Anodic behaviour of arsenopyrite and cathodic reduction of ferrate(VI) and oxygen in alkaline solutions

This paper presents the results of an electrochemical study of the anodic characteristics of arsenopyrite in strongly alkaline solutions and of the cathodic reduction of ferrate( VI) and of dissolved oxygen at an arsenopyrite surface at potentials which are relevant to the oxidation reactions. Cyclic voltammetry at both arsenopyrite disc and arsenopyrite disc/platinum ring electrodes has shown that arsenic(III) is the main product of the anodic process at potentials in the region of the rest potential during oxidation by either ferrate( VI) or oxygen. Evidence for partial passivation of both the anodic and cathodic reactions has been obtained from potentiostatic current - time transients. The initial stage of oxidation by ferrate( VI) has been shown to be mass-transport controlled and this is also true of the oxidation by oxygen in dilute solutions of sodium hydroxide.

The anodic dissolution of magnesium in chloride and sulphate solutions

The electrochemical behaviour of magnesium was studied in representative chloride and sulphate solutions including NaCl, Na2SO4, NaOH and their mixed solutions, HCl, and H2SO4: (1) by measuring electrochemical polarisation curves, (2) by using electrochemical impedance spectroscopy (EIS), and (3) by simultaneous measurement of hydrogen gas evolution and measurement of magnesium dissolution rates using inductively coupled plasma atomic emission spectrophotometry (ICPEAS). These experiments showed that a partially protective surface film played an important role in the dissolution of magnesium in chloride and sulphate solutions. Furthermore, the experimental data were consistent with the involvement of the intermediate species Mg+ in magnesium dissolution at film imperfections or on a film-free surface. At such sites, magnesium first oxidised electrochemically to the intermediate species Mg+, and then the intermediate species chemically reacted with water to produce hydrogen and Mg2+. The presence of Cl- ions increased the film free area, and accelerated the electrochemical reaction rate from magnesium metal to Mg+. (C) 1997 Elsevier Science Ltd.

Anodic-oxide-induced interdiffusion in GaAs/AlGaAs quantum wells

Enhancement of interdiffusion in GaAs/AlGaAs quantum wells due to anodic oxides was studied. Photoluminescence, transmission electron microscopy, and quantum well modeling were used to understand the effects of intermixing on the quantum well shape. Residual water in the oxide was found to increase the intermixing, though it was not the prime cause for intermixing. Injection of defects such as group III vacancies or interstitials was considered to be a driving force for the intermixing. Different current densities used in the experimental range to create anodic oxides had little effect on the intermixing. ©1998 American Institute of Physics.

Supersaturated solutions evaluated with an in vitro stratum corneum tape stripping technique

The flux of a compound across a membrane from any formulation, whether it contains penetration enhancers or not, is limited by its saturated solubility in the vehicle. Under such conditions the concentration of the permeant in the outer layers of the stratum corneum is also saturated. Consequently, when the permeation of a drug from a supersaturated solution leads to enhanced penetration, the concentration of the drug in the outer layers of the membrane is also supersaturated. Therefore, the stratum corneum may possess antinucleant properties which inhibit or retard the crystallisation process. In this study, the enhanced in vitro permeation of supersaturated solutions of piroxicam across human skin in diffusion cells was demonstrated. The amount of permeant in the stratum corneum was determined using a tape stripping technique. Supersaturated solutions up to four degrees of saturation were investigated which produced a linear relationship between the degree of saturation and the amount of piroxicam in the stratum corneum (R-2 = 0.970). Furthermore, the amount of piroxicam in the viable layers of the skin also increased with increasing degree of saturation. An analysis of the results suggested that enhanced penetration across human skin from supersaturated solutions of piroxicam may occur as a result of the antinucleating ability of the intercellular lipids of the stratum corneum. (C) 1997 Elsevier Science B.V.

