Electrochemical Behavior of Cu-9% Al-5% Ni-2% Mn Alloy in Chloride Media

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Baclofen into the lateral parabrachial nucleus induces hypertonic sodium chloride intake during cell dehydration

Background: Activation of GABAB receptors with baclofen into the lateral parabrachial nucleus (LPBN) induces ingestion of water and 0.3 M NaCl in fluid replete rats. However, up to now, no study has investigated the effects of baclofen injected alone or combined with GABAB receptor antagonist into the LPBN on water and 0.3 M NaCl intake in rats with increased plasma osmolarity (rats treated with an intragastric load of 2 M NaCl). Male Wistar rats with stainless steel cannulas implanted bilaterally into the LPBN were used.Results: In fluid replete rats, baclofen (0.5 nmol/0.2 μl), bilaterally injected into the LPBN, induced ingestion of 0.3 M NaCl (14.3 ± 4.1 vs. saline: 0.2 ± 0.2 ml/210 min) and water (7.1 ± 2.9 vs. saline: 0.6 ± 0.5 ml/210 min). In cell-dehydrated rats, bilateral injections of baclofen (0.5 and 1.0 nmol/0.2 μl) into the LPBN induced an increase of 0.3 M NaCl intake (15.6 ± 5.7 and 21.5 ± 3.5 ml/210 min, respectively, vs. saline: 1.7 ± 0.8 ml/210 min) and an early inhibition of water intake (3.5 ± 1.4 and 6.7 ± 2.1 ml/150 min, respectively, vs. saline: 9.2 ± 1.4 ml/150 min). The pretreatment of the LPBN with 2-hydroxysaclofen (GABAB antagonist, 5 nmol/0.2 μl) potentiated the effect of baclofen on 0.3 M NaCl intake in the first 90 min of test and did not modify the inhibition of water intake induced by baclofen in cell-dehydrated rats. Baclofen injected into the LPBN did not affect blood pressure and heart rate.Conclusions: Thus, injection of baclofen into the LPBN in cell-dehydrated rats induced ingestion of 0.3 M NaCl and inhibition of water intake, suggesting that even in a hyperosmotic situation, the blockade of LPBN inhibitory mechanisms with baclofen is enough to drive rats to drink hypertonic NaCl, an effect independent of changes in blood pressure. © 2013 Kimura et al.; licensee BioMed Central Ltd.

Influence of ethanol, acidity and chloride concentration on the corrosion resistance of AISI 316L stainless steel

The influence of ethanol, sulfuric acid and chloride on the corrosion resistance of 316L stainless steel was investigated by means of polarization curves and electrochemical impedance spectroscopy measurements. Over the studied range, the steel corrosion potential was independent of H2SO 4 and NaCl concentrations in aqueous solution. On the other hand, in solution containing 65 wt.% ethanol and 35 wt.% water, the corrosion potentials were higher than those obtained in aqueous solution. Besides, the steel corrosion potential was affected by the addition of H2SO4 and NaCl in solution. In solutions with and without ethanol, plus 0.35 wt.% NaCl, the presence of 1 wt.% H2SO4 inhibited the appearance of pitting corrosion. © 2013 Sociedade Brasileira de Química.

Photoelectrocatalysis based on Ti/TiO2 nanotubes removes toxic properties of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 from aqueous chloride samples

This work describes the efficiency of photoelectrocatalysis based on Ti/TiO2 nanotubes in the degradation of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 and to remove their toxic properties, as an alternative method for the treatment of effluents and water. For this purpose, the discoloration rate, total organic carbon (TOC) removal, and genotoxic, cytotoxic and mutagenic responses were determined, using the comet, micronucleus and cytotoxicity assays in HepG2 cells and the Salmonella mutagenicity assay. In a previous study it was found that the surfactant Emulsogen could contribute to the low mineralization of the dyes (60% after 4h of treatment), which, in turn, seems to account for the mutagenicity of the products generated. Thus this surfactant was not added to the chloride medium in order to avoid this interference. The photoelectrocatalytic method presented rapid discoloration and the TOC reduction was ≥87% after 240min of treatment, showing that photoelectrocatalysis is able to mineralize the dyes tested. The method was also efficient in removing the mutagenic activity and cytotoxic effects of these three dyes. Thus it was concluded that photoelectrocatalysis was a promising method for the treatment of aqueous samples. © 2013 Elsevier Ltd.

