Thermally activated peroxydisulfate in the presence of additives: A clean method for the degradation of pollutants

The kinetics and mechanism of the thermal activation of peroxydisulfate, in the temperature range from 60 to 80 degrees C, was investigated in the presence and absence of sodium formate as an additive to turn the oxidizing capacity of the reaction mixture into a reductive one. Trichloroacetic acid, TCA, whose degradation by a reductive mechanism is well reported in the literature, was used as a probe. The chemistry of thermally activated peroxydisulfate is described by a reaction scheme involving free radical generation. The proposed mechanism is evaluated by a computer simulation of the concentration profiles obtained under different experimental conditions. In the presence of formate, SO(4)(center dot-) radicals yield CO(2)(center dot-), which are the main species available for degrading TCA. Under the latter conditions, TCA is more efficiently depleted than in the absence of formate, but otherwise identical conditions of temperature and [S(2)O(8)(2-)]. We therefore conclude that activated peroxydisulfate in the presence of formate as an additive is a convenient method for the mineralization of substrates that are refractory to oxidation. such as perchlorinated hydrocarbons and TCA. This method has the advantage that leaves no toxic residues. (C) 2009 Elsevier Ltd. All rights reserved.

Investigation of the mass transfer processes during the desalination of water containing phenol and sodium chloride by electrodialysis

Oxidation processes are used in wastewater treatment when conventional processes are not effective due to the presence of recalcitrant organic contaminants, like phenol. However, the presence of ionic compounds associated with organic pollutants may retard the oxidation. In this work the transport of species contained in an aqueous solution of phenol containing sodium chloride was evaluated in an electrodialysis (ED) system. An experimental study was carried out in which the influence of the process variables on the phenol loss and sodium chloride removal was investigated. Experiments were also performed without current, in order to determine the phenol transfer due to diffusion. The phenol and salt concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental design to determine the global characteristic parameters. A phenomenological approach was used to relate the phenol, salt and water fluxes with the driving forces (concentration and electric potential gradients). Under ED conditions, two contributions were pointed out for the phenol transport, i.e. diffusion and convection, this latter coming from the water flux due to electroosmosis related to the migration of salts. The fitting of the parameters of the transport equations resulted in good agreement with the experimental results over the range of conditions investigated. (c) 2008 Elsevier B.V. All rights reserved.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of (a single synthetic polyelectrolyte and sodium chloride)

Experimental results for the activity of water in aqueous solutions of 10 single, synthetic polyelectrolytes (polysodium acrylate, polysodium methacrylate, polyammonium acrylate, polysodium ethylene sulfonate, and polysodium styrene sulfonate) and sodium chloride at 298.2 K are presented. The experimental work was performed by applying the isopiestic method with sodium chloride as a reference substance. As expected, the activity of water decreases when the concentration of a polyelectrolyte and/or sodium chloride increases. At constant concentration of a polyelectrolyte and sodium chloride, the activity of water depends on the monomer unit and the molecular mass of the polyelectrolyte. The new data are to be used in future work to develop and test models for the Gibbs excess energy of aqueous solutions of polyelectrolytes.

Phase equilibria for salt-induced lysozyme precipitation: Effect of salt concentration and pH

The salt-induced precipitation of lysozyme from aqueous solutions was studied at 25 degrees C and various pH values by cloud-point investigations, precipitation experiments (analysing the compositions of the coexisting phases) and microscopic investigations of the precipitates. Sodium sulphate as well as ammonium sulphate were used to induce the precipitation. The experimental results are discussed and used to develop a scheme of the phase equilibrium in water-rich aqueous solutions of lysozyme and either Na2SO4 or (NH4)(2)SO4. (C) 2007 Elsevier B.V All rights reserved.

Biochemical responses of the ethylene-insensitive Never ripe tomato mutant subjected to cadmium and sodium stresses