Protein film voltammetry of Rhodobacter capsulatus xanthine dehydrogenase

Xanthine dehydrogenase (XDH) from the bacterium Rhodobacter capsulatus catalyzes the hydroxylation of xanthine to uric acid with NAD(+) as the electron acceptor. R. capsulatus XDH forms an (alphabeta)(2) heterotetramer and is highly homologous to homodimeric eukaryotic XDHs. The crystal structures of bovine XDH and R. capsulatus XDH showed that the two proteins have highly similar folds; however, R. capsulatus XDH is at least 5 times more active than bovine XDH and, unlike mammalian XDH, does not undergo the conversion to the oxidase form. Here we demonstrate electrocatalytic activity of the recombinant enzyme, expressed in Escherichia coli, while immobilized on an edge plane pyrolytic graphite working electrode. Furthermore, we have determined all redox potentials of the four cofactors (Mo-VI/V, Mo-V/IV, FAD/FADH, FADH/FADH(2) and two distinct [2Fe-2S](2+/+) clusters) using a combination of potentiometric and voltammetric methods. A novel feature identified in catalytic voltammetry of XDH concerns the potential for the onset of catalysis (ca. 400 mV), which is at least 600 mV more positive than that of the highest potential cofactor. This unusual observation is explained on the basis of a pterin-associated oxidative switch during voltammetry that precedes catalysis.

Electrochemical study of UNS S32550 super duplex stainless steel corrosion in turbulent seawater using the rotating cylinder electrode

The cathodic and anodic characteristics of freshly polished and pre-reduced UNS S32550 (ASTM A479) super duplex stainless steel in a filtered and conductivity-adjusted seawater have been investigated under controlled flow conditions. A rotating cylinder electrode was used together with both steady and non-steady-state voltammetry and a potential step current transient technique to investigate the electrode reactions in the fully characterized electrolyte. Both oxygen reduction and hydrogen evolution were highly irreversible and the material exhibited excellent passivation and repassivation kinetics. Relative corrosion rates were derived and the corrosion mechanism of the alloy was found to be completely independent of the mass-transfer effects, which can contribute to flow-induced corrosion.

A numerical approach to modeling the catalytic voltammetry of surface-confined redox enzymes

A finite difference method for simulating voltammograms of electrochemically driven enzyme catalysis is presented. The method enables any enzyme mechanism to be simulated. The finite difference equations can be represented as a matrix equation containing a nonlinear sparse matrix. This equation has been solved using the software package Mathematica. Our focus is on the use of cyclic voltammetry since this is the most commonly employed electrochemical method used to elucidate mechanisms. The use of cyclic voltammetry to obtain data from systems obeying Michaelis-Menten kinetics is discussed, and we then verify our observations on the Michaelis-Menten system using the finite difference simulation. Finally, we demonstrate how the method can be used to obtain mechanistic information on a real redox enzyme system, the complex bacterial molybdoenzyme xanthine dehydrogenase.

On the steady-state assumption and its application to the rotating disk voltammetry of adsorbed enzymes

Rotating disk voltammetry is routinely used to study electrochemically driven enzyme catalysis because of the assumption that the method produces a steady-state system. This assumption is based on the sigmoidal shape of the voltammograms. We have introduced an electrochemical adaptation of the King-Altman method to simulate voltammograms in which the enzyme catalysis, within an immobilized enzyme layer, is steadystate. This method is readily adaptable to any mechanism and provides a readily programmable means of obtaining closed form analytical equations for a steady-state system. The steady-state simulations are compared to fully implicit finite difference (FIFD) simulations carried out without any steady-state assumptions. On the basis of our simulations, we conclude that, under typical experimental conditions, steady-state enzyme catalysis is unlikely to occur within electrode-immobilized enzyme layers and that typically sigmoidal rotating disk voltammograms merely reflect a mass transfer steady state as opposed to a true steady state of enzyme intermediates at each potential.

