Interaction of BSA protein with copper evaluated by electrochemical impedance spectroscopy and quartz crystal microbalance

The interaction of bovine serum albumin (BSA) protein with copper in phosphate buffer solution has been studied by a combination of electrochemical impedance spectroscopy (EIS) close to the open circuit potential, with simultaneous monitoring by the electrochemical quartz crystal microbalance (EQCM), in order to throw light on BSA adsorption. Copper films were electroplated onto gold quartz crystals and mounted in the EQCM. Experiments were conducted in the presence and absence of dissolved oxygen and of BSA and the results show the influence of O₂ on the protein/metal interaction and also show specific interactions between BSA and copper. The good reproducibility obtained in these experiments suggests future application to other systems and which should lead to a better understanding of the use of such types of protein as corrosion inhibitors.     

Arsenic species interactions with a porous carbon electrode as determined with an electrochemical quartz crystal microbalance

The interactions of arsenic species with platinum and porous carbon electrodes were investigated with an electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry in alkaline solutions. It is shown that the redox reactions in arsenic-containing solutions, due to arsenic reduction/deposition, oxidation/desorption, and electrocatalyzed oxidation by Pt can be readily distinguished with the EQCM. This approach was used to show that the arsenic redox reactions on the carbon electrode are mechanistically similar to that on the bare Pt electrode. This could not be concluded with just classical cyclic voltammetry alone due to the obfuscation of the faradaic features by the large capacitative effects of the carbon double layer.For the porous carbon electrode, a continual mass loss was always observed during potential cycling, with or without arsenic in the solution. This was attributed to electrogasification of the carbon. The apparent mass loss per cycle was observed to decrease with increasing arsenic concentration due to a net mass increase in adsorbed arsenic per cycle that increased with arsenic concentration, offsetting the carbon mass loss. Additional carbon adsorption sites involved in arsenic species interactions are created during electrogasification, thereby augmenting the net uptake of arsenic per cycle.It is demonstrated that EQCM, and in particular the information given by the behavior of the time derivative of the mass vs. potential, or massogram, is very useful for distinguishing arsenic species interactions with carbon electrodes. It may also prove to be effective for investigating redox/adsorption/desorption behavior of other species in solution with carbon materials as well.     

Effect of metals on silver electrodeposition: Application to the detection of cisplatin

In the present work, the influence of several metals (Co, Ru, Pd, Os, Pt, Cu, Pb), deposited on a carbon paste electrode, towards silver electrodeposition was tested. First, adequate conditions for the electrodeposition of metals on the electrode were found. Then, the cyclic voltammograms registered (silver deposition curves and analytical signals) showed that Co, Cu, Pt and Pd were able to accelerate silver electrodeposition. Finally, a valid methodology for the detection of cisplatin was established. It is based on the deposition of silver on a Pt (from cisplatin) modified electrode and the analytical signal corresponds to the anodic stripping of the deposited silver. A limit of detection of 3.2 × 10⁻⁹ mol dm⁻³ (1 ng cm⁻³) cisplatin was obtained.     

An electrochemical quartz crystal microbalance study into the deposition of manganese dioxide

An electrochemical quartz crystal microbalance (EQCM) has been used to study the effects of electrolyte composition (MnSO₄ and H₂SO₄ concentrations) and anodic current density on the electrodeposition of manganese dioxide. The EQCM, in tandem with the electrode voltage during deposition, has been used to characterize features of the deposition mechanism such as the relative lifetime of the Mn(III) intermediate, the rate of soluble Mn(III) hydrolysis to form MnOOH, and the porosity of the resultant manganese dioxide deposit as a function of crystal nucleation. The connection between the results obtained here and commercial electrodeposition of manganese dioxide were also discussed.     

Electrochemical behavior of thin polycrystalline rhodium layers studied by cyclic voltammetry and quartz crystal microbalance

Electrochemical behavior of thin polycrystalline Rh layers has been studied in 0.5 M H₂SO₄ solution by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The properties of surface oxide formed on freshly electrodeposited Rh are different than on electrochemically aged Rh. The analysis of frequency changes in both hydrogen and oxygen regions is presented. It is suggested that hydrogen desorption occurs simultaneously with the adsorption of HSO₄⁻ ions, whose maximum surface coverage reaches ca. 8%. The EQCM results indicate that RhO is the main species formed during Rh surface oxidation. Metal dissolution proceeds during electrode cycling to sufficiently high potentials. The amount of dissolved metal increases with an increase in potential and a decrease in scan rate.     

