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.

The nature of the interaction between polyaniline and 2,5-dimercapto-1,3,4-thiadiazole in electrochemical redox processes

The interaction between polyaniline (PAn) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was investigated by means of cyclic voltammetry and UV-visible spectroscopy. The results show that the polymerization-depolymerization reaction of DMcT or its dilithium salt Li(2)DMcT is a kinetically quasi-reversible process. PAn exhibits very weak electrochemical activity in neutral propylene carbonate. After doping with protonic acid, such as hydrochloric acid or maleic acid etc., however, it shows an extensively enhanced electroactivity. For the complex system, PAn-DMcT or PAn-Li(2)DMcT, polyaniline has no catalytic activity for the electrochemical polymerization-depolymerization reaction of DMcT or DMcT(2-). Instead, the enhancement of the electrochemical redox activity of PAn-DMcT system compared with that of PAn, DMcT, Li(2)DMcT, and PAn-Li(2)DMcT comes from the protonic doping of PAn by DMcT.

Electrochemical study of ion channel behavior in incorporated poly L-glutamate bilayer lipid membranes

The lipid layer membranes were fabricated on the glassy carbon electrode (GC) and demonstrated to be bilayer lipid membranes by impedance spectroscopy. The formation of incorporated poly L-glutamate bilayer lipid membrane was achieved. The ion channel behavior of the incorporated poly L-glutamate membrane was determined. When the stimulus calcium cations were added into the electrolyte, the ion channel was opened immediately and exhibited distinct channel current. Otherwise, the ion channel was closed. The cyclic voltammogram at the GC electrode coated with incorporated poly L-glutamate DMPC film response to calcium ion is very fast compared with that at the GC electrode coated only with DMPC film. Ion channel current is not dependent on the time but on the concentration of calcium. The mechanism of the ion channel formation was investigated.

Structural electrochemical study of hemoglobin by in situ circular dichroism thin layer spectroelectrochemistry

Secondary and tertiary or quaternary structural changes in hemoglobin (HB) during an electroreduction process were studied by in situ circular dichroism (CD) spectroelectrochemistry with a long optical path thin-layer cell. By means of singular value decomposition least-squares analysis, CD spectra in the far-UV region give two similar a components with different CD intensity, indicating slight denaturation in the secondary structures due to the electric field effect. CD spectra in the Soret band show a R --> T transition of two quaternary structural components induced by electroreduction of the heme, which changes the redox states of the center ion from Fe3+ to Fe2+ and the coordination number from 6 to 5. The double logarithmic analysis shows that electroreduction of hemoglobin follows a chemical reaction with R --> T transition. Some parameters in the electrochemical process were obtained: formal potential, E-0t = -0.167 V; electrochemical kinetic overpotential, DeltaE(0) = -0.32 V; standard electrochemical reaction rate constant, k(0) = 1.79 x 10(-5) cm s(-1); product of electron transfer coefficient and electron number, alphan=0.14; and the equilibrium constant of R --> T transition, K-c = 9.0.

Determination of the interfacial acidity of the functional alkanethiols self-assembly membrane by capacitance measurement

The acid-base equilibrium of self-assembly monolayer(SAM) of mercaptopropionic acid on gold electrode was studied by capacitance titration. The change of capacitance was due to protonation and deprotonation of the modified electrode surface. This method can be used to measure pH value in solution and capacitance of solid/liquid on SAMs surface synchronously. The shift of pK(a) was observed during the experiment as previous reports. The factors that affect the capacitance measurement were discussed in detail.

Electrochemical synthesis of polyaniline nanoparticles

Polyaniline nanoparticles were prepared on a highly oriented pyrolytic graphite (HOPG) surface from dilute polyaniline acidic solution (1 mM aniline + 1 M HClO4) using a pulsed potentiostatic method. Electrochemistry, Fourier transform infrared external reflection spectroscopy (FT-IR-ERS), X-ray photoelectron spectroscopy (XPS) and tapping-mode atomic force microscopy (TMAFM) were: used to characterize the composition and structure of the polyaniline nanoparticles. FT-IR-ERS and XPS results revealed that the polyaniline was in its emeraldine form. TMAFM measurement showed that the electropolymerized polyaniline nanoparticles dispersed on the:HOPG surface with a coverage of about 10(10) cm(-2). These nanoparticles were disk-shaped having a height of 10(-30) Angstrom and an apparent diameter varying from 200 to 600 Angstrom. The particle dimensions increased with the electropolymerization charge (Q) over the interval from 5.7 to 19.3 mu C cm(-2) (C) 2000 Elsevier Science S.A. All rights reserved.

