Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

Formation of ordered arrays of gold nanoparticles from CTAB reverse micelles

In this presentation, a reverse micelle technique was described to create colloid gold nanoparticles and their self-organization into superlattices. Gold nanoparticles were prepared by the reduction of HAuCL4 in CTAB/octane + 1-butanol/H2O reverse micelle system using NaBH4 as reducing agent. Dodecanethiol (C12H25SH) was used to passivate the gold nanoparticles immediately after formation of the gold colloid. After re-dispersing in toluene under ultrasonication, a supernatant containing nearly monodispersed dodecanethiol-capped gold nanoparticles was obtained. Self-organization of the gold nanoparticles into 1D, 2D and 3D superlattices was observed on the carbon-coated copper grid by TEM. UV-vis absorption spectra were also used to characterize the gold colloids with and without dodecanethiol capping. (C) 2001 Elsevier Science B.V. All rights reserved.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Gold-coated iron (Fe@Au) nanoparticles: Synthesis, characterization, and magnetic field-induced self-assembly

A unique reverse micelle method has been developed to prepare gold-coated iron (Fe@Au) nanoparticles. XRD, UV/vis, TEM, and magnetic measurements are utilized to characterize the nanocomposites. XRD only gives FCC patterns of gold for the obtained nanoparticles. The absorption band of the Fe@Au colloid shifts to a longer wavelength and broadens relative to that of the pure gold colloid. TEM results show that the average size of Fe@Au nanoparticles is about 10 nm, These nanoparticles are self-assembled into chains on micron scale under a 0.5 T magnetic field. Magnetic measurements show that the particles are superparamagnetic with a blocking temperature (T-B) of 42 K, At 300 K (above T-B), no coercivity (Hc) and remanence (M-r) is observed in the magnetization curve, while at 2K (below T-B) He and M, are observed to be 728 Oe and 4.12 emu/g, respectively, (C) 2001 Academic Press.

Rapid electron propagation through molecular wire monolayers sandwiched between two gold electrodes

Conjugated bisthioester 1 was synthesized applying Sonogashira coupling reactions. Using self-assembly in combination with nanoparticles deposition techniques, we developed a novel method to fabricate a "gold electrode-molecular wire monolayers-gold nanoparticles" sandwich-like structure. Rapid electron propagation through this sandwich-like structure was observed by cyclic voltammetry and ac impedance measurements.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Superlattice structure of gold nanoparticles film deposited by Langmuir-Blodgett technique

Dodecanethiol-capped gold nanoparticles could spread on water subphase and be transferred by LB technique. The superlattice structure of gold nanoparticles multilayer was discussed.

Technique for determination of gold electrode area and its application of characterization in self-assembling process

Underpotential deposition(UPD) of copper at polycrystal gold surface under different concentrations has been studied, and its reversibility and stability in high concentration (0.2M CuSO4+0.IM H2SO4) have been demonstrated by cyclic voltermmetry and EQCM. A Valid approach to determine the gold electrode area in presence of adsorbed species has been provided by using Cu UPD method. Further, the growth kinetics of decane thiol on gold has also been investigated based on such a Cu UPD technique.

Electrocatalytic mechanism for formaldehyde oxidation on the highly dispersed gold microparticles and the surface characteristics of the electrode

Electrocatalytic mechanism for the electrochemical oxidation of formaldehyde (HCHO) on the highly dispersed Au microparticles electrodeposited on the surface of the glass carbon (GC) electrode in the alkaline Na2CO3/NaHCO3 solution and the surface characteristics of the Au microparticle-modified glass carbon (Au/GC) electrode were studied with in situ FTIR spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the final products of HCHO oxidation is HCOO- at the Au/GC electrode and CO2 at the bulk Au electrode. The difference may be ascribed to the different surface characteristics between the Au/GC electrode and the bulk Au electrode. (C) 1999 Elsevier Science B.V. All rights reserved.

Electrochemical growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.

Electrochemical studies of cytochrome c disulfide at gold electrodes

The electrochemistry of disulfide in cytochrome c on gold electrodes was reported. The observed electrochemical response was used to explain why the electrochemical reaction of cytochrome c is irreversible at gold electrodes. Disulfide bonds in cytochrome c were strongly adsorbed onto the surface of gold electrodes and caused slow rate of electron transfer of the heme group. It was found that the presence of disulfides in cytochrome c was responsible for the lack of electrochemical response of the heme group on a gold electrode. The mechanisms for this effect were studied using electrochemistry and photoelectron spectroscopy. (C) 1999 Elsevier Science B.V. All rights reserved.

Langmuir-Blodgett films of octadecanethiol on gold sols subphase

An octadecanethiol monolayer was formed on an aqueous gold sols subphase, it's LB films were characterized by means of pi-A isotherms, TEM (transmission electron microscopy), XRD (X-ray diffraction) and UV-Vis spectroscopy. (C) 1998 Elsevier Science Limited. All rights reserved.

FTIR-ATR study of self-assembled thiol monolayers on gold

Self-assembled monolayers of 1-teradecanethiol on gold were characterized by means of FTIR-ATR measurements, XPS and contact angle measurements. Linear dichroism measurements using FTIR-ATR are used to estimate the orientation of the alkyl chains. An equation for calculating the orientation angles of the alkyls chains was deduced. (C) 1998 Elsevier Science Limited. All rights reserved.

Paint-freeze method to form self-assembled alkanethiol/phospholipid bilayers on gold

A paint-freeze method for preparing self-assembled alkanethiol/phospholipid bilayers on a gold surface has been described (by cyclic voltammetry, a.c impedance, polarized FTIR-ATR) to be well-ordered and packed, stable, solvent-free bilayers. The lipid order parameter was 0.67, calculated from the dichroic ratio, consistent with a well-ordered lipid film in which the methylene groups have segmental flexibility and are disordered to a degree which is typical for a lipid bilayer in the liquid-crystalline phase. Such a supported membrane provides a useful way for studies in biophysics, physiology and electrochemistry.

Electrochemical quartz crystal microbalance study of the electrochemical behavior of riboflavin at gold electrodes

The electrochemical and adsorption behaviors of riboflavin (RF) at gold electrodes has ken studied by using an electrochemical quartz crystal microbalance (EQCM). Useful information is obtained not only about electrochemical behavior but also about mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in RF solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed for pH less than or equal to 9.71. There was no electrochemical reaction for pH > 9.71. The maximum current response was obtained at about pH 8. The current response was proportional to the square root of scan rates when the concentration of RF was lower than 1.0 x 10(-4) mol L-1 (pH 6.92). On the contrary, at concentrations higher than 1.0 x 10(-4) mol L-1 (pH 6.92), it was proportional to the scan rates.