Electrodeposition of CdS from acidic aqueous thiosulfate solution—Invesitigation of the mechanism by electrochemical quartz microbalance technique

Electrochemical quartz crystal microbalance was used to study mechanism of cathodic electrodeposition of CdS from acidic aqueous solutions containing 0.01 M Cd(ClO₄)₂ and 0.1 M Na₂S₂O₃ as a source of sulfur. Experiments were performed by means of cyclic voltammetry and potentiostatic method. A comparison of gravimetric and current responses at pH 3 and 4 allowed for determination of the potential range in which side reactions of reduction of SO₃²⁻ and H⁺ ions compete most strongly with formation of CdS. The film thickness was determined by means of two methods: from AFM profiles and EQCM measurements.     

Polyaniline fibres as electrodes.: Electrochemical characterisation in acid solutions

Polyaniline fibre microelectrodes prepared from a doped solution of polyaniline protonated with 2-acrylamido-2-methyl-1-propanesulphonic acid in dichloracetic acid were characterized electrochemically for the first time. Low scan rate cyclic voltammetry was used for characterisation in different acid electrolyte solutions, hydrochloric, nitric, perchloric, sulphuric and phosphoric, at low pH values with varying positive potential limits. Electrochemical impedance spectroscopy was also utilised. The electrochemical behaviour of polyaniline (PANI) fibres was found to be similar to that of PANI films obtained by electropolymerisation on metallic electrode substrates. The conduction potential window was found to be from +0.20 to +0.60 V versus SCE, with small variations in the different acid solutions as well as with pH. The standard electrochemical redox couple hexacyanoferrate(III), was found to behave quasi-reversibly in the conduction potential region and rate constants were evaluated.     

Electrochemical quartz crystal microbalance study of redox transformations of TCNQ microcrystals in concentrated LiCl solutions

Microcrystals of 7,7,8,8-tetracyanoquinodimethane (TCNQ) immobilized on gold surface have been investigated by combined cyclic voltammetry/chronoamperometry and piezoelectric nanogravimetry at an electrochemical quartz crystal microbalance (EQCM) in dilute and concentrated LiCl solutions. It is proved that TCNQ microcrystals even when TCNQ is reduced to its highly soluble Li⁺TCNQ⁻ salt can be studied in aqueous solutions when the water activity is decreased to a low level. At high electrolyte concentrations the voltammetric and chronoamperometric responses obtained for TCNQ microcrystals show the theoretically predicted pattern characteristic to the solid-solid phase transformation under the control of the nucleation and growth kinetics. The utilization of the idea presented in this work, i.e., using electrolyte of high concentrations (or decreasing the water activity by adding an indifferent component to the liquid phase in high concentration) can open up new vistas in the study of redox transformations of immobilized microcrystals which are soluble in water.     

The liquid-like layer between metal and frozen aqueous electrolytes: An electrochemical approach employing the quartz crystal microbalance

The surface properties of any substance in the solid state differ from its bulk properties. This can give rise to the formation of a liquid-like layer (LLL) at the interface, at temperatures below the melting point. The phenomenon generated interest among both theoreticians and experimentalists for more than 150 years and was studied, employing different techniques. However, electrochemical techniques have not been implemented in studies of this phenomenon.We used, for the first time, the quartz crystal microbalance (QCM) to study the LLL at the ice/gold and the frozen electrolyte/gold interfaces. It was shown that the QCM in contact with ice or with frozen electrolyte at temperatures well below the melting point shows detectable resonance. The parameters of the resonance depend strongly on temperature, composition of the frozen phase, adsorption taking place at the gold surface (including gold surfaces modified by different thiol-derivates) and, in the case of electrolyte, on the potential applied across the interface.Corresponding theoretical models have been developed to understand the kind of information contained in the response of the QCM on the properties of the LLL. Independent data obtained with a device allowing direct optical measurement of the displacement show good agreement with the calculations of thickness of the LLL based on developed models.     

Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR) and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process.     

