Développement d’une nouvelle méthode d’analyse multi-résidus par LDTD/APCI-MS/MS pour la quantification de pesticides et de produits pharmaceutiques dans les eaux usées

Une nouvelle méthode d'extraction en phase solide (SPE) couplée à une technique d'analyse ultrarapide a été développée pour la détermination simultanée de neuf contaminants émergents (l'atrazine, le déséthylatrazine, le 17(béta)-estradiol, l'éthynylestradiol, la noréthindrone, la caféine, la carbamazépine, le diclofénac et le sulfaméthoxazole) provenant de différentes classes thérapeutiques et présents dans les eaux usées. La pré-concentration et la purification des échantillons a été réalisée avec une cartouche SPE en mode mixte (Strata ABW) ayant à la fois des propriétés échangeuses de cations et d'anions suivie d'une analyse par une désorption thermique par diode laser/ionisation chimique à pression atmosphérique couplée à la spectrométrie de masse en tandem (LDTD-APCI-MS/MS). La LDTD est une nouvelle méthode d'introduction d'échantillon qui réduit le temps total d'analyse à moins de 15 secondes par rapport à plusieurs minutes avec la chromatographie liquide couplée à la spectrométrie de masse en tandem traditionnelle (LC-MS/MS). Plusieurs paramètres SPE ont été évalués dans le but d'optimiser l'efficacité de récupération lors de l'extraction des analytes provenant des eaux usées, tels que la nature de la phase stationnaire, le débit de chargement, le pH d'extraction, le volume et la composition de la solution de lavage et le volume de l'échantillon initial. Cette nouvelle méthode a été appliquée avec succès à de vrais échantillons d'eaux usées provenant d'un réservoir de décantation primaire. Le recouvrement des composés ciblés provenant des eaux usées a été de 78 à 106%, la limite de détection a été de 30 à 122 ng L-1, alors que la limite de quantification a été de 88 à 370 ng L-1. Les courbes d'étalonnage dans les matrices d'eaux usées ont montré une bonne linéarité (R2 > 0,991) pour les analytes cibles ainsi qu’une précision avec un coefficient de variance inférieure à 15%.

An investigation into the mechanics of cutting using data from orthogonally cutting Nylon 66

Cutting force data for Nylon 66 has been examined in terms of various different models of cutting. Theory that includes significant work of separation at the tool tip was found to give the best correlation with experimental data over a wide range of rake angles for derived primary shear plane angle. A fracture toughness parameter was used as the measure of the specific work of separation. Variation in toughness with rake angle determined from cutting is postulated to be caused by mixed mode separation at the tool tip. A rule of mixtures using independently determined values of toughness in tension (mode 1) and shear (mode 11) is found to describe well the variation with rake angle. The ratio of modes varies with rake angle and, in turn, with the primary shear plane angle. Previous suggestions that cutting is a means of experimentally determining fracture toughness are now seen to be extended to identify the mode of fracture toughness as well.

A probabilistic analysis of the future potential of evaporative cooling systems in a temperate climate

The probabilistic projections of climate change for the United Kingdom (UK Climate Impacts Programme) show a trend towards hotter and drier summers. This suggests an expected increase in cooling demand for buildings – a conflicting requirement to reducing building energy needs and related CO2 emissions. Though passive design is used to reduce thermal loads of a building, a supplementary cooling system is often necessary. For such mixed-mode strategies, indirect evaporative cooling is investigated as a low energy option in the context of a warmer and drier UK climate. Analysis of the climate projections shows an increase in wet-bulb depression; providing a good indication of the cooling potential of an evaporative cooler. Modelling a mixed-mode building at two different locations, showed such a building was capable of maintaining adequate thermal comfort in future probable climates. Comparing the control climate to the scenario climate, an increase in the median of evaporative cooling load is evident. The shift is greater for London than for Glasgow with a respective 71.6% and 3.3% increase in the median annual cooling load. The study shows evaporative cooling should continue to function as an effective low-energy cooling technique in future, warming climates.

