Bismuth Modified Gold Microelectrode for Pb(II) Determination in Wine Using Alkaline Medium

Electrodeposition of bismuth on gold microelectrodes for determination of Pb(II) by square wave anodic stripping voltammetry (SWASV) was accomplished by an in situ procedure in alkaline solution. A linear calibration plot for Pb(II) in the concentration range 40 to 6700 nmol L(-1) (r=0.998) was obtained, the detection limit was found to be 12.5 nmol L(-1) (S/N = 3) and the relative standard deviation in Solutions containing 1 mu mol L(-1) Pb(II) was 4% (n = 12). The analytical performance of the proposed sensor wits tested by measuring the Pb(II) concentration in a wine sample. The result Was in good agreement with the one obtained by GFAAS.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Adsorption of Pb(2+), Cu(2+) and Cd(2+) in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butilene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO(2). Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb(2+), Cu(2+) and Cd(2+) in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd(2+), Cu(2+) and Pb(2+) from single ion solutions. Adsorption of Cu(2+) was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7. (C) 2007 Elsevier Inc. All rights reserved.

Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Electrochemical oxidation of glycine by doped nickel hydroxide modified electrode

The electrocatalytic oxidation of glycine by doped nickel hydroxide modified electrodes and their use as sensors are described. The electrode modification was carried out by a simple electrochemical coprecipitation and its electrochemical properties were investigated. The modified electrode presented activity for glycine oxidation after applying a potential required to form NiOOH (similar to 0.45 V vs Ag/AgCl). In these conditions a sensitivity of 0.92 mu A mmol(-1) L and a linear response range from 0.1 up to 1.2 mmol L(-1) were achieved in the electrolytic Solutions at PH 12.6. Limits of detection and quantification were found to be 30 and 110 mu mol L(-1), respectively. Kinetic studies performed with rotating disk electrode (RDE) and by chronoamperometry allowed to determine the heterogeneous rate constant of 4.3 x 10(2) mol(-1) Ls(-1), Suggesting that NiOOH is a good electrocatalyst for glycine oxidation. NiOOH activity to oxidize other amino acids was also investigated, (c) 2008 Elsevier B.V. All rights reserved.

Determination of ciclopirox olamine in pharmaceutical products by capillary electrophoresis with capacitively coupled contactless conductivity detection

This paper describes the determination of ciclopirox olamine in pharmaceutical formulations using capillary electrophoresis with capacitively coupled contactless conductivity detection. In an alkaline medium, ciclopirox olamine is converted into an anionic species and its detection is possible in capillary electrophoresis with capacitively coupled contactless conductivity detection without an electroosmotic flow modifier, because it is a low-mobility species. A linear working range from 2.64 to 264 mu g/mL in sodium hydroxide electrolyte as well as low detection limit (0.39 mu g/mL) and a good repeatability (RSD = 3.4% for 264 mu g/mL ciclopirox solution (n = 10)) were achieved. It was also possible to determine olamine in its cationic form when acetic acid was used as the electrolyte solution. The results obtained include a linear range from 26.4 to 184.8 mu g/mL and a detection limit of 2.6 mu g/mL olamine. The proposed methods were applied to the analysis of commercial pharmaceutical products and the results were compared with the values indicated by the manufacturer as well as those obtained using a titrimetric method recommended by American Pharmacopoeia.

Use of copper and gold electrodes as sensitive elements for fabrication of an electronic tongue: Discrimination of wines and whiskies

A low-cost method is proposed to classify wine and whisky samples using a disposable voltammetric electronic tongue that was fabricated using gold and copper substrates and a pattern recognition technique (Principal Component Analysis). The proposed device was successfully used to discriminate between expensive and cheap whisky samples and to detect adulteration processes using only a copper electrode. For wines, the electronic tongue was composed of copper and gold working electrodes and was able to classify three different brands of wine and to make distinctions regarding the wine type, i.e., dry red, soft red, dry white and soft white brands. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Behaviour of TiO(2)-SiMgO(x) hybrid composites on the solar photocatalytic degradation of polluted air