Direct electrochemically driven catalysis of bovine milk xanthine oxidase

The complex molybdoenzyme xanthine oxidase (XO) catalyses the oxidation of xanthine to uric acid. Here we report the first direct (unmediated) catalytic electrochemistry of the enzyme in the presence of xanthine. The only non-turnover response (without substrate present) is a sharp two-electron wave from the FAD cofactor at -242 mV vs. NHE (pH 8.0). Upon addition of xanthine to the electrochemical cell a pronounced electrocatalytic anodic current appears at ca. +300 mV vs. NHE, but the FAD peak remains. This is unusual as the onset of catalysis should occur at the potential of the FAD cofactor (the site at which oxygen or NAD+ binds to the enzyme in solution). The observed electrochemical catalysis is prevented by the addition of known XO inhibitors allopurinol or cyanide. (c) 2005 Elsevier B.V. All rights reserved.

Protein film voltammetry of arsenite oxidase from the chemolithoautotrophic arsenite-oxidizing bacterium NT-26

The chemolithoautotrophic bacterium NT-26 (isolated from a gold mine in the Northern Territory of Australia) is unusual in that it acquires energy by oxidizing arsenite to arsenate while most other arsenic-oxidizing organisms perform this reaction as part of a detoxification mechanism against the potentially harmful arsenite [present as As(OH)(3) at neutral pH]. The enzyme that performs this reaction in NT-26 is the molybdoenzyme arsenite oxidase, and it has been previously isolated and characterized. Here we report the direct (unmediated) electrochemistry of NT-26 arsenite oxidase confined to the surface of a pyrolytic graphite working electrode. We have been able to demonstrate that the enzyme functions natively while adsorbed on the electrode where it displays stable and reproducible catalytic electrochemistry in the presence of arsenite. We report a pH dependence of the catalytic electrochemical potential of -33 mV/pH unit that is indicative of proton-coupled electron transfer. We also have performed catalytic voltammetry at a number of temperatures between 5 and 25 degrees C, and the catalytic current (proportional to the turnover number) follows simple Arrhenius behavior.

Corrosion behaviour of AZ21, AZ501 and AZ91 in sodium chloride

The corrosion behaviour of AZ21, AZ501 and AZ91 was studied in 1 N NaCl at pH 11 by measuring electrochemical polarization curves, electrochemical AC impedance spectroscopy (EIS) and simultaneously measuring the hydrogen evolution rate and the: magnesium dissolution rate. The corrosion rates increased in the following order: AZ501 < AZ21 < AZ91. The: corrosion behaviour was related to alloy microstructure as revealed by optical and electron microscopy. The beta phase was very stable in the test solution and was an effective cathode. The beta phase served two roles, as a barrier and as a galvanic cathode. If the beta phase is present in the alpha matrix as intergranular precipitates with a small volume fraction, then the beta phase mainly serves as a galvanic cathode, and accelerates the corrosion of the alpha matrix. If the beta Fraction is high, then the beta phase may mainly act as an anodic barrier to inhibit the overall corrosion of the alloy. The composition and compositional distribution in the alpha phase is also crucial to the overall corrosion performance of dual phase alloys. Increasing the aluminum concentration in the alpha phase increases the anodic dissolution rate and also increases the cathodic hydrogen evolution rate. Increasing the zinc concentration in the alpha phase may have the opposite effect. (C) 1998 Elsevier Science Ltd. All rights reserved.

The neutral hydrogen content of Fornax cluster galaxies

We present a new set of deep H I observations of member galaxies of the Fornax cluster. We detected 35 cluster galaxies in H I. The resulting sample, the most comprehensive to date, is used to investigate the distribution of neutral hydrogen in the cluster galaxies. We compare the H I content of the detected cluster galaxies with that of field galaxies by measuring H I mass-to-light ratios and the H I deficiency parameter of Solanes et al. (1996). The mean H I mass-to-light ratio of the cluster galaxies is 0.68 +/- 0.15, significantly lower than for a sample of H I-selected field galaxies (1.15 +/- 0.10), although not as low as in the Virgo cluster (0.45 +/- 0.03). In addition, the H I content of two cluster galaxies (NGC1316C and NGC1326B) appears to have been affected by interactions. The mean H I deficiency for the cluster is 0.38 +/- 0.09 (for galaxy types T = 1-6), significantly greater than for the field sample (0.05 +/- 0.03). Both these tests show that Fornax cluster galaxies are H I-deficient compared to field galaxies. The kinematics of the cluster galaxies suggests that the H I deficiency may be caused by ram-pressure stripping of galaxies on orbits that pass close to the cluster core. We also derive the most complete B-band Tully-Fisher relation of inclined spiral galaxies in Fornax. A subcluster in the South-West of the main cluster contributes considerably to the scatter. The scatter for galaxies in the main cluster alone is 0.50 mag, which is slightly larger than the intrinsic scatter of 0.4 mag. We use the Tully-Fisher relation to derive a distance modulus of Fornax relative to the Virgo cluster of -0.38 +/- 0.14 mag. The galaxies in the subcluster are (1.0 +/- 0.5) mag brighter than the galaxies of the main cluster, indicating that they are situated in the foreground. With their mean velocity 95 km s(-1) higher than that of the main cluster we conclude that the subcluster is falling into the main Fornax cluster.

