Solid contact PVC membrane electrodes based on neutral or charged carriers for the selective reading of anionic sulfamethoxazole and their application to the analysis of aquaculture water

Sulfamethoxazole (SMX) is among the antibiotics employed in aquaculture for prophylactic and therapeutic reasons. Environmental and food spread may be prevented by controlling its levels in several stages of fish farming. The present work proposes for this purpose new SMX selective electrodes for the potentiometric determination of this sulphonamide in water. The selective membranes were made of polyvinyl chloride (PVC) with tetraphenylporphyrin manganese (III) chloride or cyclodextrin-based acting as ionophores. 2-nitrophenyl octyl ether was employed as plasticizer and tetraoctylammonium, dimethyldioctadecylammonium bromide or potassium tetrakis (4-chlorophenyl) borate was used as anionic or cationic additive. The best analytical performance was reported for ISEs of tetraphenylporphyrin manganese (III) chloride with 50% mol of potassium tetrakis (4-chlorophenyl) borate compared to ionophore. Nersntian behaviour was observed from 4.0 × 10−5 to 1.0 × 10−2 mol/L (10.0 to 2500 µg/mL), and the limit of detection was 1.2 × 10−5 mol/L (3.0 µg/mL). In general, the electrodes displayed steady potentials in the pH range of 6 to 9. Emf equilibrium was reached before 15 s in all concentration levels. The electrodes revealed good discriminating ability in environmental samples. The analytical application to contaminated waters showed recoveries from 96 to 106%.

Sulfadiazine-selective determination in aquaculture environment: Selective potentiometric transduction by neutral or charged ionophores

Solid-contact sensors for the selective screening of sulfadiazine (SDZ) in aquaculture waters are reported. Sensor surfaces were made from PVC membranes doped with tetraphenylporphyrin-manganese(III) chloride, α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin ionophores that were dispersed in plasticizer. Some membranes also presented a positive or a negatively charged additive. Phorphyrin-based sensors relied on a charged carrier mechanism. They exhibited a near-Nernstian response with slopes of 52 mV decade−1 and detection limits of 3.91 × 10−5 mol L−1. The addition of cationic lipophilic compounds to the membrane originated Nernstian behaviours, with slopes ranging 59.7–62.0 mV decade−1 and wider linear ranges. Cyclodextrin-based sensors acted as neutral carriers. In general, sensors with positively charged additives showed an improved potentiometric performance when compared to those without additive. Some SDZ selective membranes displayed higher slopes and extended linear concentration ranges with an increasing amount of additive (always <100% ionophore). The sensors were independent from the pH of test solutions within 2–7. The sensors displayed fast response, always <15 s. In general, a good discriminating ability was found in real sample environment. The sensors were successfully applied to the fast screening of SDZ in real waters samples from aquaculture fish farms. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in locus measurements of sulfadiazine or parent-drugs.

Representations of gender in the writings of St. Francis Xavier: an interdisciplinary approach

Francis Xavier’s Letters and Writings are eloquent narratives of a journey that absorbed the Saint’s entire life. His experiences and idiosyncrasies, values and categorizations are presented in a clear literate discourse. The missionary is rarely neutral in his opinions as he sustains his unmistakable and omnipresent objective: the conversion of peoples and the expansion of the Society of Jesus. Parallel with this objective, the reader is introduced to the individuals that Xavier meets or that he summons in his epistolary discourse. Letters and Writings presents us with a structured narrative peopled by all those who are subject to and objects of Xavier’s apostolic mission, by helpful and unhelpful persons of influence, and by leading and secondary actors. What is then the position of women, in the collective sense as well as in the individual sense, in the travels and goals that are the centre of Xavier’s Letters and Writings? What is the role of women, that secondary and suppressed term in the man/woman binomial, a dichotomy similar to the civilized/savage and European/native binomials that punctuate Xavier’s narratives and the historic context of his letters? Women are not absent from his writings, but it would be naïve to argue in favour of the author’s misogyny as much as of his “profound knowledge of the female heart”, to quote from Paulo Durão in "Women in the Letters of Saint Francis Xavier" (1952), the only paper on this subject published so far. We denote four great categories of women in the Letters and Writings: European Women, Converted Women, Women Who Profess another Religion, and Women as the Agents and Objects of Sin, the latter of which traverses the other three categories. They all depend on the context, circumstances and judgements of value that the author chooses to highlight and articulate.

