Influência da geometria da plataforma na determinação de chumbo em zidovudina (AZT) por ET AAS

The aim of this work was to compare the performances of the L'vov and integrated platforms in order to overcome the interferences found on lead determination in zidovudine by ET AAS. Pyrolysis and atomization temperatures found with integrated platform were 700 and 1400°C, respectively. The characteristic masses were 12.7 ± 1.2 pg with integrated platform and 11.1 ± 1.3 pg with grooved platform. The ratio between the slopes of zidovudine and aqueous curves shows a decrease in the interferences when the L'vov platform is used (bAZT/b aq = 0.97 ± 0.10) and the detection limit found was 0.03 µg.g-1. That ratio was 0.85 ± 0.07 with the integrated platform.

Determinação de As em amostras orgânicas de interesse ambiental por espectrometria de absorção atômica com atomização eletrotérmica após combustão em bomba de O2

The toxicity of the major As species present in the environment justifies the effort for quantifying the element in environmental organic samples, which can vary from animal and vegetal tissues to coal and industrial residues. This paper comments about the applicability of the O2 bomb digestion, as a general procedure for all environmental organic materials. A rapid and straightforward method is suggested, which consists in burning the sample in the bomb at high O2 pressure, dissolving the vapours in diluted HNO3 and determining As in the resulting solution by atomic absorption spectrometry with electrothermal atomization. The method was applied to certified materials and plant samples.

Comportamento da atomização eletrotérmica de ouro, prata, bismuto, cádmio, chumbo e estanho em soluções aquosas e em etanol, a partir de diferentes superfícies atomizadoras

The atomization behavior of Au, Ag, Bi, Cd, Pb, and Sn from pyrolitic graphite coating (L'vov platform) with the use Pd and Mg solutions, and zirconium coated platform with the analytes in nitric acid 0.2% v/v and in ethanol was investigated. In ethanol medium, the sensitivity gain was three-fold for Bi and Cd using Zr as modifier. Without modifier, the ethanol medium is appropriate only for Au and Cd. In nitric acid medium, the Zr coated platform elevates sensitivity at least two-fold for Bi and Cd. The method was applied to the determination of Ag, Au and Bi of certified steel samples, after on-line preconcentration, sorption on a minicolumn filled with C-18 bonded to silica gel and elution with ethanol. The concentrations obtained agreed with the recommended values.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

Determinação de As, Cd e Pb em amêndoas e mesocarpo de babaçu, sapucaia, xixá e castanha-do-pará por espectrometria de absorção atômica

This work describes methods for the simultaneous determination of Cd and Pb by graphite furnace atomic absorption spectrometry and As by hydride generation atomic absorption spectrometry in Brazilian nuts. The samples (~ 0.300 g) were digested to clear solutions in a closed vessel microwave oven. The pyrolysis and atomization temperatures for simultaneous determinations of Cd and Pb were 1100 and 2100 °C, respectively, using 0.5% (w v-1) NH4H2PO4 + 0.03% (w v-1) Mg(NO3)2 as chemical modifier. The limits of detection (3Δ) were 3.8 μg kg-1 for As, 0.86 μg kg-1 for Cd and 13 μg kg-1 for Pb. The reliability of the entire procedures was confirmed by peach leaves (No. 1547 - NIST) certified reference material analysis and addition and recovery tests. The found concentrations presented no statistical differences at the 95% confidence level.

Construção de espectrômetro de emissão atômica com atomização eletrotérmica em filamento de tungstênio (WCAES)

It is here discussed the development of a low cost analytical instrument with capacity for metals determination using atomic emission measurements in an electrothermal atomization system with a tungsten coil atomizer. The main goal was to show a new frontier for using this atomizer and to demonstrate that the simple instrumental arrangement here proposed has potential for portability and for solving analytical tasks related to metals determination. Atomic emission of calcium was selected for the adjustment of instrumental parameters and to evaluate the main characteristics of the lab-built instrument. Cobalt was determined in medicines and one alloy to demonstrate its feasibility.

