Surface plasmon resonance and electrochemistry for detection of small molecules using catalyzed deposition of metal ions on gold substrate

Small molecules are difficult to detect by conventional surface plasmon resonance (SPR) spectroscopy due to the fact that the changes in the refractive index resulted from the binding process of small biomolecules are quite small. Here, we report a simple and effective method to detect small biomolecule using SPR spectroscopy and electrochemistry by catalyzed deposition of metal ions on SPR gold film. As an example, the ascorbic acid-mediated deposition of Ag on gold film was monitored by in situ SPR spectrum. The deposition of Ag atom on gold film resulted in an obvious decrease of depth in SPR angular scan curves of reflectance intensity and minimum reflectivity angle. The depth change of the SPR reflectance intensity and minimum reflectivity angle curves mainly relied on the amount of Ag atom deposited on gold film that can be controlled by the concentration of ascorbic acid. By monitoring the deposition of Ag atom on gold film, ascorbic acid was detected in the concentration range of 2 x 10(-5) M to 1 x 10(-3) M. After each of detections, the SPR sensor surface was completely regenerated by a potential step that stripped off the Ag atom. Furthermore, the regeneration process of the sensor surface provides the feasibility for detecting the concentration of ascorbic acid by electrochemical method.

Photochemical formation of silver and gold nanostructures at the air-water interface and their electrocatalytic properties

In this paper, we report a simple method of fabricating silver and gold nanostructures at the air - water interface, which can be spontaneously assembled through the reduction of AgNO3 and HAuCl4 with ultraviolet (UV) irradiation in the presence of polyacrylic acid (PAA), respectively. It was found that the building blocks in the silver nanostructure are mainly interwoven silver nanofilaments, while those of the gold nanostructure are mainly different sizes of gold nanoparticles and some truncated gold nanoplates, and even coalescence into networks. At the air - water interface, these silver and gold nanostructures can be easily transferred onto the surface of indium tin oxide (ITO) slides and used for electrochemical measurements. After a replacement reaction with H2PdCl4, the silver nanostructure is transformed into a Ag - Pd bimetallic nanostructure, with good electrocatalytic activity for O-2 reduction. The gold nanostructure can also show high electrocatalytic activity to the oxidation of nitric oxide (NO) with a detection limit of about 10 mu M NaNO2 at S/N = 3.

A method to construct polyelectrolyte multilayers film containing gold nanoparticles

Gold nanoparticles in polyelectrolyte multilayers film can be easily prepared by repeating immersion of a substrate in poly(diallyl dimethylammonium) chloride (PDDA)-AuCl4- complexes solution followed by reduction Au3+ through heating. UV-vis spectroscopy, cyclic voltammetry (CV) and tapping-mode atomic force microscopy (AFM) are used to confirm the successful construction of the polyelectrolyte multilayers film and the formation of gold nanoparticles. The multilayers film shows electrocatalytic activity to dioxygen reduction.

Preparation of novel silver-gold bimetallic nanostructures by seeding with silver nanoplates and application in surface-enhanced Raman scattering

Novel silver-gold bimetallic nanostructures were prepared by seeding with silver nanoplates in the absence of any surfactants. During the synthesis process, it was found that the frameworks of silver nanoplates were normally kept though the basal plane of silver nanoplates became rugged. The real morphology of these nanostructures depended on the molar ratio of gold ions to the seed particles. When the molar ratio of gold ions to silver atoms increased from 0.5 to 4, porous or branched silver-gold bimetallic nanostructures could be made. The growth mechanism was qualitatively discussed based on template-engaged replacement reactions and seed-mediated deposition reactions. Due to the unusual structures, they exhibited interesting optical properties. Moreover, they were shown to be an active substrate for surface-enhanced Raman scattering measurements.

Thermal annealing of Au nanorod self-assembled nanostructured materials: Morphology and optical properties

Three-dimensional Au nanorod and An nanoparticle nanostructured materials were prepared by layer-by-layer self-assembly. The plasmonic properties of the An nanorod and An nanoparticle self-assembled nanostructured materials (abbreviated as AuNR and AuNP SANMs) are tunable by the controlled self-assenibly process. The effect of thermal annealing at 180 and 500 degrees C to the morphologies, plasmonic properties and surface-enhanced Raman scattering (SERS) responses of these SANMs were investigated. According to the experimental results, these properties correlate with the structure of the SANMs.

Rapid synthesis of hexagon-shaped gold nanoplates by microwave assistant method

The microwave (MW)-based thermal process was applied to the preparation of hexagon-shaped gold nanoplates. The fort-nation of gold nanoplates occurs rapidly in a single step, carried out by directly heating a reaction mixture of HAuCl4 with sodium citrate in an MW reactor. And the gold nanoplates were characterized by UV-visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The experimental results indicated that the sizes and morphologies of the gold nanomaterials strongly depend both on the heating methods and molar ratio of HAuCl4 to sodium citrate in the initial reaction mixture. At the molar ratio 5 : 4 (HAuCl4 to sodium citrate), hexagonal nanoplates with large Au (111) crystallographic facet were preferentially synthesized by the MW assistant method.

Self-assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surf ace-enhanced Raman scattering (SERS) substrate by self-assembled silver nanoparticles on a monolayer of 4-aminophenyl-group-modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4-aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping-mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p-aminothiophenol (p-ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10(-9) m. This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon-based materials for SERS with high sensitivity.

Investigations on the adsorption behavior of Neutral Red on mercaptoethane sulfonate protected gold nanoparticles

A detailed investigation on the adsorption behavior of Neutral Red (NR) molecules on mercaptoethane sulfonate-monolayer protected gold clusters (MES-MPCs) has been conducted by the spectroscopic method. It is found that cationic NR molecules are adsorbed on the negatively charged MPCs surfaces via electrostatic attractive forces. The absorption study shows that the optical properties of NR molecules are significantly influenced upon the adsorption. Based on the electrostatic adsorption nature and the excellent stability of MES-MPCs against the electrolytes, this association can be released by the addition of electrolyte salts, which can be monitored by both absorption and fluorescence spectroscopy. In addition, dication Ca2+ is found to be more effective in the release of NR than univalent Na+. Moreover, the MES-MPCs exert energy transfer quenching of NR fluorescence by both static and dynamic quenching. However, static quenching seems to be the dominating quenching mechanism. Furthermore, this energy transfer quenching exhibits strong dependence of Au core size, and 5.0 nm MPCs show stronger ability in quenching the NR fluorescence than that of 2.7 nm MPCs.

Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.