The photocatalytic performance of TiO(2)-SiMgO(x) ceramic plates for trichloroethylene abatement in gas phase has been evaluated under sun irradiance conditions. A continuous flow Pyrex glass reactor fixed on the focus of a compound parabolic collector has been used. The performance of the hybrid photocatalyst has been evaluated as the variation of TCE conversion and reaction products formation with the solar irradiance at different total gas flow, TCE concentration, and water vapour content. SiMgO(x) not only provides adsorbent properties to the photocatalyst, but it also allows the effective use of the material during low solar irradiance conditions. The adsorption-desorption phenomena play a pivotal role in the behaviour of the system. Thus, TCE conversion curves present two different branches when the sun irradiance increases (sunrise) or decreases (sunset). CO(2), COCl(2) and DCAC were the most relevant products detected. Meanwhile CO(2) concentration was insensitive to the branch analysed, COCl(2) or DCAC were not indicating the ability of these compounds to be adsorbed on the composite. An increase of the UV irradiation at total TCE conversion promotes the CO(2) selectivity. The excess of energy arriving to the reactor favours the direct reaction pathway to produce CO(2). The photonic efficiency, calculated as a function of the rate of CO(2) formation, decreases linearly with the solar irradiance up to around 2 mW cm(-2), where it becomes constant. For decontamination systems high TCE conversion is pursuit and then high solar irradiance values are required, in spite of lower photonic efficiency values. The present photocatalyst configuration, with only 17% of the reactor volume filled with the photoactive material, allows total TCE conversion for 150 ppm and 1 L min(-1) in a wide sun irradiance window from 2 to 4 mW cm(-2). The incorporation of water vapour leads to an increase of the CO(2) selectivity keeping the TCE conversion around 90%, although significant amounts of COCl(2) were observed. (c) 2010 Elsevier B.V. All rights reserved.

Effect of accelerated carbonation on cementitious roofing tiles reinforced with lignocellulosic fibre

The present work evaluated the effects of accelerated carbonation on mechanical and physical characteristics of cementitious roofing tiles reinforced with vegetable fibre. The maximum load and toughness of the tiles have increased approximately 25% and 80% respectively as a consequence of the accelerated carbonation. Water absorption and apparent porosity decreased with carbonation while bulk density increased as a clear indication of the densification of the composite. The improvement on the mechanical performance suggests that the fibres retained their tensile strength in the inorganic matrix. Results of specimens extracted from the tested tiles after approximately 480 days in laboratory environment and further aged indicate that soak and dry cycles promoted some leaching of hydration products and more voids and lower density when performed before carbonation. The results indicate the utilization of accelerated carbonation as an effective procedure to mitigate the degradation suffered by the cellulose fibres in the less aggressive medium. (C) 2009 Elsevier Ltd. All rights reserved.

Alkaline phosphatase as a reporter of sigma(S) levels and rpoS polymorphisms in different E-coli strains

sigma(S) is responsible for the transcriptional regulation of genes related to protection against stresses and bacterial survival and it accumulates in the cell under conditions of stress, such as nutrient limitation. An increase in the levels of sigma(S) causes a reduction in the expression of genes that are transcribed by RNA polymerase associated with the principal sigma factor, sigma(70). phoA, that encodes alkaline phosphatase (AP) is expressed under phosphate shortage conditions, and is also repressed by sigma(S). Here we show that in a Pi-limited chemostat, accumulation of rpoS mutations is proportional to the intrinsic level of sigma(S) in the cells. Acquisition of mutations in rpoS relieves repression of the PHO genes. We also devised a non-destructive method based on the rpoS effect on AP that differentiates between rpo(S+) and rpoS mutants, as well as between high and low-sigma(S) producers. Using this method, we provide evidence that sigma(S) contributes to the repression of AP under conditions of Pi excess and that AP variation among different strains is at least partly due to intrinsic variation in sigma(S) levels. Consequently, a simple and non-destructive AP assay can be employed to differentiate between strains expressing different levels of sigma(S) on agar plates.