Determinación simultánea de Cr, Ni y V en orina mediante et aas

A procedure for the simultaneous determination of Cr, Ni, and V in urine by electrothermal atomic absorption spectrometry (ET AAS) was optimized by factorial design, and performed at a pyrolysis and atomization temperatures of 1300 and 2500 ºC, respectively, using 15 µg de Mg(NO3)2 as chemical modifier. Characteristics mass of 14, 6 and 220 ρg and detection limits of the method of 0.07, 0.38 and 0.75 µg L-1 were obtained for Cr, Ni and V respectively. The methodology was validated using a Liphochek Urine Metals Control sample (Bio-Rad) (P=0.05). The methodology was applied to samples of voluntary Venezuelan people, not environmentally exposed to specific emissions, and results ranging from < LOD-1.1 and 1.3-3.3 µg L-1 was observed for Cr and V, respectively, and not detectable levels for Ni.

Simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation process by GFAAS

A method has been developed for the simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation by GFAAS. The integrated platform of transversely heated graphite atomizer was treated with tungsten to form a coating of tungsten carbide. Six samples of commercial solid antibiotics were analyzed by injecting 20 µL of digested samples into the pretreated graphite platform with co-injection of 5 µL of 1000 mg L-1 Pd as chemical modifier. Samples were mineralized in a closed-vessel microwave-assisted acid-digestion system using nitric acid plus hydrogen peroxide. The pyrolysis and atomization temperatures of the heating program of the atomizer were selected as 600°C and 2200°C, respectively. The calculated characteristic mass for Cd and Pb was 1.6 pg and 42 pg, respectively. Limits of detection (LOD) based on integrated absorbance were 0.02 µg L-1 Cd and 0.7 µg L-1 Pb and the relative standard deviations (n = 10) for Cd and Pb were 5.7% and 8.0%, respectively. The recoveries of Cd and Pb added to the digested samples varied from 91% to 125% (Cd) and 80% to 112% (Pb).

Enhancing the Usability of Drug Materials by Electrostatic Atomisation

Electrospraying or electrostatic atomisation is a process of liquid disruption by electrostatic forces. When liquid is brought into an electric field, charge is induced to its surface. Once the repulsive electrostatic force exceeds the liquid surface tension, the liquid disrupts into small highly charged droplets. The size of the electrosprayed droplets can range from hundreds of micrometers down to a few tens of nanometers. Electrospraying can be used not only to produce droplets, but also solid particles. The research presented in this thesis concentrates on producing drug particles by this method. In the experiments, a drug powder was dissolved in a convenient solvent and the solution was atomised. The solvent was then evaporated from the formed droplets in a drying medium and inside each droplet, a dense cluster of the dissolved drug remained. From the pharmaceutical point of view, the most important characteristics of the produced particles are size distribution, porosity, crystal form and degree of crystallinity. These properties affect the dissolution behaviour and ultimately the drug bioavailability in the body. The effects of electrostatic atomization on the aforementioned characteristics are generally not well understood. The research focused on studying these particle properties and finding possible correlations with the spraying parameters. The produced droplets were dried either under atmospheric or reduced pressure, the latter in order to improve the drying process. Special emphasis was put on implementing the spraying under reduced pressure, and the effects of the drying pressure on particle properties. Based on the results, the possibilities to enhance the dissolution of poorly soluble drugs by this method were estimated. In the course of experiments, it was also discovered that electrospraying may have a profound effect on the polymorphic form of the produced drug particles. In the light of the obtained results, it was concluded that electrospraying may offer a valuable tool to overcome some of the challenges met in modern drug development and formulation.

Lead and cadmium content of Brazilian beers

The elements called heavy metals when ingested are not completely eliminated from animal bodies and are responsible for chronic and acute intoxications. Sixty-three samples of beer, produced in the states of São Paulo, Paraná, Rio de Janeiro, Rio Grande do Sul, Minas Gerais, and Pará, were analysed for lead and cadmium content by atomic absorption spectrometry with graphite furnace atomization and Zeeman correction. The concentrations of Pb and Cd of dark differed significantly from light beers, being higher in the former. No significant difference was found between the beers produced in predominantly rural areas and the ones produced in industrialized areas. The concentrations of lead and cadmium in all samples were bellow the maximum accepted by present Brazilian regulations and ranged from not detected to 290mugPb/L and from not detected to 14.3mugCd/L. The average concentrations were 37mugPb/L and 1.6mugCd/L.