In order to further address the known interaction between ethylene and components of the oxidative system, we have used the ethylene-insensitive Never ripe (Nr) tomato (Solanum lycopersicum L) mutant, which blocks ethylene responses. The mutant was compared to the control Micro-Tom (MT) cultivar subjected to two stressful situations: 100 mM NaCl and 0.5 mM CdCl(2). Leaf chlorophyll, lipid peroxidation and antioxidant enzyme activities in roots, leaves and fruits, and Na and Cd accumulation in tissues were determined. Although we verified a similar growth pattern and Na and Cd accumulation for MT and Nr, the mutant exhibited reduced leaf chlorophyll degradation following stress. In roots and leaves, the patterns of catalase (CAT), glutathione reductase (GR), ascorbate peroxidase (APX), guaiacol peroxidase (GPOX), superoxide dismutase (SOD) enzyme activity as well as malondialdehyde (MDA) and hydrogen peroxide (H(2)O(2)) production under the stressful conditions tested were very similar between MT and Nr mutant. However, Nr fruits showed increased H(2)O(2) production, reduced and enhanced APX activity in NaCl and CdCl(2), respectively, and enhanced GPOX in NaCl. Moreover, through non-denaturing PAGE, a similar reduction of SOD I band intensity in both, control MT and Nr mutant, treated with NaCl was observed. In leaves and fruits, a similar SOD activity pattern was observed for all periods, genotypes and treatments. Overall the results indicate that the ethylene signaling associated with NR receptor can modulate the biochemical pathways of oxidative stress in a tissue dependent manner, and that this signaling may be different following Na and Cd exposure. (C) 2011 Elsevier B.V. All rights reserved.

Influence of Urea and Ammonium Sulfate on Soil Acidity Indices in Lowland Rice Production

Urea and ammonium sulfate are principal nitrogen (N) sources for crop production. Two field experiments were conducted during three consecutive years to evaluate influence of urea and ammonium sulfate application on grain yield, soil pH, calcium (Ca) saturation, magnesium (Mg) saturation, base saturation, aluminum (Al) saturation, and acidity (H + Al) saturation in lowland rice production. Grain yield was significantly influenced by urea as well as ammonium sulfate fertilization. Soil pH linearly decreased with the application of N by ammonium sulfate and urea fertilizers. However, the magnitude of the pH decrease was greater by ammonium sulfate than by urea. The Ca and Mg saturations were decreased at the greater N rates compared to low rates of N by both the fertilizer sources. The Al and acidity saturation increased with increasing N rates by both the fertilizer sources. However, these acidity indices were increased more with the application of ammonium sulfate compared with urea. Rice grain yield had negative associations with pH, Ca saturation, Mg saturation, and base saturation and positive associations with Al and acidity saturation. This indicates that rice plant is tolerant to soil acidity.

Separation of Steroids and the Determination of Estradiol Content in Transdermic Patches by Microemulsion Electrokinetic Chromatography

A novel microemulsion electrokinetic capillary chromatography (MEEKC) method has been developed which separates a range of nine steroids. A microemulsion containing ethyl acetate, butan-1-ol, sodium dodecyl sulfate, 15% (v/v) acetonitrile and 12 mmol L(-1) sodium tetraborate aqueous buffer at pH 9.2 was used with direct UV detection at 200 nm. The method was validated for the determination of 17 beta-estradiol content, a hormone steroid, in transdermal patches. Adequate sensitivity (DL = 0.88 mu g mL(-1); QL = 2.65 mu g mL(-1)) without interference from sample excipients was obtained. 17 beta-Estradiol migrates in approximately 5.4 min. Estrone was used as internal standard and acceptable precision (< 1.2% RSD), linearity (r = 0.9996; range from 40.0 to 60.0 mu g mL(-1)), and recovery (100.4 +/- A 0.9% at three concentration levels) were obtained. The principal advantage of the method is that it is rapid and avoids the need of time consuming and expensive sample pre-treatment steps.

Dissolution parameters for sodium diclofenac-containing hypromellose matrix tablet

Sodium diclofenac (SD) release from dosage forms has been studied under different conditions. However, no dissolution method that is discriminatory enough to reflect slight changes in formulation or manufacturing process, and which could be effectively correlated with the biological properties of the dosage form, has been reported. This study sought to develop three different formulae of SD-containing matrix tablets and to determine the effect of agitation speed in its dissolution profiles. F1, F2 and F3 formulations were developed using hypromellose (10, 20 and 30%, respectively for F1, F2 and F3) and other conventional excipients. Dissolution tests were carried out in phosphate buffer pH 6.8 at 37 degrees C using apparatus 11 at 50, 75 or 100 rpm. Dissolution efficiency (DE), T(50) and T(90) were determined and plotted as functions of the variables agitation speed and hypromellose concentration. Regarding DE, F2 showed more sensitivity to variations in agitation speed than F1 and F3. Increasing hypromellose concentration reduced DE values, independent of agitation speed. Analysis of T(50) and T(90) suggests that F1 is less sensitive to variations in agitation speed than F2 and F3. Most discriminatory dissolution conditions were observed at 50 rpm. Results suggest that the comparison of dissolution performance of SD matrix tablets should take into account polymer concentration and agitation conditions. (C) 2009 Published by Elsevier B.V.

