Portugaliae
Electrochimica Acta

DNA and guanine are efficient fluorescence quenchers of the cationic conjugated polymer, poly {9,9-bis[N,N-(trimethylammonium)hexyl] fluorene-co-l,4-phenylene} (CCP). Studies with CCPs, of average chain length ~6, 12 and 100 repeat units, with single strand (ss) DNA, double strand (ds) DNA, and guanine, in 25/75 acetonitrile/water (v/v) mixtures result in Stern-Volmer quenching plots that show upward curvature. Initial Stern-Volmer constants, kSV, are in the range ≈ 3-20 x 107 M-1 which is much higher than possible by diffusional encounter quenching. Aggregation studies in acetonitrile/water mixtures show that aggregation is also an effective quencher of CCP fluorescence, and we note that both aggregation and quenching by DNA or guanine is accompanied by a reduction in solution absorbance at 380 nm. Comparison of the relationship between changes in absorbance and changes in emission intensity suggest that both solvent and chemical induced fluorescence quenching are due to aggregation. We interpret the correlated changes in absorption and emission, high quenching constants, and upward curving Stern-Volmer plots as evidence that the dominant mechanism for fluorescence quenching by DNA or guanine is via induced aggregation of the polymer. The upward curvature of Stern- Volmer plots and high kSV values for DNA and guanine are indicative of “aggregate energy migration quenching” in which CCP aggregates around a DNA or guanine molecule to form an aggregate complex in which excitation energy migrates between and along the polymer chains until it is quenched at an aggregate trap.

A comprehensive photophysical and spectroscopic Raman study guided by Density Functional Theory and Hartree-Fock calculations has been done in a series of fully oxidized oligothiophenes with variable chain length, up to four rings. A comparison with the properties of oligoenes and oligothiophenes is proposed.

The corrosion rates in the presence of nizoral (NZR), an antifungal drug, as mild steel corrosion inhibitor in 0.1 M H2SO4 was measured by the weight loss method in the temperature range from 30 – 50 ºC. Results obtained revealed that NZR acts as an inhibitor for mild steel in sulphuric acid solution. Inhibition efficiency increased with increase in concentration of the inhibitor but decreased with increase in temperature. The addition of KI increased the inhibition of NZR to a considerable extent. The experimental results suggest that the presence of iodide ions in the solution stabilized the adsorption of Nizoral molecules on the mild steel surface thereby improving the inhibition efficiency of Nizoral. The adsorption characteristics of the inhibitor were approximated by Langmuir adsorption isotherm and kinetic/thermodynamic adsorption model of El-Awady et al. Mechanism of physical adsorption is proposed from the activation and thermodynamic parameters calculated.

The use of stainless steel 304(SS) tanks to deposit thiourea in industry has been evaluated by studying the corrosion behaviour in 1% thiourea solution, before and after zinc plating. Weight loss method, 1% copper sulphate test, polarization study and AC impedance spectra have been used. The corrosion resistance of SS decreased when zinc was used for electrodeposition. Hence SS vessels electroplated with zinc should not be used to store thiourea solution, in industry.

The effect of iodide ion on the corrosion inhibition of aluminium in NaOH in the presence of Gum Arabic (GA) was studied using weight loss and hydrogen evolution techniques at 303 and 313 K. The results obtained showed that inhibition efficiency increased with increasing GA concentration. The inhibiting action of GA was considerably enhanced by the addition of KI. The adsorption of KI, GA alone and in combination with iodide ion was found to obey Temkin adsorption isotherm. The inhibiting effect of GA and (GA+KI) increased with increase in temperature of the corrosion medium, indicating chemical adsorption mechanism. Synergism parameter evaluated was found to be greater than unity for the different concentrations of GA, which shows that the enhanced inhibition of GA caused by the addition of iodide ion is due to synergistic effect. It could be deduced from the thermodynamic parameters obtained that adsorption of GA alone and in combination with KI onto the metal surface is spontaneous.

Inhibitive and adsorption properties of ethanol extract of Phyllanthus amarus for the corrosion of mild steel in H2SO4 were investigated using gravimetric, thermometric and gasometric methods. Ethanol extract of Phyllanthus amarus leaves is a good adsorption inhibitor for the corrosion of mild steel in H2SO4. Thermodynamic consideration indicates that the adsorption of the extract is exothermic and spontaneous. Also, the adsorption characteristic of the inhibitor is consistent with the assumptions of Langmuir adsorption isotherm. From the results and findings of the study, a physical adsorption mechanism is proposed for the adsorption of ethanol extract of Phyllanthus amarus on mild steel surface. The inhibition potentials of ethanol extract of Phyllanthus amarus leaves are enhanced by its phytochemical constituents.

The adsorption of [(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-(4-methoxy-phenyl)-methyl]-urea on iron in phosphoric media was studied by using electrochemical technique. The adsorption mechanism was investigated using adsorption isotherms. The experimental data fit localized adsorption models. The values for free energy of adsorption, ΔG0ads, were also calculated at each surface coverage, θ, of the studied compound by applying the mathematical model of Bockris – Swinkels adsorption isotherm. The variation of free energy of adsorption, ΔG0ads with surface coverage, θ, was interpreted in terms of deviation from ideal condition assumed in Langmuir model. A possible adsorption model of HPU2 molecules on to the metal surface was suggested.

1-(3-methyl-4H-1,4-benzothiazin-2-yl)ethanone (1,4-BT) was synthesised via a new mechanism. 1,4-BT was thereafter tested as corrosion inhibitor of mild steel in hydrochloric solution at 293 K by weight loss measurements and electrochemical techniques (potentiodynamic polarisation, polarisation resistance, impedance spectroscopy (EIS)). Inhibiting efficiency (E%) increased with concentration and reached highest values up to 98% even at low concentration with changing the mechanism of the corrosion process. Results obtained showed that the inhibitor studied was an efficient inhibitor, especially in cathodic domain. The temperature effect on the corrosion behaviour of mild steel in 1 M HCl with and without 1,4-BT at 5 10-3 M was studied in the temperature range from 293 to 333 K. E% remains the same even at high temperature. The adsorption free energy and activation parameters for the mild steel dissolution reaction, in the presence of 1,4-BT, were determined. 1,4-BT is adsorbed on the mild steel surface according to a Langmuir isotherm adsorption model.

The effect of some amidopoly ethylamine, with different numbers of ethylamine units, on the corrosion of zinc electrode in ZnCl2, NH4Cl and (ZnCl2 + NH4Cl) electrolytes has been studied using galvanostatic polarization measurements. The inhibition efficiency was found to increase with increasing concentration, number of ethylamine units per molecule and with decreasing the temperature. Inhibition is explained on the basis of adsorption of amidopoly ethylamine molecules on the zinc electrode surface through their ethylamine groups. The inhibitors are adsorbed on the zinc electrode surface according to Langmuir adsorption isotherm. Some thermodynamic parameters are calculated and explained for the tested systems from the data obtained at different temperatures.

The effect of some phenyl phthalimide derivatives on the corrosion of carbon steel in 0.5 M H2SO4 solution was studied using weight loss and galvanostatic polarization techniques. The percentage inhibition efficiency was found to increase with increasing concentration of inhibitor and with decreasing temperature. Inhibition was explained by adsorption of these compounds on the metal surface. The adsorption follows Freundlich adsorption isotherms. Some thermodynamic functions were computed and discussed.