Optimization of the extraction of carrageenan from Kappaphycus alvarezii using response surface methodology

This study aims to optimize an alternative method of extraction of carrageenan without previous alkaline treatment and ethanol precipitation using Response Surface Methodology (RSM). In order to introduce an innovation in the isolation step, atomization drying was used reducing the time for obtaining dry carrageenan powder. The effects of extraction time and temperature on yield, gel strength, and viscosity were evaluated. Furthermore, the extracted material was submitted to structural analysis, by infrared spectroscopy and nuclear magnetic resonance spectroscopy (¹H-NMR), and chemical composition analysis. Results showed that the generated regression models adequately explained the data variation. Carrageenan yield and gel viscosity were influenced only by the extraction temperature. However, gel strength was influenced by both, extraction time and extraction temperature. Optimal extraction conditions were 74 ºC and 4 hours. In these conditions, the carrageenan extract properties determined by the polynomial model were 31.17%, 158.27 g.cm-2, and 29.5 cP for yield, gel strength, and viscosity, respectively, while under the experimental conditions they were 35.8 ± 4.68%, 112.50 ± 4.96 g.cm-2, and 16.01 ± 1.03 cP, respectively. The chemical composition, nuclear magnetic resonance spectroscopy, and infrared spectroscopy analyses showed that the crude carrageenan extracted is composed mainly of κ-carrageenan.

Study of the physicochemical characteristics of soursop powder obtained by spray-drying

This study aimed at contributing to the development of new foodstuffs made by soursop pulp powder obtained by spraydrying. Different concentrations of maltodextrin DE 20 (15, 30, and 45%) were added to commercial soursop pulp, which was dehydrated afterwards. The following analyses were carried out: water activity, moisture, pH, soluble solids, acidity, ascorbic acid, hygroscopicity, degree of caking, and rehydration time. The results obtained for the three powder treatments (15, 30 and 45% of maltodextrin) were, respectectively: water activity (0.19a±0.00; 0.20a±0.00; 0.18a±0.01); moisture (1.17c±0.12; 1.47b±0.05; 1.82a±0.06); pH (3.75a±0.05; 3.73a±0.06; 3.70a±0.03); soluble solids (89.67a±0.00; 89.84a±0.00; 90.00a±0.06); acidity (3.01a±0.02; 1.91b±0.03; 1.24c±0.03); ascorbic acid (18.90a±0.00; 14.48b±0.00; 11.26b±0.78); hygroscopicity (5.93a±0.40; 3.82b±0.16; 3.28b±0.38); degree of caking (78.36a±2.86; 35.38b±6.07; 24.77b4.89), and rehydration time (02.03a±0.46; 01.16ab±0.50; 0.59b±0.30). The soursop powders with 30 and 45% of maltodextrin had few significant differences in terms of physicochemical and hygroscopic characteristics, which allow us to consider the percentage of 30% of maltodextrin, in this study, as the best percentage for soursop pulp atomization.

Encapsulation de Dehalococcoides: avantage pour la déhalogénation des solvants chlorés en sites contaminés

Le tétrachloroéthène (PCE) et les éthènes chlorés qui lui sont apparentés ont été abondamment utilisés pour plusieurs applications en industrie dès le début du 20e siècle. Ils sont cependant comptés parmi les polluants les plus communs des sols et de l’eau et beaucoup d’efforts sont déployés afin de les éliminer. Nous croyons que la conversion des éthènes chlorés en éthènes par des microorganismes est une solution prometteuse. Le premier aspect du projet visait donc à établir les conditions pour lesquelles un consortium enrichi en Dehalococcoides ethenogenes permettrait la conversion complète de PCE en éthène. Les expériences réalisées nous ont permis de souligner le rôle de l’acide lactique ajouté aux cultures comme source de carbone et source indirecte d’électrons pour la déhalorespiration. Nous avons également pu établir l’effet de la concentration initiale de biomasse dans les cultures sur le profil de déhalogénation du PCE. Le deuxième aspect du projet visait à développer un protocole d’encapsulation du consortium dans une matrice polymérique afin de profiter des nombreux avantages potentiels de l’encapsulation. Nous avons testé trois montages d’encapsulation différents : atomisation avec jet d’air, atomisation avec vibrations ultrasoniques et « drop-wise ». Le dernier montage prévoyait l’encapsulation des cultures dans des billes d’alginate enrobées de chitosane gélifié par du lignosulfonate. C’est le seul montage qui nous a permis d’encapsuler le consortium de façon efficace sans effet significatifs négatifs sur son activité de déchlorination. Aussi, la comparaison des profils de déhalogénation du PCE de cellules encapsulées et cellules libres a montré une plus faible accumulation de TCE, 1,2-DCE et VC dans les échantillons de cellules encapsulée et, par conséquent, une conversion plus rapide et plus complète du PCE en éthène. Finalement, nous avons observé une tendance favorable à l’idée que les microorganismes encapsulés bénéficient d’un effet de protection contre de faibles concentrations d’oxygène.