Determination of Vecuronium Bromide in Pharmaceuticals: Development, Validation and Comparative Study of HPLC and CZE Analytical Methods

Vecuronium bromide is a neuromuscular blocking agent used for anesthesia to induce skeletal muscle relaxation. HPLC and CZE analytical methods were developed and validated for the quantitative determination of vecuronium bromide. The HPLC method was achieved on an amino column (Luna 150 x 4.6 mm, 5 mu m) using UV detection at 205 nm. The mobile phase was composed of acetonitrile:water containing 25.0 mmol L(-1) of sodium phosphate monobasic (50:50 v/v), pH 4.6 and flow rate of 1.0 mL min(-1). The CZE method was achieved on an uncoated fused-silica capillary (40.0 cm total length, 31.5 cm effective length and 50 mu m i.d.) using indirect UV detection at 230 nm. The electrolyte comprised 1.0 mmol L(-1) of quinine sulfate dihydrate at pH 3.3 and 8.0% of acetonitrile. The results were used to compare both techniques. No significant differences were observed (p > 0.05).

Separation and partitioning of Green Fluorescent Protein from Escherichia coli homogenate in poly(ethylene glycol)/sodium-poly(acrylate) aqueous two-phase systems

The partitioning of Green Fluorescent Protein (GFP) in poly(ethylene glycol)/Na-poly(acrylate) aqueous two-phase systems (PEG/NaPA-ATPS) has been investigated. The aqueous two-phase systems are formed by mixing the polymers with a salt and a protein solution. The protein partitioning in the two-phase system was investigated at 25 degrees C. The concentration of the GFP was measured by fluorimetry. It was found that the partitioning of GFP depends on the salt type, pH and concentration of PEG. The data indicates that GFP partitions more strongly to the PEG phase in presence of Na2SO4 relative to NaCl. Furthermore, the GFP partitions more to the PEG phase at higher pH. The partition to the PEG phase is strongly favoured in systems with larger tie-line lengths (i.e. systems with higher polymer concentrations). The molecular weight of PEG is important since the partition coefficient (K) of GFP gradually decreases with increasing PEG size, from K ca. 300-400 for PEG 400 to K equal to 1.19 for PEG 8000. A separation process was developed where GFP was separated from a homogenate in two extraction steps: the GFP is first partitioned to the PEG phase in a PEG 3000/NaPA 8000 system containing 3 wt% Na2SO4, where the K value of GFP was 8. The GFP is then re-extracted to a salt phase formed by mixing the previous top-phase with a Na2SO4 solution. The K-value of GFP in this back-extraction was 0.22. The total recovery based on the start material was 74%. (c) 2008 Elsevier B.V. All rights reserved.

Protein partitioning in poly(ethylene glycol)/sodium polyacrylate aqueous two-phase systems

The partition of hemoglobin, lysozyme and glucose-6-phospate dehydrogenase (G6PDH) in a novel inexpensive aqueous two-phase system (ATPS) composed by poly(ethylene glycol) (PEG) and sodium polyacrylate (NaPA) has been studied. The effect of NaCl and Na2SO4, pH and PEG molecular size on the partitioning has been studied. At high pH (above 9), hemoglobin partitions strongly to the PEG-phase. Although some precipitation of hemoglobin occurs, high recovery values are obtained particularly for lysozyme and G6PDH. The partitioning forces are dominated by the hydrophobic and electrochemical (salt) effects, since the positively charged lysozyme and negatively charged G6PDH partitions to the non-charged PEG and the strongly negatively charged polyacrylate enriched phase, respectively. (c) 2007 Elsevier B.V. All rights reserved.

Bioavailability of dietary sodium copper chlorophyllin and its effect on antioxidant defence parameters of Wistar rats

BACKGROUND: There has been growing interest in sodium copper chlorophyllin (Cu-Chl) as a food colourant and supplement owing to its beneficial biological activities. Studies have revealed that this green pigment inhibits experimental carcinogenesis and interacts with proteins and genotoxic agents. Health-related activities have also been associated with the prevention of lipid peroxidation. However, intestinal absorption of this pigment has been considered insignificant, raising questions of whether eventual biological properties are related to pre- or post-absorptive actions. In this study, intestinal absorption of Cu-Chl and its appearance in serum and organs were estimated by high-performance liquid chromatography analysis in rat feeding experiments. The effect of ingested Cu-Chl on lipid peroxidation was analysed by measuring thiobarbituric acid-reactive substances and antioxidant enzyme activities in hepatic and brain tissues of oxidative stress-induced rats. RESULTS: The two main components of commercial Cu-Chl, namely Cu-chlorin e(6) and Cu-chlorin e(4), showed different digestive behaviours, and only Cu-chlorin e4 was found in serum, liver and kidneys. Antioxidant activity in vivo could be observed in brain and seemed to be related to in situ protection but not to antioxidant enzyme modulation. CONCLUSION: As at least one of the major components of Cu-Chl is effectively absorbed, further pharmacolkinetic studies are encouraged to access absorption rates and the role of ingested copper chlorophyllins in mammals. (C) 2009 Society of Chemical Industry

