Buildup of gold nanoparticle multilayer thin films based on the covalent-bonding interaction between boronic acids and polyols

A novel method for the fabrication of gold nanoparticle multilayer films based on the covalent-bonding interaction between boronic acid and polyols, poly(vinyl alcohol) (PVA), was developed. The multilayer buildup was monitored by UV-vis absorbance, spectroscopy, which showed a linear increase of the film absorbance with the number of adsorbed Au layers and indicated the stepwise and uniform assembling process. The atomic force microscopy (AFM) image showed that a compact gold multilayer thin film was successfully assembled. The residual boronic acid group on the surface of thin film Could incorporate glycosylated-protein horseradish peroxidase (HRP), and good catalytic activity for H2O2 could be observed.

Simple and convenient preparation of Au-Pt core-shell nanoparticles on surface via a seed growth method

Au-Pt core-shell nanoparticles were prepared on glass surface by a seed growth method. Gold nanoparticles were used as seeds and ascorbic acid-H2PtCL6 solutions as growth solutions to deposit Pt shell on the surface of gold nanoparticles. These core-shell nanoparticles and their growth process were examined by UV-Vis spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and field-emission environmental scanning electron microscopy and the results indicated that the deposition speed was fast and nanoparticles with obvious core-shell structure could be obtained after 2 min. Moreover, this seed growth method for preparation of the core-shell nanoparticles is simple and convenient compared with other seed growth methods with NH4OH as a mild reductant. In addition, electrochemical experiments indicated that these Au-Pt core-shell nanoparticles had similar electrochemical properties to those of the bulk Pt electrode.

An approach for fabricating self-assembled monolayer of Ag nanoparticles on gold as the SERS-active substrate

In this paper, an approach for fabricating an active surface-enhanced Raman scattering (SERS) substrate is adopted. This approach is based on the assembling of silver nanoparticles film on gold substrate. Rhodamine 6G (R6G) and p-aminothiophenol (P-ATP) were used as probe molecules for SERS experiments, showing that this new active substrate has sensitivity to SERS response. Tapping-mode atomic force microscopy (AFM) was also used to investigate the surface morphology following the fabricating process of the active SERS substrate, which showed that large quantities of silver nanoparticles were uniformly coated on the substrate.

In situ electrochemical SERS studies on electrodeposition of aniline on 4-ATP/Au surface

The electrochemical polymerization of 0.01 M aniline in 1 M H2SO4 aqueous solution on roughened Au surface modified with a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) has been investigated by in situ electrochemical surface-enhanced Raman scattering spectroscopy (SERS). The repeat units and possible structures of the electrodeposited polyaniline (PANI) film were proposed; i.e., aniline monomer is coupled in head-to-tail predominately at the C-4 of aniline and amine of 4-ATP, and the thin PANI film is orientated vertically to substrate surface. Simultaneous Raman spectra during potential scanning indicate clearly that the ultrathin PANI film (in initial growth of the film) consists of semiquinone radical cation (IP+), para-disubstituted benzene (IP and IP+) and quinine diimine (NP) while it is oxidized, and without quinine diimine and semiquinone radical cation while reduced. Meanwhile, the results confirm that 4-ATP monolayer shows a strong promotion on the electrodeposition of aniline monomer, and a possible polymerization mechanism was proposed.

Electrochemical study of 4-ferrocene thiophenol monolayers assembled on gold nanoparticles

In this paper, 4-ferrocene thiophenol was employed as a novel capping agent to synthesize electroactive gold nanoparticles. Transmission electron microscopy showed an average core diameter of 2.5 nm. The optical and electrochemical properties of the 4-ferrocene thiophenol capped gold nanoparticles were characterized by UV-Vis spectroscopy and cyclic voltammograms. Surface plasmon absorbance was detected at 522 nm. Cyclic voltammograms revealed the adsorbed layer reaction controlled electrode process, and the formal potential of electroactive ferrocene centers shifted anodically compared with ferrocene in solution, which could be attributed to the electron-withdrawing phenyl moiety linked to ferrocene.

