Determination of Cu, Ni and Pb in Aqueous Medium by FAAS after Pre-Concentration on 2-Aminothiazole Modified Silica Gel

This work describes the synthesis and characterization of 2-aminothiazole modified silica gel (SiAT), and the results of a study of the adsorption and pre-concentration (in batch and using a flow-injection system coupled to an absorption atomic spectrometer) of Cu(II), Ni(II) and Pb(II) in aqueous medium. The adsorption capacities for each metal ions in mmol g -1 were: Cu(II)= 1.18, Ni(II)= 1.15 and Pb(II)= 1.10. The results obtained in the flow experiments showed a recovery of practically 100% of the metal ions adsorbed in a mini-column packed with 100 mg of SiAT, using 100 μL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the application of a flow-injection system for the pre-concentration and quantification by FAAS of metal ions at trace level in natural water samples digested and not digest by an oxidizing UV photolysis.

Efficacy of homeopathic treatment against natural infection of sheep by gastrointestinal nematodes.

The efficacy of the homeopathic treatment with the Fator Vermes, administered according to the manufacturer's recommendations, was evaluated against gastrointestinal nematodes infections in sheep. The experiment was divided into two phases: in the first phase (January/06/2004 to April/30/2004), the animals of the treated (n=10) and control (n=10) groups were treated individually with conventional anthelmintics to avoid deaths. In the second phase (April/30/2004 to July/06/2004), the sheep from the group that received the Fator Vermes were treated as they had been in the previous phase, while the control group animals were treated with conventional anthelmintics at 14 day intervals. In the first phase of the experiment, there was no significant difference (P>0.05) between group means regarding egg counts in feces (EPG), weight gain, or packed cell volume (PCV). Meanwhile, in the second phase, the control group sheep had a significantly higher weight gain, higher PCV values, and lower EPG counts. Infective larvae of Haemonchus spp., Trichostrongylus spp., Cooperia spp., and Oesophagostomum spp. were identified in the fecal cultures. After six months of daily treatment with the Fator Vermes, it was not possible to substantiate the product's benefits in both sheep health and productivity or in the prophylaxis of gastrointestinal nematode infections.

Analysis of agonist and antagonist effects on thyroid hormone receptor conformation by hydrogen/deuterium exchange

Thyroid hormone receptors (TRs) are ligand-gated transcription factors with critical roles in development and metabolism. Although x-ray structures of TR ligand-binding domains (LBDs) with agonists are available, comparable structures without ligand (apo-TR) or with antagonists are not. It remains important to understand apo-LBD conformation and the way that it rearranges with ligands to develop better TR pharmaceuticals. In this study, we conducted hydrogen/deuterium exchange on TR LBDs with or without agonist (T 3) or antagonist (NH3). Both ligands reduce deuterium incorporation into LBD amide hydrogens, implying tighter overall folding of the domain. As predicted, mass spectroscopic analysis of individual proteolytic peptides after hydrogen/ deuterium exchange reveals that ligand increases the degree of solvent protection of regions close to the buried ligand-binding pocket. However, there is also extensive ligand protection of other regions, including the dimer surface at H10-H11, providing evidence for allosteric communication between the ligand-binding pocket and distant interaction surfaces. Surprisingly, Cterminal activation helix H12, which is known to alter position with ligand, remains relatively protected from solvent in all conditions suggesting that it is packed against the LBD irrespective of the presence or type of ligand. T 3, but not NH3, increases accessibility of the upper part of H3-H5 to solvent, and we propose that TR H12 interacts with this region in apo-TR and that this interaction is blocked by T 3 but not NH3.Wepresent data from site-directed mutagenesis experiments and molecular dynamics simulations that lend support to this structural model of apo-TR and its ligand-dependent conformational changes. (Molecular Endocrinology 25: 15-31, 2011). Copyright © 2011 by The Endocrine Society.

Study of adsorption and preconcentration by using a new silica organomodified with [3-(2,2′-dipyridylamine)propyl] groups

In this work, a silica surface chemically modified with [3-(2,2′-dipyridylamine)propyl] groups, named [3-(2,2′- dipyridylamine)propyl]silica (Si-Pr-DPA) was prepared, characterized, and evaluated for its heavy metal adsorption characteristics from aqueous solution. To our knowledge, we are the first authors who have reported the present modification. The material was characterized using infrared spectroscopy, SEM, and NMR 29Si and 13C solid state. Batch and column experiments were conducted to investigate for heavy metal removal from dilute aqueous solution by sorption onto Si-Pr-DPA. From a number of studies the affinity of various metal ions for the Si-Pr-DPA sorbent was determined to follow the order Fe(III) > Cr(III) >> Cu(II) > Cd(II) > Pb(II) > Ni(II). Two standard reference materials were used for checking the accuracy and precision of the method. The proposed method was successfully applied to the analysis of environmental samples. This ligand material has great advantage for adsorption of transition-metal ions from aqueous medium due to its high degree of organofunctionalization associated with the large adsorption capacity, reutilization possibility, and rapidity in reaching the equilibrium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of disease biomarkers in Eucalyptus by comprehensive two-dimensional gas chromatography and multivariate data analysis

