Electrochemical detection of dopamine and cytochrome c at a nanostructured gold electrode

A nanostructured gold surface consisting of closely packed outwardly growing spikes is investigated for the electrochemical detection of dopamine and cytochrome c. A significant electrocatalytic effect for the electrooxidation of both dopamine and ascorbic acid at the nanostructured electrode was found due to the presence of surface active sites which allowed the detection of dopamine in the presence of excess ascorbic acid to be achieved by differential pulse voltammetry. By simple modification with a layer of Nafion, the enhanced electrocatalytic properties of the nanostructured surface was maintained while increasing the selectivity of dopamine detection in the presence of interfering species such as excess ascorbic and uric acids. Also, upon modification of the nanostructured surface with a monolayer of cysteine, the electrochemical response of immobilised cytochrome c in two distinct conformations was observed. This opens up the possibility of using such a nanostructured surface for the characterisation of other biomolecules and in bio-electroanalytical applications.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

Engineering a nanostructured ``super surface'' with superhydrophobic and superkilling properties

We present a nanostructured ``super surface'' fabricated using a simple recipe based on deep reactive ion etching of a silicon wafer. The topography of the surface is inspired by the surface topographical features of dragonfly wings. The super surface is comprised of nanopillars 4 mm in height and 220 nm in diameter with random inter-pillar spacing. The surface exhibited superhydrophobicity with a static water contact angle of 154.0 degrees and contact angle hysteresis of 8.3 degrees. Bacterial studies revealed the bactericidal property of the surface against both gram negative (Escherichia coli) and gram positive (Staphylococcus aureus) strains through mechanical rupture of the cells by the sharp nanopillars. The cell viability on these nanostructured surfaces was nearly six-fold lower than on the unmodified silicon wafer. The nanostructured surface also killed mammalian cells (mouse osteoblasts) through mechanical rupture of the cell membrane. Thus, such nanostructured super surfaces could find applications for designing selfcleaning and anti-bacterial surfaces in diverse applications such as microfluidics, surgical instruments, pipelines and food packaging.

A DNA nanomachine induced by single-walled carbon nanotubes on gold surface

Single-walled carbon nanotubes (SWNTs) can selectively induce human telomeric i-motif DNA formation at pH 7.0. Based on this property, we design a DNA nanomachine induced by SWNTs on gold surface. The motor DNA is human telomeric G-quadruplex DNA. The reversible hybridization between the motor DNA and its complementary human telomeric i-motif DNA can be modulated by SWNTs without changing solution pH. Up to now, to our knowledge, there is no report to show that a DNA nanomachine is induced by SWNTs or a DNA nanomachine can detect i-motif formation at pH 7.0. Our work may provide a new concept for designing an SWNT-induced DNA nanomachine and for the detection of i-motif DNA structure at pH 7.0. DNA hybridization, conformational transition and i-motif formation have been characterized on surface or in solution by fluorescence confocal microscopy, circular dichroism, DNA melting and gel electrophoresis. The folding and unfolding kinetics of the DNA nanomachine on gold surface were studied by Fourier transform-surface plasmon resonance (FT-SPR). All these results indicate that SWNTs can induce the DNA nanomachine to work efficiently and reversibly.

Application of Ru(bpy)(3)(2+) in control and formation of gold surface nanostructure through oxidation-reduction cycling

It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy)(3)(2+) with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC. procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy)(3)(2+), and the surface roughness was decreasing with the increasing of Ru(bpY)(3)(2+) concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

A method for cathodic polymerization of aniline by in situ electrogenerated intermediate at gold surface

Polyaniline (PANI) was cathodically synthesized at an evaporated gold electrode using an in situ electrogenerated intermediate as oxidant during reduction of the dissolved oxygen. The obtained PANI layer showed an electrochemical response similar to that synthesized by the conventionally anodic polymerization, and the average rate for the growth of PANI layer at polycrystalline gold electrode was 1.59 nm h(-1), while that at the Au (111) electrode was 4.93 nm h(-1). Based on these results, the thickness of the resulted layer can be easily controlled at molecular level for potential nanodevice applications. The obtained PANI layer showed morphology from an island-like nanostructure to an ultrathin film, depending on the crystal orientation of the electrode used.