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose: The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated. Methods: The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH 2 and 8. Results: The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid–base properties, point of zero charge—pHpzc). The solution pH influences both the sorbent’s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH 2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH 2 experimental data to which the Freundlich model fitted better. Conclusion: Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.

Natural organic matter fractionation along the treatment of water for human consumption

The main objective of this study was to characterize the organic matter present in raw water and along the treatment process, as well as its seasonal variation. A natural organic matter fractionation approach has been applied to Lever water treatment plant located in Douro River, in Oporto (Portugal). The process used was based on the sorption of dissolved organic matter in different types of ion exchange resins, DAX-8, DAX-4 and IRA-958, allowing its separation into four fractions: very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), charged hydrophilic (CHA) and hydrophilic neutral (NEU). The dissolved organic carbon (DOC) determination was used to quantify dissolved organic matter. Samples were collected monthly, during approximately one year, from raw water captured at the surface and under the bed of the river, and after each step of the treatment: pre-filtration in sand/anthracite filters, ozonation, coagulation/flocculation, counter current dissolved air flotation and filtration (CoCoDAFF) and chlorination. The NEU fraction showed a seasonal variation, with maximum values in autumn for the sampling points corresponding to raw water captured at the surface and under the bed of the river. It was usually the predominating fraction and did not show a significant decrease throughout the treatment. Nevertheless their low concentration, the same occurred for the CHA and VHA fractions. There was an overall decrease in the SHA fraction throughout the water treatment (especially after CoCoDAFF and ozonation) as well as in the DOC. The TSUVA254 values obtained for raw water generally varied between 2.0 and 4.0 L mgC-1 m-1 and between 0.75 and 1.78 L mgC-1 m-1 for treated water. It was observed a decrease of TSUVA values along the treatment, especially after ozonation. These results may contribute to a further optimization in the process of treating water for human consumption.

Caracterização da matéria orgânica natural em águas para consumo humano

O tratamento de água para consumo humano tem por objectivos não só a sua qualidade em termos de parâmetros químicos e físicos, como também microbiológicos. Considerando que a MON pode afectar os sistemas de tratamento, a sua redução minimiza a formação de subprodutos de desinfecção, como por exemplo os trihalometanos e diminui o crescimento de microrganismos ao longo do sistema de distribuição. Nesse sentido tem havido recentemente uma grande evolução na investigação relativamente à remoção de matéria orgânica natural. O principal objectivo deste trabalho foi o de caracterizar a matéria orgânica presente na água bruta e ao longo do processo de tratamento, assim como a sua evolução sazonal. Os dados obtidos a partir desta caracterização poderão contribuir para uma futura optimização no processo de tratamento de águas de consumo. O processo utilizado baseou-se na sorção da matéria orgânica dissolvida em diferentes tipos de resinas de permuta iónica, DAX-8, DAX-4 e IRA-958, permitindo a sua separação em várias fracções: ácidos muito hidrofóbicos (VHA), ácidos ligeiramente hidrofóbicos (SHA), compostos hidrofílicos carregados (CHA) e hidrofílicos neutros (NEU). De acordo com os resultados obtidos apenas a fracção NEU demonstrou ter uma tendência sazonal, apresentando valores máximos no Verão, nos pontos de amostragem referentes à água bruta superficial (PA802) e água bruta superficial após pré-tratamento por filtração (PA800). Os valores de COD não mostraram uma variação sazonal para as amostras de água bruta superficial que rondaram os 2 mg C/L ao longo do período de amostragem (Julho a Outubro), durante o qual se verificou uma baixa pluviosidade e temperaturas médias muito semelhantes. Os compostos NEU predominam em todos os pontos de amostragem não apresentando uma tendência definida ao longo do tratamento. Observou-se uma diminuição das fracções SHA e CHA ao longo do tratamento. Não se pode indicar uma tendência definida relativamente à fracção VHA. Verifica-se globalmente uma diminuição do teor de MON ao longo do tratamento. Este trabalho demonstrou que na água bruta superficial existe uma predominância dos compostos NEU, seguidos dos SHA, dos VHA e finalmente dos compostos CHA. Na água bruta captada no sub-leito do rio, verifica-se apenas a existência dos compostos NEU, sendo as restantes fracções praticamente nulas. Os valores mais elevados de TSUVA254nm foram obtidos para as amostras que não sofreram qualquer tratamento, água bruta do sub-leito (PA903) e superficial (PA802), e água bruta após pré-filtração (PA800). Nos restantes pontos de amostragem, apesar de se verificarem valores inferiores, não se observa uma diminuição deste parâmetro ao longo do tratamento, nem uma variação sazonal. Os valores de TSUVA254nm obtidos são geralmente inferiores a 3 L.mgC-1.m-1, correspondendo a materiais não húmicos, que são considerados biodegradáveis. Para as amostras de água tratada os valores oscilam entre os 1,23 e 1,58 L.mgC-1.m-1, valores inferiores a 2 L.mgC-1.m-1, o que é considerado um valor de referência ao nível do tratamento, segundo a USEPA.