Self-assembly of 4-ferrocene thiophenol capped electroactive gold nanoparticles onto gold electrode

Gold nanoparticles capped by 4-ferrocene thiophenol with an average core size of 2.5 nm and surface plasmon absorbance at 522 nm were place-exchanged with 1,8-octanedithiol, and then self-assembled onto the gold electrode via tail SH group. The self-assembly was characterized by X-ray photoelectron spectroscopy. Cyclic voltammograms examined the coverage fraction of the self-assembled monolayers of the electroactive gold nanoparticles and the formal potential of the indicated SAMs. Further experiments exhibited that the electrode process was controlled by surface confined faradic reactions.

Electroactive gold nanoparticles protected by 4-ferrocene thiophenol monolayer

Numerous reports have focused on ferrocene-terminated electroactive self-assembled monolayers (SAMs) on a flat An surface but only a few on ferrocene SAMs on An colloid. In this paper, we employ 4-ferrocene thiophenol as a novel capping agent to produce electroactive gold nanoparticles in consideration of the peculiar pi-conjugated structure. Transmission electron microscopy shows the narrow-dispersed gold core with an average core diameter of ca. 2.5 nm. UV/vis spectra examine the pi-conjugated structure of 4-ferrocene thiophenol and surface plasmon absorbance of the indicated gold nanoparticles. X-ray photoelectron spectroscopy reveals electronic properties of the An core and thiol ligands. Electrochemical measurement shows that the oxidation peak current is proportional to the scan rate, indicating the electrode process is controlled by adsorbed layer reaction. The formal potential of the Fc-MPCs is compared with that of free ferrocene in MeCN solution and the Fc-SAMs. The shifts are attributed to the phenyl moiety in the 4-ferrocene thiophenol and dielectric constant of the solvation environment.

Electrochemical Metalloimmunoassay Based on Enlargement of Gold Nanoparticle Label Treated with Ag Enhancement System

A novel sensitive electrochemical immunoassay with colloidal gold as the antibody labeling tag and subsequent signal amplification by silver enhancement is described. Colloidal gold was treated by a light-sensitive silver enhancement system which made silver deposit on the surface of colloidal gold(form Au/Ag core-shell structure), followed by the release of the metallic silver atoms anchored on the antibody by oxidative dissolution of them in an acidic solution and the indirect determination of the dissolved Ag+ ions by anodic stripping voltammetry(ASV) at a carbon fiber microelectrode. The electrochemical signal is directly proportional to the amount of analyte(goat IgG) in the standard or a sample. The method was evaluated by means of a noncompetitive heterogeneous immunoassay of immunoglobulin G(IgG) with a concentration as low as 0.2 ng/ mL. The high performance of the method is related to the sensitive ASV determination of silver(I) at a carbon fiber microelectrode and to the release of a large number of Ag+ ions from each silver shell anchored on the analyte(goat IgG).

One-pot synthesis and characterization of novel silver-gold bimetallic nanostructures with hollow interiors and bearing nanospikes

One-pot preparation of shell-type silver-gold bimetallic nanostructures with hollow interiors and bearing nanospikes, based on colloid seed-engaged replacement reaction and colloid-mediated deposition reactions, has been reported. Heating-induced evolution of Ag-Au bimetallic nanoshells can lead to spontaneous production of nanospikes on the colloid surface. The hollow interior structure and bimetallic nature of the as-prepared colloids are characterized by transmission electron microscopy (TEM), UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS).

Site-selective self-assembly of MPA-bridged CuHCF multilayers on APTMS-supported gold colloid electrodes

(3-Aminopropyl)trimethoxysilane (APTMS)-supported gold colloid electrode was constructed by virtue of a recently developed solution-based self-assembly strategy. The preparing procedure of 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers on a planar macroelectrode (Bharathi et al. Langmuir 2001, 17, 7468) was copied to the as-prepared colloid electrode. The optical spectra, atomic force microscopy, and electrochemistry demonstrate successful copy of the multilayer system on a macroelectrode to the as-prepared colloid electrode. Remarkably, it was found that multilayer growth is highly selective to the nanoscale sites where gold nanoparticles are immobilized, and multilayer growth does not take place on the sites without nanoparticles. Interestingly, a preliminary electrochemical investigation indicates that electrochemical properties of multilayers systems on the colloid electrode are different from their counterparts on a planar macroelectrode, which might be due to high curvature effects of the gold nanoparticles. This indicates a different motif of multilayers on the colloid electrode from that on a planar macroelectrode.