Simulation of the future performance of low-energy evaporative cooling systems using UKCP09 climate projections

Recent activity in the development of future weather data for building performance simulation follows recognition of the limitations of traditional methods, which have been based on a stationary (observed) climate. In the UK, such developments have followed on from the availability of regional climate models as delivered in UKCIP02 and recently the probabilistic projections released under UKCP09. One major area of concern is the future performance and adaptability of buildings which employ exclusively passive or low-energy cooling systems. One such method which can be employed in an integral or retrofit situation is direct or indirect evaporative cooling. The effectiveness of evaporative cooling is most strongly influenced by the wet-bulb depression of the ambient air, hence is generally regarded as most suited to hot, dry climates. However, this technology has been shown to be effective in the UK, primarily in mixed-mode buildings or as a retrofit to industrial/commercial applications. Climate projections for the UK generally indicate an increase in the summer wet-bulb depression, suggesting an enhanced potential for the application of evaporative cooling. The paper illustrates this potential by an analysis of the probabilistic scenarios released under UKCP09, together with a detailed building/plant simulation of case study building located in the South-East of England. The results indicate a high probability that evaporative cooling will still be a viable low-energy technique in the 2050s.

Influence of probabilistic climate projections on building energy simulation

The Chartered Institute of Building Service Engineers (CIBSE) produced a technical memorandum (TM36) presenting research on future climate impacting building energy use and thermal comfort. One climate projection for each of four CO2 emissions scenario were used in TM36, so providing a deterministic outlook. As part of the UK Climate Impacts Programme (UKCIP) probabilistic climate projections are being studied in relation to building energy simulation techniques. Including uncertainty in climate projections is considered an important advance to climate impacts modelling and is included in the latest UKCIP data (UKCP09). Incorporating the stochastic nature of these new climate projections in building energy modelling requires a significant increase in data handling and careful statistical interpretation of the results to provide meaningful conclusions. This paper compares the results from building energy simulations when applying deterministic and probabilistic climate data. This is based on two case study buildings: (i) a mixed-mode office building with exposed thermal mass and (ii) a mechanically ventilated, light-weight office building. Building (i) represents an energy efficient building design that provides passive and active measures to maintain thermal comfort. Building (ii) relies entirely on mechanical means for heating and cooling, with its light-weight construction raising concern over increased cooling loads in a warmer climate. Devising an effective probabilistic approach highlighted greater uncertainty in predicting building performance, depending on the type of building modelled and the performance factors under consideration. Results indicate that the range of calculated quantities depends not only on the building type but is strongly dependent on the performance parameters that are of interest. Uncertainty is likely to be particularly marked with regard to thermal comfort in naturally ventilated buildings.

Stabilizing Nonstationary Electrochemical Time Series

Electrochemical systems are ideal working-horses for studying oscillatory dynamics. Experimentally obtained time series, however, are usually associated with a spontaneous drift in some uncontrollable parameter that triggers transitions among different oscillatory patterns, despite the fact that all controllable parameters are kept constant. Herein we present an empirical method to stabilize experimental potential time series. The method consists of applying a negative galvanodynamic sweep to compensate the spontaneous drift and was tested for the oscillatory electro-oxidation of methanol on platinum. For a wide range of applied currents, the base system presents spontaneous transitions from quasi-harmonic to mixed mode oscillations. Temporal patterns were stabilized by galvanodynamic sweeps at different rates. The procedure resulted in a considerable increase in the number of oscillatory cycles from 5 to 20 times, depending on the specific temporal pattern. The spontaneous drift has been associated with uncompensated oscillations, in which the coverage of some adsorbed species are not reestablished after one cycle; i.e., there is a net accumulation and/or depletion of adsorbed species during oscillations. We interpreted the rate of the galvanodynamic sweep in terms of the time scales of the poisoning processes that underlies the uncompensated oscillations and thus the spontaneous slow drift.

Governança e coordenação em arranjos multinível de políticas públicas transversais: assistência social, educação e saúde no Programa Bolsa Família

Este estudo apresenta o desenvolvimento teórico e a aplicação de um modelo voltado à análise de arranjos de governança de políticas públicas que ocorrem quando múltiplas organizações estão envolvidas em lidar com questões complexas. A seguinte pergunta de pesquisa foi proposta: Como opera o conjunto de instrumentos de coordenação empregados na governança de uma política pública transversal? Um estudo de caso exploratório sobre o Programa Bolsa Família foi realizado, especificamente na sua dimensão relacionada à coordenação entre os setores de assistência social, educação e saúde. Os métodos de pesquisa consistiram em análise de conteúdo de documentos e transcrições de entrevistas semiestruturadas com atores-chave do Programa nos três setores de políticas. Os resultados demonstram como diferentes modos de governança coexistem no arranjo multinível estudado, revelando diversos elementos de coordenação cuja operação concomitante resulta em um modo de governança misto. Contribui-se, assim, para o aperfeiçoamento do Programa e para o desenvolvimento teórico, metodológico e aplicado dos conceitos de governança e de coordenação, ficando demonstrado ser possível integrá-los na análise de políticas públicas transversais.