Manufacture of low-sodium Minas fresh cheese: Effect of the partial replacement of sodium chloride with potassium chloride

We investigated the effect of sodium reduction by partial substitution of sodium chloride (NaCl) with potassium chloride (KCl) on the manufacture of Minas fresh cheese during 21 d of refrigerated storage. Four treatments of low-sodium Minas fresh cheese were manufactured, with partial replacement of NaCl by KCl at 0, 25, 50, and 75% (wt/wt), respectively. The cheeses showed differences in the content of moisture, ash, protein, salt, and lipid contents, as well as on the extent of proteolysis and hardness throughout the storage period. However, no difference was observed among treatments within each storage day tested. The partial substitution of NaCl by KCl decreased up to 51.8% the sodium concentration of the cheeses produced. The consumer test indicated that it is possible to manufacture a low-sodium Minas fresh cheese that is acceptable to consumers by partial substitution of NaCl by KCl at 25% (wt/wt) in the salting step.

A new nitrosyl ruthenium complex nitric oxide donor presents higher efficacy than sodium nitroprusside on relaxation of airway smooth muscle

Nitric oxide (NO) has been demonstrated to be the primary agent in relaxing airways in humans and animals. We investigated the mechanisms involved in the relaxation induced by NO-donors, ruthenium complex [Ru(terpy)(bdq)NO(+)](3+) (TERPY) and sodium nitroprusside (SNP) in isolated trachea of rats contracted with carbachol in an isolated organs chamber. For instance, we verified the contribution of K(+) channels, the importance of sGC/cGMP pathway, the influence of the extra and intracellular Ca(2+) sources and the contribution of the epithelium on the relaxing response. Additionally, we have used confocal microscopy in order to analyze the action of the NO-donors on cytosolic Ca(2+) concentration. The results demonstrated that both compounds led to the relaxation of trachea in a dependent-concentration way. However, the maximum effect (E(max)) of TERPY is higher than the SNP. The relaxation induced by SNP (but not TERPY) was significantly reduced by pretreatment with ODQ (sGC inhibitor). Only TERPY-induced relaxation was reduced by tetraethylammonium (K(+) channels blocker) and by pre-contraction with 75 mM KCl (membrane depolarization). The response to both NO-donors was not altered by the presence of thapsigargin (sarcoplasmic reticulum Ca(2+)-ATPase inhibitor). The epithelium removal has reduced the relaxation only to SNP, and it has no effect on TERPY. The both NO-donors reduced the contraction evoked by Ca(2+) influx, while TERPY have shown a higher inhibitory effect on contraction. Moreover, the TERPY was more effective than SNP in reducing the cytosolic Ca(2+) concentration measured by confocal microscopy. In conclusion, these results show that TERPY induces airway smooth muscle relaxation by cGMP-independent mechanisms, it involves the fluxes of Ca(2+) and K(+) across the membrane, it is more effective in reducing cytosolic Ca(2+) concentration and inducing relaxation in the rat trachea than the standard drug, SNP. (C) 2011 Elsevier B.V. All rights reserved.

Isolation, functional, and partial biochemical characterization of galatrox, an acidic lectin from Bothrops atrox snake venom

Snake venom lectins have been studied in regard to their chemical structure and biological functions. However, little is known about lectins isolated from Bothrops atrox snake venom. We report here the isolation and partial functional and biochemical characterization of an acidic glycan-binding protein called galatrox from this venom. This lectin was purified by affinity chromatography using a lactosyl-sepharose column, and its homogeneity and molecular mass were evaluated by high-performance liquid chromatography, sodium dodecyl sulfate-polyacrylamide gel electrophoresis, and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The purified galatrox was homogeneous and characterized as an acidic protein (pI 5.2) with a monomeric and dimeric molecular mass of 16.2 and 32.5 kDa, respectively. Alignment of N-terminal and internal amino acid sequences of galatrox indicated that this protein exhibits high homology to other C-type snake venom lectins. Galatrox showed optimal hemagglutinating activity at a concentration of 100 mu g/ml and this effect was drastically inhibited by lactose, ethylenediaminetetraacetic acid, and heating, which confirmed galatrox`s lectin activity. While galatrox failed to induce the same level of paw edema or mast cell degranulation as B. atrox crude venom, galatrox did alter cellular viability, which suggested that galatrox might contribute to venom toxicity by directly inducing cell death.