La conservation du patrimoine urbain, catalyseur du renouvellement des pratiques urbanistiques? : une réflexion théorique sur l'appropriation de la notion de patrimoine urbain par l'urbanisme

Cette thèse questionne l’apport de la conservation du patrimoine urbain à l’urbanisme. Il y est avancé que l’association entre la conservation du patrimoine urbain et l'urbanisme, dans leur cadre conceptuel actuel, plutôt que d’être le catalyseur du renouvellement de l’urbanisme, a perpétué une appréhension fragmentée et une atomisation de l'établissement, consacrant ainsi le paradigme fonctionnaliste, qui conditionne encore largement les pratiques urbanistiques contemporaines, au Québec notamment. En effet, bien que depuis les années 1960 la conservation du patrimoine soit présentée comme le fil rouge dans le redéploiement de la compétence d’édifier, plusieurs études soulignent les résultats mitigés de nombreuses expériences de conservation ainsi qu’une contribution limitée relativement à la formulation des projets urbains. Plus particulièrement, malgré la reconnaissance de l’intérêt de la patrimonialisation et de la fécondité potentielle de l’idée de patrimoine en général, l’urbanisme n’est pas parvenu à en définir les termes de la contribution, tant au plan conceptuel que processuel, en regard de sa propre projectualité. De ce fait, il ne réussit pas à affranchir la réflexion patrimoniale du registre de la conservation afin de se l’approprier véritablement. Cette thèse explique les causes de cette incapacité à partir d’une analyse des conditions de l’appropriation de la notion de patrimoine urbain mises de l’avant par l’approche giovannonienne. Celle-ci, fondamentalement urbanistique, propose une conception du patrimoine urbain qui s’émancipe du monument historique et du registre de la conservation. Indissociable d’une projectualité urbanistique, l’intérêt pour le patrimoine urbain de Giovannoni relève d’une reconnaissance du déjà là qui fonde des modalités de prises en charge de l’existant. Celles-ci posent les bases d’un renouvellement de la manière de penser l’urbanisme. La notion giovannonienne de patrimoine urbain, qui réfère à l’ensemble urbain patrimonial, devient l’élément de base d’une analyse morphologique urbanistique qui permet de conceptualiser l’agglomération contemporaine comme ensemble marqué par les ruptures et les discontinuités. Prenant appui sur une démarche dialogique, l’approche giovannonienne relève d’une mise en tension des singularités et d’une appréhension conjointe des différentes registres, ceux des formes et des forces, de l’existant et du souhaité, du penser et du faire. Giovannoni dépasse ainsi l’opposition entre continuité et rupture portée par les pratiques afin de penser l’articulation du nouveau à l’ancien. La confrontation de l’approche giovannonienne aux différentes perspectives qui ont marqué l’urbanisme moderne, montre que ces modalités de prise en charge de l’existant sont conditionnelles à l’accomplissement des promesses de la considération du patrimoine urbain. Autrement, l’association de la conservation du patrimoine urbain et de l’urbanisme culmine dans une double assimilation : l’assimilation du patrimoine urbain au monument historique d’architecture conduit à confondre projet d’urbanisme et projet de conservation.

Systematic construction of models for the exchange hole of density functional theory.

Dans ce travail, nous étendons le nombre de conditions physiques actuellement con- nues du trou d’échange exact avec la dérivation de l’expansion de quatrième ordre du trou d’échange sphérique moyenne exacte. Nous comparons les expansions de deux- ième et de quatrième ordre avec le trou d’échange exact pour des systèmes atomiques et moléculaires. Nous avons constaté que, en général, l’expansion du quatrième ordre reproduit plus fidèlement le trou d’échange exact pour les petites valeurs de la distance interélectronique. Nous démontrons que les ensembles de base de type gaussiennes ont une influence significative sur les termes de cette nouvelle condition, en étudiant com- ment les oscillations causées par ces ensembles de bases affectent son premier terme. Aussi, nous proposons quatre modèles de trous d’échange analytiques auxquels nous imposons toutes les conditions actuellement connues du trou d’échange exact et la nou- velle présentée dans ce travail. Nous évaluons la performance des modèles en calculant des énergies d’échange et ses contributions à des énergies d’atomisation. On constate que les oscillations causeés par les bases de type gaussiennes peuvent compromettre la précision et la solution des modèles.