Influence of anode material on the electrochemical oxidation of 2-naphthol: Part 1. Cyclic voltammetry and potential step experiments

The anodic oxidation of 2-naphthol has been studied by cyclic voltammetry and chronoamperometry, using a range of electrode materials such as Ti-Ru-Sn ternary oxide, lead dioxide and boron-doped diamond (BDD) anodes. The results show that polymeric films, which cause electrode fouling, are formed during oxidation in the potential region of supporting electrolyte stability. IR spectroscopy verified the formation of this organic film. While the Ti-Ru-Sn ternary oxide surface cannot be reactivated, PbO₂ and BDD can be restored to their initial activity by simple anodic treatment in the potential region of electrolyte decomposition. In fact, during the polarization in this region, complex oxidation reactions leading to the complete incineration of polymeric materials can take place on these electrodes due to electrogenerated hydroxyl radicals. Moreover, it was found that BDD deactivation was less pronounced and its reactivation was faster than that of the other electrodes.     

Electrochemical chlorination of azulene derivatives: Insight into the mechanism of anodic oxidative chlorination

The cyclic voltammetry behavior of a series of five 1-substituted azulenes has been investigated as well as the electrochemical chlorination of these compounds. In the case of azulene compounds containing electron withdrawing groups which have higher oxidation potentials than that of the chloride ion, the electrochemical chlorination led usually to 3-chloro derivatives. The electrochemical chlorination fails for azulenes with lower oxidation potentials. Additionally some polyhalogenated compounds were obtained by controlled potential electrolyses. The paper also discusses the reaction mechanism of the electrochemical halogenation of 1-substituted azulenes.     

Zn electrodeposition in the presence of surfactants: Part I. Voltammetric and structural studies

The zinc electrodeposition onto steel substrates in the presence of surfactants with different charged head groups, namely anionic sodium dodecylsulphate (SDS), cationic dodecyltrimethylammonium bromide (CTAB), and non-ionic octylphenolpoly(ethyleneglycolether)_n, n = 10 (Triton X-100) was studied by cyclic voltammetry. The effect of the switching potential and scanning rate on the deposition process was investigated. The structural characterisation and the chemical composition of the samples prepared potentiostaticaly, in the potential range where the voltammetric cathodic peaks appear, was performed by X-ray powder diffraction (XRD) and by energy-dispersive X-ray analysis (EDS), respectively. The experimental results show that the voltammetric behaviour, namely the deposition potential depends on the presence, nature and concentration of the tested surfactants. Zn deposition occurs at potential values more positive than the estimated equilibrium potential, peak C1, simultaneously with hydrogen formation. This fact is confirmed by XRD measurements. Zn bulk deposits prepared in the absence of surfactants and in the presence of SDS are more crystalline and with a higher grain size than the ones obtained in the presence of CTAB and Triton X-100. These facts may be justified by an increase on the overpotential deposition as the electrochemical study confirms.     

Mechanistic study of electrochemical oxidation of catechols in the presence of 4-hydroxy-1-methyl-2(1H)-quinolone: Application to the electrochemical synthesis

Electrochemical oxidation of catechols (1a-1c) has been studied in the presence of 4-hydroxy-1-methyl-2(1H)-quinolone (3) as a nucleophile in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (1a-1c) participate in Michael addition reactions with 3 to form the corresponding benzofuran (or isochromeno[4,3-c]quinoline) derivatives (6a-6c). The electrochemical synthesis of (6a-6c) has been successfully performed in an undivided cell in good yield and purity. The oxidation mechanism was deduced from voltammetric data and by coulometry at controlled-potential. The products have been characterized after purification by IR, ¹H NMR, ¹³C NMR and MS.     

Mechanistic study of electrochemical oxidation of 4-tert-butylcatechol: A facile electrochemical method for the synthesis of new trimer of 4-tert-butylcatechol

The electrochemical trimerization of 4-tert-butylcatechol via anodic oxidation of 4-tert-butylcatechol (1) is described. The mechanism of trimerization has been studied in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The electrochemical synthesis of trimer 3a has been successfully performed in an undivided cell in good yield and purity.     

Ion exchange properties of polypyrrole studied by electrochemical quartz crystal microbalance (EQCM)

The electrochemical polymerization of pyrrole in aqueous solution was studied as a function of a variety of parameters, such as magnitude of current density and monomer concentration. The possibility of quantitative replacement of counterions by solution anions was studied in detail using the electrochemical quartz crystal microbalance (EQCM) technique. It was found that the polymer structure can be manipulated, even after synthesis. The manipulation was revealed to be dependent on various factors, including the nature of the counterion and of the electrolyte concentration. On the basis of these observations, a two-layer structure is suggested for polypyrrole-based polymers. © 1999 Society of Chemical Industry     

A quartz crystal microbalance study of the kinetics of interaction of benzotriazole with copper