Review of stress corrosion cracking of pipeline steels in "low" and "high" pH solutions

This paper reviews the current understanding of the mechanisms of stress corrosion cracking of pipeline steels. The similarities, the differences and the influencing factors are considered for the high pH stress corrosion cracking caused by a concentrated bicarbonate-carbonate solution, and for the low pH stress corrosion cracking due to a diluter solution. For high pH stress corrosion cracking, it is well accepted that the mechanism involves anodic dissolution for crack initiation and propagation. In contrast, it has been suggested that the low pH stress corrosion cracking is associated with the dissolution of the crack tip and sides, accompanied by the ingress of hydrogen into the pipeline steel. But the precise influence of hydrogen on the mechanism needs to be further studied. (C) 2003 Kluwer Academic Publishers.

Operational regimes for a simplified one-step artificial chaperone refolding method

The artificial chaperone method for protein refolding developed by Rozema et al. (Rozema, D.; Gellman, S. H. J. Am. Chem. Soc. 1995, 117 (8), 2373-2374) involves the sequential dilution of denatured protein into a buffer containing detergent (cetyltrimethylammonium bromide, CTAB) and then into a refolding buffer containing cyclodextrin WD). In this paper a simplified one-step artificial chaperone method is reported, whereby CTAB is added directly to the denatured solution, which is then diluted directly into a refolding buffer containing P-cyclodextrin (P-CD). This new method can be applied at high protein concentrations, resulting in smaller processing volumes and a more concentrated protein solution following refolding. The increase in achievable protein concentration results from the enhanced solubility of CTAB at elevated temperatures in concentrated denaturant. The refolding yields obtained for the new method were significantly higher than for control experiments lacking additives and were comparable to the yields obtained with the classical two-step approach. A study of the effect of beta-CD and CTAB concentrations on refolding yield suggested two operational regimes: slow stripping ( beta-CDXTABsimilar to1), most suited for higher protein concentrations, and fast stripping (beta-CD/CTABsimilar to2.7), best suited for lower protein concentrations. An increased chaotrope concentration resulted in higher refolding yields and an enlarged operational regime.

Immobilisation of electroactive macrocyclic complexes within titania films

The 4-carboxyphenyl-appended macrocyclic ligand trans-6,13-dimethyl-6-((4-carboxybenzyl)amino)-1,4,8,11-tetraazacyclotetradecane-6-amine (HL10) has been synthesised and complexed with Co-III. The mononuclear complexes [Co(HL10)(CN)](2+) and [CoL10(OH)](+) have been prepared and the crystal structures of their perchlorate salts are presented, where the ligand is bound in a pentadentate mode in each case while the 4-carboxybenzyl-substituted pendent amine remains free from the metal. The cyano-bridged dinuclear complex [CoL10-mu-NC-Fe(CN)(5)](2-) was also prepared and chemisorbed on titania-coated ITO conducting glass. The adsorbed complex is electrochemically active and cyclic voltammetry of the modified ITO working electrode in both water and MeCN solution was undertaken with simultaneous optical spectroscopy. This experiment demonstrates that reversible electrochemical oxidation of the Fe-II centre is coupled with rapid changes in the optical absorbance of the film.