In this paper is reported the use of the chromatographic profiles of volatiles to determine disease markers in plants - in this case, leaves of Eucalyptus globulus contaminated by the necrotroph fungus Teratosphaeria nubilosa. The volatile fraction was isolated by headspace solid phase microextraction (HS-SPME) and analyzed by comprehensive two-dimensional gas chromatography-fast quadrupole mass spectrometry (GC. ×. GC-qMS). For the correlation between the metabolic profile described by the chromatograms and the presence of the infection, unfolded-partial least squares discriminant analysis (U-PLS-DA) with orthogonal signal correction (OSC) were employed. The proposed method was checked to be independent of factors such as the age of the harvested plants. The manipulation of the mathematical model obtained also resulted in graphic representations similar to real chromatograms, which allowed the tentative identification of more than 40 compounds potentially useful as disease biomarkers for this plant/pathogen pair. The proposed methodology can be considered as highly reliable, since the diagnosis is based on the whole chromatographic profile rather than in the detection of a single analyte. © 2013 Elsevier B.V..

Continuous production of xylooligosaccharides in a packed bed reactor with immobilized-stabilized biocatalysts of xylanase from Aspergillus versicolor

The production of xylooligosaccharides (XOS) using a packed-bed enzymatic reactor was studied at lab-scale. For this, a xylanase from Aspergillus versicolor was immobilized on different supports. The optimal derivative was xylanase immobilized on glyoxyl-agarose supports. This derivative preserved 85% of its catalytic activity; it was around 700-fold more stable than the soluble enzyme after incubation at 60. °C and was able to be reused for at least 10 1. h-cycles retaining full catalytic activity. About 18% of oligosaccharides with prebiotic interest (X2-X6) were produced by the glyoxyl derivative in batch hydrolysis. The production of xylobiose was 2.5-fold higher using the immobilized preparation than with soluble enzyme and small concentrations of xylose (<0.1%) were observed only at the end of the reaction. The derivative was employed on a packed bed reactor, and the continuous operation with no recirculation reached 56% and 70% of the end of reaction with flow rates of 60. mL/h and 12. mL/h, respectively. In continuous operation with recirculation at a flow rate of 60. mL/h, the reaction was completed after four hours. © 2013 Elsevier B.V.

Cross linked Poly (4-Vinylpyridine-Ethylene Glycol Dimethacrylate) Used for Preconcentration of Cd(II) and its Determination by Flow Injection Flame Atomic Absorption Spectrometry

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hydrogen sulphide removal from air by biotrickling filter using open-pore polyurethane foam as a carrier

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The Use of Headspace Solid-Phase Microextraction (HS-SPME) to Assess the Quality and Stability of Fruit Products: An Example Using Red Mombin Pulp (Spondias purpurea L.)

The present study aimed to evaluate the volatiles profile of red mombin (Spondias purpurea) pulp and its powder produced by spray-drying (SD) as an example to show utility of headspace solid-phase microextraction (HS-SPME) in the analysis of parameters such as the quality and stability of fruit products. Volatiles profiles of the pulp were identified by gas chromatography-mass spectrometry (GC-MS), quantified by gas chromatography-flame ionization detector (GC-FID) and compared to the profile of the powder stored at 0, 60 and 120 days in plastic (PP) or laminated packages (LP). The results showed that the technique was able to identify 36 compounds in the red mombin pulp, 17 out of which have been described for the first time in this fruit, showing that red mombin fresh pulp appears to be unique in terms of volatiles composition. However, only 24 compounds were detected in the powder. This decrease is highly correlated (r(2) = 0.99), at least for the majority of compounds, to the degree of volatility of compounds. Furthermore, the powder stored in PP or LP showed no statistical differences in the amounts of its components for a period of 120 days of storage. Finally, this work shows how HS-SPME analysis can be a valuable tool to assess the quality and stability of fruit products.

Optimization of in situ derivatization SPME by experimental design for GC-MS multi-residue analysis of pharmaceutical drugs in wastewater

This paper presents the development of a procedure, which enables the analysis of nine pharmaceutical drugs in wastewater using gas chromatography-mass spectrometry (GC-MS) associated with solid-phase microextraction (SPME) for the sample preparation. Experimental design was applied to optimize the in situ derivatization and the SPME extraction conditions. Ethyl chloroformate (ECF) was employed as derivatizing agent and polydimethylsiloxane-divinylbenzene (PDMS-DVB) as the SPME fiber coating. A fractional factorial design was used to evaluate the main factors for the in situ derivatization and SPME extraction. Thereafter, a Doehlert matrix design was applied to find out the best experimental conditions. The method presented a linear range from 0.5 to 10 mu g/L, and the intraday and interday precision were lower than 16%. Applicability of the method was verified from real influent and effluent samples of a wastewater treatment plant, as well as from samples of an industry wastewater and a river.