Conditional reasoning: A key to assessing computer-based knowledge-building communication processes

This article describes a methodological approach to conditional reasoning in online asynchronous learning environments such as Virtual-U VGroups, developed by SFU, BC, Canada, consistent with the notion of meaning implication: If part of a meaning C is embedded in B and a part of a meaning B is embedded in A, then A implies C in terms of meaning [Piaget 91]. A new transcript analysis technique was developed to assess the flows of conditional meaning implications and to identify the occurrence of hypotheses and connections among them in two human science graduate mixed-mode online courses offered in the summer/spring session of 1997 by SFU. Flows of conditional meaning implications were confronted with Virtual-U VGroups threads and results of the two courses were compared. Findings suggest that Virtual-U VGroups is a knowledge-building environment although the tree-like Virtual-U VGroups threads should be transformed into neuronal-like threads. Findings also suggest that formulating hypotheses together triggers a collaboratively problem-solving process that scaffolds knowledge-building in asynchronous learning environments: A pedagogical technique and an built-in tool for formulating hypotheses together are proposed. © Springer Pub. Co.

A low-voltage low-sensitivity sinusoidal VCO for DPLL realizations

A quasi-sinusoidal linearly tunable OTA-C VCO built with triode-region transconductors is presented. Oscillation upon power-on is ensured by RHP poles associated with gate-drain capacitances of OTA input devices. Since the OTA nonlinearity stabilizes the amplitude, the oscillation frequency f0 is first-order independent of VDD, making the VCO adequate to mixed-mode designs. A range of simulations attests the theoretical analysis. As part of a DPLL, the VCO was prototyped on a 0.8μm CMOS process, occupying an area of 0.15mm2. Nominal f0 is 1MHz, with K VCo=8.4KHz/mV. Measured sensitivity to VDD is below 2.17, while phase noise is -86dBc at 100-KHz offset. The feasibility of the VCO for higher frequencies is verified by a redesign based on a 0.35μm CMOS process and VDD=3.3V, with a linear frequency-span of l3.2MHz - 61.5MHz.

Effect of microwave disinfection procedures on torsional bond strengths of two hard chairside denture reline materials

Purpose: This study evaluated the potential effects of denture base resin water storage time and an effective denture disinfection method (microwave irradiation at 650 W for 6 minutes) on the torsional bond strength between two hard chairside reline resins (GC Reline and New Truliner) and one heat-polymerizing denture base acrylic resin (Lucitone 199). Materials and Methods: Cylindrical (30 x 3.9 mm) denture base specimens (n = 160) were stored in water at 37°C (2 or 30 days) before bonding. A section (3.0 mm) was removed from the center of the specimens, surfaces prepared, and the reline materials packed into the space. After polymerization, specimens were divided into four groups (n = 10): Group 1 (G1) - tests performed after bonding; Group 2 (G2) - specimens immersed in water (200 ml) and irradiated twice (650 W for 6 minutes); Group 3 (G3) - specimens irradiated daily until seven cycles of disinfection; Group 4 (G4) - specimens immersed in water (37°C) for 7 days. Specimens were submitted to a torsional test (0.1 Nm/min), and the torsional strengths (MPa) and the mode of failure were recorded. Data from each reline material were analyzed by a two-way analysis of variance, followed by Neuman-Keuls test (p = 0.05). Results: For both Lucitone 199 water storage periods, before bonding to GC Reline resin, the mean torsional strengths of G2 (2 days - 138 MPa; 30 days - 132 MPa), G3 (2 days - 126 MPa; 30 days - 130 MPa), and G4 (2 days - 130 MPa; 30 days - 137 MPa) were significantly higher (p < 0.05) than G1 (2 days - 108 MPa; 30 days - 115 MPa). Similar results were found for Lucitone 199 specimens bonded to New Truliner resin, with G1 specimens (2 days - 73 MPa; 30 days - 71 MPa) exhibiting significantly lower mean torsional bond strength (p < 0.05) than G2 (2 day - 86 MPa; 30 days - 90 MPa), G3 (2 days - 82 MPa; 30 days - 82 MPa), and G4 specimens (2 days - 78 MPa; 30 days - 79 MPa). The adhesion of both materials was not affected by water storage time of Lucitone 199 (p > 0.05). GC reline showed a mixed mode of failure (adhesive/cohesive) and New Truliner failed adhesively. Conclusions: Up to seven microwave disinfection cycles did not decrease the torsional bond strengths between the hard reline resins, GC Reline and New Truliner to the denture base resin Lucitone 199. The effect of additional disinfection cycles on reline material may be clinically significant and requires further study. Copyright © 2006 by The American College of Prosthodontists.