Effect of ionic strength solution on the stability of chitosan-DNA nanoparticles

Chitosan-DNA nanoparticles employed in gene therapy protocols consist of a neutralised, stoichiometric core and a shell of the excess of chitosan which stabilises the particles against further coagulation. At low ionic strength, these nanoparticles possess a high stability; however, as the ionic strength increases, it weakens the electrostatic repulsion which can play a decisive part in the formation of highly aggregated particles. In this study, new results about the effect of ionic strength on the colloidal stability of chitosan-DNA nanoparticles were obtained by studying the interaction between chitosans of increasing molecular weights (5, 10, 16, 29, 57 and 150 kDa) and calf thymus DNA. The physicochemical properties of polyplexes were investigated by means of dynamic light scattering, static fluorescence spectroscopy, optic microscopy, transmission electronic microscopy and gel electrophoresis. After subsequent addition of salt to the nanoparticles solution, secondary aggregation increased the size of the polyplexes. The nanoparticles stability decreased drastically at the ionic strengths 150 and 500 mM, which caused the corresponding decrease in the thickness of the stabilising shell. The morphologies of chitosan/DNA nanoparticles at those ionic strengths were a mixture of large spherical aggregates, toroids and rods. The results indicated that to obtain stable chitosan-DNA nanoparticles, besides molecular weight and N/P ratio, it is quite important to control the ionic strength of the solution. © 2013 Copyright Taylor and Francis Group, LLC.

Effect of Na-chloride on the bioleaching of a chalcopyrite concentrate in shake flasks and stirred tank bioreactors

Oxidative dissolution of chalcopyrite at ambient temperatures is generally slow and subject to passivation, posing a major challenge for developing bioleaching applications for this recalcitrant mineral. Chloride is known to enhance the chemical leaching of chalcopyrite, but much of this effect has been demonstrated at elevated temperatures. This study was undertaken to test whether 100-200 mM Na-chloride enhances the chemical and bacterial leaching of chalcopyrite in shake flasks and stirred tank bioreactor conditions at mesophilic temperatures. Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and abiotic controls were employed for the leaching experiments. Addition of Na-chloride to the bioleaching suspension inhibited the formation of secondary phases from chalcopyrite and decreased the Fe(III) precipitation. Neither elemental S nor secondary Cu-sulfides were detected in solid residues by X-ray diffraction. Chalcopyrite leaching was enhanced when the solution contained bacteria, ferrous iron and Na-chloride under low redox potential (< 450 mV) conditions. Scanning electron micrographs and energy-dispersive analysis of X-rays revealed the presence of precipitates that were identified as brushite and jarosites in solid residues. Minor amounts of gypsum may also have been present. Electrochemical analysis of solid residues was in concurrence of the differential effects between chemical controls, chloride ions, and bacteria. Electrochemical impedance spectroscopy was used to characterize interfacial changes on chalcopyrite surface caused by different bioleaching conditions. In abiotic controls, the impedance signal stabilized after 28 days, indicating the lack of changes on mineral surface thereafter, but with more resistive behavior than chalcopyrite itself. For bioleached samples, the signal suggested some capacitive response with time owing to the formation of less conductive precipitates. At Bode-phase angle plots (middle frequency), a new time constant was observed that was associated with the formation of jarosite, possibly also with minor amount or elemental S, although this intermediate could not be verified by XRD. Real impedance vs. frequency plots indicated that the bioleaching continued to modify the chalcopyrite/solution interface even after 42 days. © 2013 The Authors.

Mechanisms of SnO2 Nanoparticles Formation and Growth in Acid Ethanol Solution Derived from SAXS and Combined Raman-XAS Time-Resolved Studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of calcium chloride on the pH values of several formulations of calcium hydroxide mixed with chlorhexidine digluconate

This study evaluated the effect of the addition of 5% calcium chlorite (CaCl2) on pH values in calcium hydroxide pastes (CH), with or without 2% chlorhexidine digluconate (CHX) used as vehicle, in several periods analysis. Polyethylene tubes were filled with CH mixed with water (G1), 2% CHX solution (G2) or gel (G3), or CHX solution or gel with 5% CaCl2 (G4 and G5, respectively). All tubes were individually immersed in distilled water. After 12, 24 hours, 7, 14 and 28 days, pH value was evaluated directly in water which the tubes were stored. Data were submitted to ANOVA and Tukey tests (α=0.05). In 24 hs and 14 days, pH values were similar to all groups. In 12 hs, the G1 presented lower pH value than other groups except to G4 (p < 0.05), and G4 presented lower pH value than G5 (p < 0.05). In 7 days, G1 presented lower pH value than G4 and G5 (p < 0.05). In 28 days, G1 and G5 presented lower pH values than G2 and G4 (p < 0.05) and among other groups there are no statistical differences (p > 0.05). The pH values increased in long-term analysis to all CH pastes. The association of 5% calcium chloride with 2% CHX solution as vehicle of CH paste provided a pH value increase in relation to CH mixed with distilled water. The CHX gel interfered negatively on pH value in comparison to CHX solution when mixed with CaCl2.

