Au nanoparticle and polydopamine co-modified biosensor: A strategy for in situ and label-free surface plasmon resonance immunoassays

This article reports a surface plasmon resonance (SPR) strategy capable of label-free yet amplified in situ immunoassays for sensitive and specific detection of human IgG (hIgG), a serum marker that is important for the diagnosis of certain diseases. Primarily, a wavelength-modulated Kretschman configuration SPR analyzer was constructed, and Au film SPR biosensor chips were fabricated. Specifically, based on Au nanoparticles (AuNPs) adsorbed on the surface of the Au film, the AuNP/Au film was coated with polydopamine (PDA) to fix streptavidin (SA), and then the biotinylated antibodies were connected to the surface of the biosensor chip. The SPR analyzer was utilized for in situ real-time monitoring of hIgG. Due to the immunological recognition between the receptor and target, the surface plasmon waves produced by the attenuated total reflection were affected by the changes in the surface of the biosensor chip. The resonance wavelength (λ_R) of the output spectra gradually redshifted, and the redshift degrees were directly related to the target concentration. The biosensor can realize the in situ detection of hIgG, displaying satisfactory sensitivity, excellent specificity and stability. Briefly, by monitoring the shift in λ_R after specific binding, a new SPR immunoassay can be customized for label-free, in situ and amplified hIgG detection. The operating principle of this research could be extended as a common protocol for many other targets of interest.     

Detection of ozone gas using gold nanoislands and surface plasmon resonance

Gold nanoislands interact with gaseous ozone to produce a surface plasmon resonance shift, similarly to the interaction of ozone and gold nanoparticles in water. Gold nanoislands are produced by sputtering, which significantly simplifies the synthesis and produces controlled size for the gold nanoislands. The shift of surface plasmon resonance peak was monitored while gold nanoislands were exposed to variable concentration of gaseous ozone. The shift was then correlated with ozone concentration. Our current results indicate sensing gaseous ozone at concentration of as low as 20 μg/L is achievable. Gold nanoislands were reversed to their original wavelength and were able to cycle between the wavelengths as ozone was introduced and removed. Potentially, this system can be useful as a sensor that identifies the presence of ozone at low part-per-billion concentrations of ozone in gaseous media.