A novel electrochemical SPR biosensor

In this paper, we demonstrate for the first time that upon electrochemical oxidation/reduction, the transition in the conductivity of polyaniline (PAn) film on gold electrode surface leads to a large change of surface plasmon resonance (SPR) response due to a change in the imaginary part of dielectric constant of PAn film. Based on the amplifying response of SPR to the redox transformation of PAn film as a direct result of the enzymatic reaction between horseradish peroxidase (HRP) and PAn in the presence of H2O2, a novel PAn-mediated HRP sensor has been fabricated. The electrochemical SPR biosensor, unlike a usual binding assay with SPR, can afford a larger SPR response, and can also be reused by reducing the PAn film electrochemically to its reduced state. This method opens up a new route to the fabrication of SPR biosensor. (C) 2001 Elsevier Science BN. All rights reserved.

Amplification of antigen-antibody interactions based on biotin labeled protein-streptavidin network complex using impedance spectroscopy

Antibody was covalently immobilized by amine coupling method to gold surfaces modified with a self-assembled monolayer of thioctic acid. The electrochemical measurements of cyclic voltammetry and impedance spectroscopy showed that the hexacyanoferrate redox reactions on the gold surface were blocked due to the procedures of self-assembly of thioctic acid and antibody immobilization. The binding of a specific antigen to antibody recognition layer could be detected by measurements of the impedance change. A new amplification strategy was introduced for improving the sensitivity of impedance measurements using biotin labeled protein- streptavidin network complex. This amplification strategy is based on the construction of a molecular complex between streptavidin and biotin labeled protein. This complex can be formed in a cross-linking network of molecules so that the amplification of response signal will be realized due to the big molecular size of complex. The results show that this amplification strategy causes dramatic improvement of the detection sensitivity of hIgG and has good correlation for detection of hIgG in the range of 2-10 mug/ml. (C) 2001 Elsevier Science B.V. All rights reserved.

Electrochemical preparation and characterization of silicotungstic heteropolyanion monolayer electrostatically linked aminophenyl on carbon electrode surface

In this paper, an organic-inorganic composite film of heteropolyanion was Formed by attaching a Keggin-type heteropolyanion, SiW12O404-, on carbon electrode surface derivatized by 4-aminophenyl monolayer. The composite film thus grafted on carbon electrode surface has good stability because of the ionic bonding character between SiW12O404- and surface aminophenyl groups. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used to characterize the composite film. Compared with SiW12O404- electrodeposited on a bare glassy carbon electrode (GCE), the composite film gives three more sharp and well-defined redox couples attributed to two one- and two-electron processes, and the analyses of the voltammograms of SiW12O404- anion in the composite film modified on GCE shows that its surface coverage is close to a closest packing monolayer. STM characterization shows that a two-dimensional order heteropolyanion monolayer was formed on HOPG substrate. The composite film provides a favorable environment for electron and proton transfer between SiW12O404- ion and electrode surface, which may make it suitable for various applications in sensors and microelectronics devices.

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.

Effect of urea on synchronous fluorescence spectra and electrochemical behaviour of cytochrome c

The changes of the synchronous fluorescence spectra and the electrochemical behaviour of cytochrome c with the urea concentration are studied. It has been found that with the increase of urea concentration, there occur sequentially the deaggregation of cytochrome c molecules, the increase of exposure extent of the heme group to the solvent, the disruption of Fe-S bond of the heme group and the change in the electrochemical behaviour of cytochrome c. It is suggested that the reason why the electrochemical reaction of cytochrome c is irreversible is that cytochrome c molecules exist in the concentrated solution as oligomers which are electrochemically inactive.

Electrochemical identification of intermediate forms of urea denaturation of horse heart cytochrome c

The electrochemical identification of the urea denaturation of horse heart cytochrome c in bulk solution at the 4,4'-dithiodipyridine-modified gold electrode is reported. The results are similar to the three-step transitions of equilibrium studies (Myer et al., Biochemistry, 19 (1980) 199) of urea denaturation of cytochrome c in bulk solution. This method permits a clear resolution of which of the three steps of urea denaturation is electrochemically related. In addition, by analysing the effects of urea on the structural forms of cytochrome c and on the solution properties, as well as the cyclic voltammetric responses of the protein, the individual forms of the urea denaturation of cytochrome c can be understood. The results reflect the superposition of protein denaturation on the electrode surface and in solution.

Synthesis of N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide and electrochemical behaviour of its monolayers on a gold electrode

A new viologen derivative of N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide has been prepared and characterized by elemental analysis, IR, H-1 NMR, MS and TG-DTA. X-Ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry have been used to characterize the monolayers formed by this compound on the bulk gold electrodes by self-assembly.