The kinetics of interaction of benzotriazole (C₆H₅N₃, BTAH) with the surface of copper in salt water were studied using an electrochemical quartz crystal microbalance and X-ray photoelectron spectroscopy (XPS). Upon injecting BTAH into the electrolyte, three regions appear in the time response of the microbalance. Region I (at short time of few minutes), exhibits rapid linear growth of mass with time, which is attributed to the formation of a protective Cu(I)BTA complex. Region II reveals attachment of BTAH at a slower rate onto the inner Cu(I)BTA complex. Region III is a plateau indicating that the BTAH film attains an equilibrium mass and thickness, which increase with the concentration of BTAH. The intensity of the N1s peak in the XPS spectra increases with the time of immersion, indicating more BTAH on the surface. The results suggest a duplex inhibitor film composed of an inner thin layer of Cu(I)BTA and an outer layer of physically adsorbed BTAH which increases in thickness with time and BTAH concentration. They also offer an explanation for the much documented findings of simultaneous increase of the polarization resistance and decrease of double layer capacity with inhibitor concentration and time of immersion.     

The influence of lead upd on the oxidation of glucose at platinum electrodes an electrochemical quartz crystal microbalance study

The oxidation of glucose at Pt electrodes with upd deposits of Pb in acid media has been investigated using the electrochemical quartz crystal microbalance (EQCM). Glucose alone has a small effect on the mass response but changes in upd Pb coverage have a large effect. This allows changes in upd Pb coverage to be followed easily despite the fact that the associated current is largely obscured in the cyclic voltammogram. Cyclic voltammetry at low glucose concentrations shows a multiple peak structure in the double layer region of potential at low upd coverages that is charged to the more familiar single peak as upd coverage increases. Mass responses also reveal some blockage of Pb upd by glucose or species derived from it during cyclic voltammetry. Data from mass transients show that the deliberate formation of poisons prior to addition of Pb²⁺ ions to the electrolyte results in a substantial suppression of upd coverage especially between −0.1 and 0.1 V (sce). Finally, mass transients accompanying injections of Pb²⁺ in the presence of glucose in the electrolyte reveal the suppression of adsorption of Pb²⁺ cations on an oxidised Pt surface by species derived from glucose.     

Electrochemical quartz crystal microbalance study on carbon oxides adsorption in the presence of electrosorbed hydrogen on Pd alloys with Pt and Rh

CO₂ and CO adsorption on Pd-Pt and Pd-Rh alloys has been studied by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). Adsorbed CO₂ inhibits partially hydrogen adsorption on Pt and Rh surface atoms but does not block significantly hydrogen absorption into alloy bulk. In the presence of adsorbed CO both hydrogen adsorption and absorption are strongly suppressed. On electrodes covered with adsorbed CO the oxidation of previously absorbed hydrogen is significantly shifted into higher potentials. The EQCM response in CO₂/CO adsorption experiments is affected by both the effects connected with the changes in mass attached to the resonator and the non-mass effects including changes in metal-solution interactions and variation of solution density and viscosity in the vicinity of the electrode. Differences in the EQCM behavior suggest that the products of CO₂ and CO adsorption on the alloys studied are not totally identical.     

Electrochemistry in confined microsystems: Part 1. CV-SECM of reversible system at a confined disk ultramicroelectrode

This work is the first part of a series of papers concerning the study of electrochemical method in case of ultramicroelectrode (UME) confinement in integrated chemical microsystems. This paper is devoted to the discussion of numerical simulation obtained in the case of a transient electrochemical method - i.e. cyclic voltammetry (CV) - applied to a finite disk ultramicroelectrode confined in front of an insulating surface. This configuration corresponds to scanning electrochemical microscopy (SECM) in negative feedback configuration. We describe a new electrochemical method, with acronym CV-SECM, based on the coupling of cyclic voltammetry with scanning electrochemical microscopy. The main advantage of this method is the obtention of a time resolved measurement simultaneously with a high local resolution. The results of the simulation show that adjusting the scan speed of the potential sweep allows the exploration of a controlled range of distance between the UME and the insulating surface. The reverse peak current obtained in cyclic voltammetry exhibits unexpected variations with the approach distance of the UME: (i) a regime of depletion of the electroactive reactant during the forward scan at short distance, associated to a decrease of the peak current and (ii) a regime of accumulation of the electroactive product at larger distance, associated to an increase of the reverse peak current identified in comparison with the free diffusion regime.