Bond strength of hard chairside reline resins to a rapid polymerizing denture base resin before and after thermal cycling

Purpose: This study assessed the shear bond strength of 4 hard chairside reline resins (Kooliner, Tokuso Rebase Fast, Duraliner II, Ufi Gel Hard) to a rapid polymerizing denture base resin (QC-20) processed using 2 polymerization cycles (A or B), before and after thermal cycling. Materials and Methods: Cylinders (3.5 mm x 5.0 mm) of the reline resins were bonded to cylinders of QC-20 polymerized using cycle A (boiling water-20 minutes) or B (boiling water; remove heat-20 minutes; boiling water-20 minutes). For each reline resin/polymerization cycle combination, 10 specimens (groups CAt e CBt) were thermally cycled (5 and 55°C; dwell time 30 seconds; 2,000 cycles); the other 10 were tested without thermal cycling (groups CAwt ad CBwt). Shear bond tests (0.5 mm/min) were performed on the specimens and the failure mode was assessed. Data were analyzed by 3-way ANOVA and Newman-Keuls post-hoc test (α=.05). Results: QC-20 resin demonstrated the lowest bond strengths among the reline materials (P<.05) and mainly failed cohesively. Overall, the bond strength of the hard chairside reline resins were similar (10.09±1.40 to 15.17±1.73 MPa) and most of the failures were adhesive/cohesive (mixed mode). However, Ufi Gel Hard bonded to QC-20 polymerized using cycle A and not thermally cycled showed the highest bond strength (P<.001). When Tokuso Rebase Fast and Duraliner II were bonded to QC-20 resin polymerized using cycle A, the bond strength was increased (P=.043) after thermal cycling. Conclusions: QC-20 displayed the lowest bond strength values in all groups. In general, the bond strengths of the hard chairside reline resins were comparable and not affected by polymerization cycle of QC-20 resin and thermal cycling.

Futebol brasileiro: uma análise comparativa das fórmulas de disputa do campeonato brasileiro da série A nos últimos 15 anos (1995-2010)

In Brazil, the football is more than just a sport, it's a passion and part of country's DNA almost a century ago. By this prerogative the club national championship, nowadays known as Brazilian Championship and organized by Brazilian Football Confederation, it is a mark in this modality. During the soccer history, were made several changes of nomenclature, rules and dispute mode, that generated many controversies, contributing for discussing about credibility of the championship. There were many changes about dispute mode, alternating the mixed mode (eliminatory + classificatory and vice versa) and a dispute mode based on classification. This research aimed to described and to analyzed the changes that have occurred in dispute types of the Brazilian Championship, series A, in the last 15 years (1995 to 2010). It was analyzed each edition, with data like average of public, matches and participants number, period that the championship was conducted, beyond the dispute mode. In the last 15 years, have been used five different types and it was observed that the current mode to consecutive points is the most appropriate, because this mode showed the best public average, greater coherence to elect the competition champion and this mode also encouraged the clubs about planning, organization and professional management. This issues contributed to a significant improvement in quality of Championship

Fadiga em compósitos 5HS carbono/epóxi processados via RTM: relação entre cargas axiais no plano e modos de delaminação

Pós-graduação em Engenharia Mecânica - FEG

Desenvolvimento e validação de um novo protocolo para ciclagem térmica de materiais dentários

Pós-graduação em Odontologia Restauradora - ICT