Physicothermal properties of aqueous sodium chloride solutions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Application of Mossbauer spectroscopy to the study of corrosion resistance in NaCl solution of plasma nitrided AISI 316L stainless steel

Corrosion research in steels is one of the areas in which Mossbauer spectroscopy has become a required analytical technique, since it is a powerful tool for both identifying and quantifying distinctive phases (which contain Fe) with accuracy. In this manuscript, this technique was used to the study of corrosion resistance of plasma nitrided AISI 316L samples in the presence of chloride anions. Plasma nitriding has been carried out using dc glow-discharge, nitriding treatments, in medium of 80 vol.% H-2 and 20 vol.% N-2, at 673 K, and at different time intervals: 2, 4, and 7 h. Treated samples were characterized by means of phase composition and morphological analysis, and electrochemical tests in NaCl aerated solution in order to investigate the influence of treatment time on the microstructure and the corrosion resistance, proved by conversion electron Mossbauer spectroscopy (CEMS), glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM) and potentiodynamic polarization. A modified layer of about 8 gin was observed for all the nitrided samples, independently of the nitriding time. A metastable phase, S phase or gamma(N), was produced. It seems to be correlated with gamma`-Fe-4 N phase. If the gamma(N) fraction decreases, the gamma` fraction increases. The gamma(N) magnetic nature was analyzed. When the nitriding time increases, the results indicate that there is a significant reduction in the relative fraction of the magnetic gamma(N) (in) phase. In contrast, the paramagnetic gamma(N) (p) phase increases. The GAXRD analysis confirms the Mossbauer results, and it also indicates CrN traces for the sample nitrided for 7 h. Corrosion results demonstrate that time in the plasma nitriding treatment plays an important role for the corrosion resistance. The sample treated for 4 h showed the best result of corrosion resistance. It seems that the epsilon/gamma` fraction ratio plays an important role in thin corrosion resistance since this sample shows the maximum value for this ratio. (c) 2008 Published by Elsevier B.V.

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.

Intravenous Hypertonic Saline Solution (7.5%) and Oral Electrolytes to Treat of Calves with Noninfectious Diarrhea and Metabolic Acidosis

Objective The aim of this study was to compare the efficacy of treating osmotic diarrhea and dehydration in calves with hypertonic saline solution (HSS) IV, isotonic electrolyte solution (IES) PO, and a combination of these 2 solutions (HSS + IES). Experimental Design Eighteen male calves 830 days of age were used to evaluate the efficacy of 3 methods of fluid therapy after induction of osmotic diarrhea and dehydration. The diarrhea and dehydration were induced by administration of saccharose, spironolactone, and hydrochlorothiazide for 48 hours. The animals were randomly divided into 3 experimental groups: Group 1: 7.2% hypertonic saline solution-HSS (5 mL/kg IV); Group 2: oral isotonic electrolyte solution IES (60 mL/kg PO); or Group 3: HSS+IES. Clinical signs and laboratory finding observed 48 hours post-induction (Time 0) included diarrhea, dehydration, lethargy, and metabolic acidosis. Results Calves treated with HSS + IES experienced decreases in hematocrit, total protein concentration, albumin concentration, urea nitrogen concentration, and plasma volume as well as increases in blood pH, blood bicarbonate concentration, and central venous pressure between 1 and 3 hours post-treatment. These findings also were observed in animals treated with IES, however, at a slower rate than in the HSS + IES-treated animals. Animals treated with HSS continued to display signs of dehydration, lethargy, and metabolic acidosis 24 hours post-treatment. Conclusion Treatment with a combination of HSS and IES produced rapid and sustainable correction of hypovolemia and metabolic acidosis in calves with noninfections diarrhea and dehydration.

An EQCM-D study of the influence of chloride on the lead anodic oxidation

The influence of chloride on the electrodeposition of lead films and their dissolution in anodic stripping voltammetric experiments was examined. Gold substrates were plated with lead films, and mass changes were monitored by using the electrochemical quartz crystal microbalance with dissipation factor (EQCM-D). The results showed that the amount of electrodeposited lead is slightly dependent on the chloride concentration. The charge/mass ratio data indicated the presence of Pb(I) and Pb(II) as a result of film dissolution, and the precipitation and deposition of PbCl2 onto the electrode surface. Scanning electron microscopy images revealed that the morphology of the lead film was strongly influenced by chloride present in the plating solution and that much rougher films were obtained in comparison with those obtained in the absence of chloride. The rate of the anodic dissolution was higher for lead films with higher surface areas, which lead to an increase in their stripping voltammetric currents. (C) 2012 Elsevier Ltd. All rights reserved.