Self-assembling process of alkanethiol monolayers on gold surface via underpotential deposition

It was demonstrated feasible that underpotential deposition(UPD) of copper on a monolayer-modified gold substrate can be used to determine the gold electrode area. The deposition and stripping of a Cu adlayer can take Place reversibly and stably at a bared or a self-assembled monolayer modified gold electrode. The growth kinetics of decanethiol/Au was also investigated via Cu UPD. The difference between the assembling kinetics determined by UPD and that by quartz crystal microbalance measurements reveals the configuration transmutation of the assembled molecules from a disordered arrangement to an ordered arrangement during the self-assembling processes.

DNA-templated assembly and electropolymerization of aniline on gold surface

Biomolecule template gives new opportunities for the fabrication of novel materials with special features. Here we report a route to the formation of DNA-polyaniline (PAn) complex, using immobilized DNA as a template. A gold electrode was first modified with monolayer of 2-aminoethanethiol by self-assembly. Thereafter, by simply immersing the gold electrode into DNA solution, DNA molecules can be attached onto the gold surface, followed by the DNA-templated assembly and electropolymerization of protonated aniline. The electrostatic interactions between DNA and aniline can keep the aniline monomers aligning along the DNA strands. Investigations by surface plasmon resonance (SPR), electrochemistry and reflection absorption UV/Vis-Near IR spectroscopy substantially convince that PAn can be electrochemically grown around DNA template on gold surface. This work may be provides fundamental aspects for building PAn nanowires with DNA as template on solid surface if DNA molecules can be individually separated and stretched.

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Sensing of 2,4-dichlorophenoxyacetic acid by surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectra of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was obtained by employing a bi-layer gold substrate, assembled by the reduction of Au(III) over gold-seeded nanoparticles immobilized on functionalized glass substrates. The SERS signal was linear with the logarithm of the solution concentrations between 1.0 x 10(-7) mol L(-1) and 1.0 x 10(-3) mol L(-1), indicating that the bi-layer gold substrate affords a significant dynamic range for SERS, providing an excellent analytical response within this concentration range, and revealing the high sensitivity of the gold surface towards such analyte. In addition, using the same gold substrate, a similar calibration curve was obtained for crystal-violet (CV), and it was possible to identify the concentration limit corresponding to the transition from the average SERS to the nonlinear SERS response. (C) 2010 Elsevier B.V. All rights reserved.

Fast assembly of non-thiolated DNA on gold surface at lower pH

In a typical protocol for attaching DNA to a gold electrode, thiolated DNA is incubated with the electrode at neutral pH overnight. Here we report fast adsorption of non-thiolated DNA oligomers on gold electrodes at acidic pH (i.e., pH ~3.0). The peak-to-peak potential difference and the redox peak currents in typical cyclic voltammetry of [Fe(CN)6]3- are investigated to monitor the attachment. Compared with incubation at neutral pH, the lower pH can significantly promote the adsorption processes, enabling efficient adsorption even in 30min. The adsorption rate is DNA concentration-dependent, while the ionic strength shows no influence. Moreover, the adsorption is base-discriminative, with a preferred order of A>C≫G, T, which is attributed to the protonation of A and C at low pH and their higher binding affinity to gold surface. The immobilized DNA is functional and can hybridize with its complementary DNA but not a random DNA. This work is promising to provide a useful time-saving strategy for DNA assembly on gold electrodes, allowing fast fabrication of DNA-based biosensors and devices. © 2013 Elsevier Inc.

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Annealing effects on nanostructured gold-polymethylmethacrylate composites: Small-angle x-ray scattering analysis

Composites formed of a polymer-embedded layer of sub-10 nm gold nanoclusters were fabricated by very low energy (49 eV) gold ion implantation into polymethylmethacrylate. We used small angle x-ray scattering to investigate the structural properties of these metal-polymer composite layers that were fabricated at three different ion doses, both in their original form (as-implanted) and after annealing for 6 h well above the polymer glass transition temperature (150 degrees C). We show that annealing provides a simple means for modification of the structure of the composite by coarsening mechanisms, and thereby changes its properties. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720464]