Aggregation-based fabrication and assembly of roughened composite metallic nanoshells: Application in surface-enhanced Raman scattering

This paper reports an aggregation-based method for the fabrication of composite Au/Ag nanoshells with tunable thickness and surface roughness. It is found that the resultant roughened composite Au/Ag nanoshells can attract each other spontaneously to form films at the air-water interface. Importantly, such films can be transferred onto the solid substrates without being destroyed and show excellent surface-enhanced Raman scattering (SERS) enhancement ability. Their strong enhancement ability may stem from the unique two-dimensional structure itself.

Chitosan mediated assembly of gold nanoparticles multilayer

We initiate a systematic exploration of a natural polymer, chitosan, as a structural material for designing functional layers on electrode surfaces in this work. Au colloid films are organized on chitosan layer by adsorption. We have successfully constructed a multilayer An nanoparticle assembly through electrostatic interactions on chitosan functionalized quartz substrates by the alternate treatment of the substrate with solution of citrate-stabilized gold nanoparticles (negatively charged) and chitosan solution (positively charged). The resulting substrates were characterized by UV-Vis spectrometry, atomic force microscopy (AFM), and electrochemical impedance spectroscopy (EIS) measurements. These assemblies of colloid An multilayer are highly stable, and can be kept for a long time in distilled water, only being removed by scratching or extreme electrochemical conditions.

Toluidine blue modified self-assembled silica gel coated gold electrode as biosensor for NADH

A toluidine blue modified gold electrode was constructed using self-assembled silica gel technique. Firstly, toluidine blue was encapsulated within 3D network of silica self-assembly monolayer on the surface of gold electrode. Secondly, another layer of silica sol was further assembled to protect from leaching of mediator or possible contamination. The electrochemical characteristics of toluidine blue immobilized within self-assembled silica gel were studied in detail. The modified electrode was applied for electrochemical oxidation of NADH with satisfactory results.

Gold nanoparticles as fine tuners of electrochemical properties of the electrode/solution interface

Recently, a novel approach for preparing SERS and SPR substrates was developed, which indicates a potential application in tailoring the interfacial structure of an electrode surface. In this study, (3-mercaptopropyl)trimethoxysilane (MPTMS) was selected as a polymeric adhesive layer, and a low concentration of colloid Au solution was used to achieve a more accurate control over interface morphology at nanoscale dimensions due to slow self-assembling kinetics of gold nanoparticle's. Subsequent seeding growth of these MPTMS-supported submonolayers of gold nanoparticles in Au3+/NH2OH aqueous solution enlarges particle size and eventually results in the generation of conductive gold films (similar to previous (3-aminopropyl)trimethoxysilane-supported gold films). Such tunable interface structure was evaluated by atomic force microscopy (AFM). Also, ac impedance spectroscopy (ACIS) and cyclic voltammograms were performed to evaluate electrochemical properties of the as-prepared interfaces by using Fe(CN)(6) (3-/4-) couples as a probe. Furthermore, relevant theories of microarray electrodes were introduced into this study to explain the highly tunable electrochemical properties of the as-prepared interfaces. As a result, it is concluded that the electrochemical properties toward Fe(CN)(6) (3-/4-) couples are highly dependent on the active nanoelectrode (nanoparticles) area fraction and nanoparticles are fine-tuners of interfacial properties because the number density. (numbers/unit area) and size of nanoparticles are highly tunable by self-assembling and seeding growth time scale control. This is in agreement with the theoretical expectations for a microarray electrode if a single nanoparticle tethered to a blocking SAM is taken as a nanoelectrode and 2-D nanoparticle assemblies are taken as nanoelectrode arrays.

Investigation of electrochemical charging behaviors of "naked" gold nanoparticles ensembles in aqueous media

Gold nanopartides were Immobilized onto the electrode surface by simple self-assembly technique. Interestingly, the ensembles of these nanopartides exhibit quantized charging behaviors in aqueous solution. Possible mechanism for such behaviors was proposed.