Kinetic and Thermodynamic Studies on the Adsorption of Reactive Red 239 by Carra Sawdust Treated with Formaldehyde

In this study, carra sawdust pre-treated with formaldehyde was used to adsorb reactive red 239 (RR239). The effects of several experimental conditions, including the concentration of dye, sorbent dosage, temperature, ionic strength, stirring speed and solution pH, on the kinetics of the adsorption process have been studied, and the experimental data were fitted to pseudo-second-order model. A study of the intra-particle diffusion model indicates that the mechanism of dye adsorption using carra sawdust is rather complex and is most likely a combination of external mass transfer and intra-particle diffusion. The experimental data obtained at equilibrium were analyzed using the Langmuir and Freundlich isotherm models, and the results indicated that at this concentration range, both models can be applied for obtaining the equilibrium parameters. The maximum dye uptake obtained at 298 K was found to be 15.1 mg g(-1). In contrast to the usual systems, the reactive dye studied in the present work is strongly attached to the sawdust even after several washes with water, allowing it to be discarded as a solid waste.

LIQUID-PHASE MICROEXTRACTION FOR SIMULTANEOUS CHROMATOGRAPHIC ANALYSIS OF THREE ANTIDEPRESSANT DRUGS IN PLASMA

A method using Liquid Phase Microextraction for simultaneous detection of citalopram (CIT), paroxetine (PAR) and fluoxetine (FLU), using venlafaxine as internal standard, in plasma by high performance liquid chromatography with fluorescence detection was developed. The linearity was evaluated between 5.0 and 500 ng mL(-1) (r > 0.99) and the limit of quantification was 2.0, 3.0 and 5.0 ng mL-1 for CIT. PAR and FLU, respectively. Therefore, it can be applied to therapeutic drug monitoring, pharmacokinetics or bioavailability studies and its advantages are that it necessary relatively inexpensive equipment and sample preparation techniques.

Minimal processing of jucara's heart palm packed in brine acidified

The jucara's palm (Euterpe edulis), native to the Atlantic Forest is one of the palms most exploited for the removal of heart palm and the tree was removed in large areas. The aim of this study was to examine the feasibility of the methodology of "minimally processed" in jucara's palm. The raw material was obtained by COOPERAGUA, Sete Barras (SP) through a Sustainable Management Plan culminating in a permit issued by IBAMA, Forestry Foundation and DPRN. The process began with the withdrawal of external sheaths and cut, with subsequent immersion in a solution of sodium metabisulphite (Na2S2O5 - 200 ppm), sanitize with a chlorine solution and soak in brine acidified to wait until the filling. The cuttings were placed in polyethylene bags containing acidified solution at concentrations A 0.225%, B 0.375%, C 0.6%, D 0.825% determined by titration curve. The staining became clearer in treatments C and D, due to more acidity, resulting in higher inactivation of enzymes. Even with these positive results, were concluded that minimal processing of jucara is not effective due to the blackout, preventing its commercialization. To stop it requires the bleaching step, which does not characterize it as minimally processed.

Evaluation of Solid-Phase Microextraction using a Polythiophene Film and Liquid Chromatography with Spectrophotometric Detection for the Determination of Antidepressants in Plasma Samples

Polythiophene (PTh) phase electropolymerized on the stainless steel wire was evaluated as solid-phase microextraction (SPME), and analysis by liquid chromatography with spectrophotometric detection (LC-UV) for determination of new-generation antidepressants, selective serotonin reuptake inhibitors (SSRIs) (citalopram, paroxetine, fluoxetine and sertraline), in plasma samples. The influence of electropolymerization variables (scan rate, potential range and scan cycles) was evaluated on SPME performance. The SPME variables (extraction time, temperature, matrix pH, ionic strength and desorption procedure), as well as the influence of plasma proteins on sorption mechanisms were also evaluated. The SPME/LC-UV method developed for determination of antidepressants in plasma sample presented a linear range between the limit of quantification (LOQ, 200-250 ng mL(-1)) to 4000 ng mL(-1), and interday precision with coefficient of variation (CV) ranged from 11 to 15%. The proposed method can be a useful tool for the determination of antidepressants in human plasma samples in urgent toxicological analysis after the accidental or suicidal intake of higher doses of medications.

Solid-phase microextraction combined with comprehensive two-dimensional gas chromatography for fatty acid profiling of cell wall phospholipids

The combination of solid-phase microextraction (SPME) with comprehensive two-dimensional gas chromatography is evaluated here for fatty acid (FA) profiling of the glycerophospholipid fraction from human buccal mucosal cells. A base-catalyzed derivatization reaction selective for polar lipids such as glycerophospholipid was adopted. SPME is compared to a miniaturized liquidliquid extraction procedure for the isolation of FA methyl esters produced in the derivatization step. The limits of detection and limits of quantitation were calculated for each sample preparation method. Because of its lower values of limits of detection and quantitation, SPME was adopted. The extracted analytes were separated, detected, and quantified by comprehensive two-dimensional gas chromatography with flame ionization detection (FID). The combination of SPME and comprehensive two-dimensional gas chromatography with FID, using a selective derivatization reaction in the preliminary steps, proved to be a simple and fast procedure for FA profiling, and was successfully applied to the analysis of adult human buccal mucosal cells.