Portugaliae
Electrochimica Acta

Electrochemical aptasensor arrays have been recently used to detect several proteins reported as disease biomarkers, mainly due to their known advantages, that include high affinity, sensitivity, specificity and low costs, among others. This study describes the development of a label-free electrochemical multi-aptasensor array, for the simultaneous detection of human osteopontin (OPN), using two specific aptamers. To enable multiplexed protein assay, RNA and DNA aptamers were immobilized in the dual-screen-printed gold working electrodes via streptavidin-biotin interaction, and using the [Fe(CN)6]3−/4− as the redox probe for cyclic voltammetry measurements. The multi-aptasensor array herein developed exhibited a good response and selectivity to detect human OPN in the presence of other interfering proteins. Considering these preliminary results, the DNA/RNA dual aptasensor array could potentially be used as an analytical tool for the specific detection of human OPN, and for cancer diagnosis overall.

The corrosion behaviour of pure tin in an aqueous solution simultaneously containing Cl- and SO42- ions has been studied using electrochemical techniques, optical and scanning electron microscopy. Measurements were conducted under different chloride and sulphate ions concentrations. The potentiodynamic polarisation curves showed that the pitting potential, Epit, is independent from the variation of pH, temperature and chloride and sulphate concentration of the solution. In its turn, an increase of these parameters stimulates shifting of corrosion potential to more active values and leads to an increase of the corrosion and passive current densities. The electrochemical features were strongly supported by optical and scanning electron micrographs of the corroded surfaces of the pure tin samples after potentiodynamic polarisation experiments and immersion tests.

The inhibition of mild steel corrosion in a 1 M HCl solution by some natural free acids and antioxidants has been investigated by weight loss measurement, potentiodynamic polarization and DFT calculations. The experimental results have shown that these compounds exhibited a good corrosion inhibition. The inhibition efficiency increased with the inhibitor concentration. The adsorption of the inhibitor molecules onto the metal surface was found to respond to Langmuir adsorption isotherm for ascorbic, oleic and stearic acids, and to Temkin adsorption isotherm for palmitic acid. Tafel plot analysis revealed that these compounds acted as mixed type inhibitors, with more polarized cathodic than anodic curves. Regarding quantum chemical calculations, parameters such as energies of highest occupied molecular orbital and lowest unoccupied molecular orbital, energy gap, dipole moment, electronegativity, global hardness, softness, global electrophilicity, fraction of transferred electrons, ∆E Back-donation, Fukui and local softness indices have been performed on the tested inhibitors to investigate their structural and electronic properties, in order to provide an adsorption mechanism, and reveal the reactivity and selectivity of the molecules’ centers. The experimental results were in good agreement with theoretical results. The results for the natural acids were used to predict the linoleic acid inhibition efficiency.

The corrosion inhibition of carbon steel in a 1.0 M HCl solution, using 4-amino-2-(4 chlorophenyl)-8-(2,3-dimethoxyphenyl)-6-oxo-2,6-dihydropyrimido[2,1b][1,3]thiazine-3,7-dicarbonitrile (ACMPT) was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and quantum chemical calculations. Polarization curves indicate that the studied compound was acting as a mixed inhibitor with predominant cathodic effectiveness. The inhibition efficiency decreased with an increased temperature, and the thermodynamic and activation parameters obtained from this study were discussed. The adsorption behavior of ACMT follows Langmuir’s isotherm. In addition, Density Function Theory (DFT) calculations were performed on the studied molecule. The theoretical parameters obtained from this method are in good agreement with the experimental results.

The objective of this work is to achieve an analytical predictive model to study the influence of surface topography on the corrosion resistance of UNS S31600 stainless steel, in a solution of sodium chloride NaCl, at 6% by weight as electrolyte, applying the finite element method. The surface topography was given by the average roughness variation of a UNS S31600 work piece in superfinish turning, of which correlation with the corrosion resistance was examined. The analytical results show that corrosion physico-chemical parameters, polarization resistance, corrosion rate, corrosion potential, and current density have a very remarkable correlation with the surface roughness obtained by the superfinish turning. This is due to a very significant affinity between the plastic deformation depth obtained by turning, and the pits development on the work piece surface. The whole work was completed by an empirical analysis, in order to validate the analytical results obtained in comparison with the experimental results.