Transcriptional Processing of the pst Operon of Escherichia coli

The pst operon of Escherichia coli is composed of five genes that encode a high-affinity phosphate transport system. pst belongs to the PHO regulon, which is a group of genes and operons that are induced in response to phosphate limitation. The pst operon also has a regulatory role in the repression of PHO genes` transcription under phosphate excess conditions. Transcription of pst is initiated at the promoter located upstream to the first gene, pstS. Immediately after its synthesis, the primary transcript of pst is cleaved into shorter mRNA molecules in a ribonuclease E-dependent manner. Other ribonucleases, such as RNase III and MazF, do not play a role in pst mRNA processing. RNase E is thus at least partially responsible for processing the pst primary transcript.

Culture medium for isolating chitinolytic bacteria from seawater and plankton

Chitin degradation is a key step in the cycling of nutrients in marine ecosystems and chitinolytic bacteria are the primary agents of this process. Chitinases, produced by bacteria, have potential applications in agriculture, medicine and in a wide range of biotechnological processes. We utilized a simple, rapid and cost-effective method of colloidal chitin preparation and a culture medium, in which colloidal chitin is the sole carbon source for the purpose of counting and isolating chitinolytic bacteria from seawater and plankton. This culture medium could be useful to isolate bacteria with the ability to produce extracellular chitinases for biotechnological applications.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

Insights into the mechanism of progressive RNA degradation by the archaeal exosome

Initially identified in yeast, the exosome has emerged as a central component of the RNA maturation and degradation machinery both in Archaea and eukaryotes. Here we describe a series of high-resolution structures of the RNase PH ring from the Pyrococcus abyssi exosome, one of them containing three 10-mer RNA strands within the exosome catalytic chamber, and report additional nucleotide interactions involving positions N5 and N7. Residues from all three Rrp41-Rrp42 heterodimers interact with a single RNA molecule, providing evidence for the functional relevance of exosome ring-like assembly in RNA processivity. Furthermore, an ADP-bound structure showed a rearrangement of nucleotide interactions at site N1, suggesting a rationale for the elimination of nucleoside diphosphate after catalysis. In combination with RNA degradation assays performed with mutants of key amino acid residues, the structural data presented here provide support for a model of exosome-mediated RNA degradation that integrates the events involving catalytic cleavage, product elimination, and RNA translocation. Finally, comparisons between the archaeal and human exosome structures provide a possible explanation for the eukaryotic exosome inability to catalyze phosphate-dependent RNA degradation.

Radical acetylation of 2`-deoxyguanosine and L-histidine coupled to the reaction of diacetyl with peroxynitrite in aerated medium

Diacetyl, like other alpha-dicarbonyl compounds, is reportedly cytotoxic and genotoxic. A food and cigarette contaminant, it is related with alcohol hepatotoxicity and lung disease. Peroxynitrite is a potent oxidant formed in vivo by the diffusion-controlled reaction of the superoxide radical anion with nitric oxide, which is able to form adducts with carbon dioxide and carbonyl compounds. Here, we investigate the nucleophilic addition of peroxynitrite to diacetyl forming acetyl radicals, whose reaction with molecular oxygen leads to acetate. Peroxynitrite is shown to react with diacetyl in phosphate buffer (bell-shaped pH profile with maximum at 7.2) at a very high rate constant (k(2) = 1.0 X 10(4) M-1 s(-1)) when compared with monocarbonyl substrates (k(2) < 10(3) M-1 s(-1)). Phosphate ions (100-500 MM) do not affect the rate of spontaneous peroxynitrite decay, but the H2PO4- anion catalyzes the nucleophilic addition of the peroxynitrite anion to diacetyl. The intermediacy of acetyl radicals is suggested by a three-line spectrum (a(N) = a(H) = 0.83 mT) obtained by EPR spin trapping of the reaction mixture with 2-methyl-2-nitrosopropane. The peroxynitrite reaction is accompanied by concentration-dependent oxygen uptake. Stoichiometric amounts of acetate from millimolar amounts of peroxynitrite and diacetyl were obtained under nonlimiting conditions of dissolved oxygen. In the presence of either L-histidine or 2`-deoxyguanosine, the peroxynitrite/diacetyl system afforded the corresponding acetylated molecules identified by HPLC-MS"". These studies provide evidence that the peroxynitrite/diacetyl reaction yields acetyl radicals and raise the hypothesis that protein and DNA nonenzymatic acetylation may occur in cells and be implicated in aging and metabolic disorders in which oxygen and nitrogen reactive species are putatively involved.