Estudo de tecnologias domóticas e a sua aplicação em projectos

Actualmente a área da domótica (automação de casas e edifícios) encontra-se em franca expansão, com principal relevância nos países mais desenvolvidos, com um crescimento de mercado de mais de 10% ao ano. Existem inúmeras razoes para a crescente implantação da domótica em edifícios, entre as quais a maior eficiência energética, o aumento da segurança e a redução do custo de aquisição das tecnologias. No que diz respeito as habitações particulares, acrescenta-se essencialmente o aumento do conforto devido ao grau de automação trazido pela domótica. Apesar da domótica não ser uma área cientifico-tecnológica recente, a rápida evolução das tecnologias associadas, nomeadamente a nível das redes de comunicação com e sem fios, foi uma das razoes fundamentais para a elaboração desta Tese. Acresce o facto de o candidato estar actualmente envolvido profissionalmente na área, pelo qual esta Tese assume uma particular importância. Realizou-se um estudo comparativo das tecnologias de domótica mais relevantes, escolhidas quer pelas suas características técnicas quer pela sua implantação de mercado e potencial futuro - KNX/EIB, LonWorks, HomePlug, ZigBee e Z-Wave. Destas, comprovou-se que as duas primeiras são aquelas que, actualmente, tem maior adequabilidade para serem aplicadas em projectos de domótica. Foi por isso efectuado um estudo mais elaborado das tecnologias LonWorks e KNX/EIB, incluindo a forma pratica de instalação/programação, a elaboração de dois demonstradores e de dois projectos (de acordo com um caderno de encargos real), usando as duas tecnologias. Concluiu-se que a tecnologia LonWorks apresenta vantagens no que respeita a escalabilidade (dimensão) dos sistemas. Em termos futuros, prevê-se a necessidade da interoperabilidade entre os nos/redes cablados (tradicionais) com nos/redes sem fio, seguindo a tendência para os ambientes inteligentes (“ambient intelligence/assisted living”, “smart spaces”, “ubiquitous computing).

Regimes de neutro em média tensão em subestações de distribuição de energia elétrica

A existência do regime de neutro em subestações de distribuição de energia elétrica é essencial para o bom funcionamento de toda a rede. Existe um vasto leque de opções no que diz respeito aos regimes de neutro. Cada opção tem as suas vantagens e desvantagens, e cabe às empresas do setor elétrico a escolha do regime de neutro mais adequado em função das caraterísticas da rede. A escolha do regime de neutro tem influência direta no desempenho global de toda a rede de média tensão. O principal objetivo desta dissertação é o estudo e a análise das vantagens e inconvenientes dos vários regimes de neutro: neutro isolado, neutro impedante, ligado diretamente à terra, neutro ressonante, analisando as suas vantagens e inconvenientes. É feito um estudo aprofundado do regime de neutro ressonante, também designado por regime de neutro com a Bobine de Petersen. Este trabalho descreve, ainda, de forma sucinta a situação de Portugal relativamente aos regimes de neutro que utiliza e a sua perspetiva futura. Por fim é apresentado um caso de estudo, que diz respeito a uma rede de média tensão (30 kV) alimentada pela subestação de Serpa. Foram estudados os regimes de neutro como a bobine de Petersen, reatância de neutro e neutro isolado. Foi também estudada a influência na ocorrência de um defeito fase-terra e a influência na ocorrência de defeitos francos e resistivos em vários pontos da rede.

Effects of emotional valence and three-dimensionality of visual stimuli on brain activation: an fMRI study

BACKGROUND: Examining changes in brain activation linked with emotion-inducing stimuli is essential to the study of emotions. Due to the ecological potential of techniques such as virtual reality (VR), inspection of whether brain activation in response to emotional stimuli can be modulated by the three-dimensional (3D) properties of the images is important. OBJECTIVE: The current study sought to test whether the activation of brain areas involved in the emotional processing of scenarios of different valences can be modulated by 3D. Therefore, the focus was made on the interaction effect between emotion-inducing stimuli of different emotional valences (pleasant, unpleasant and neutral valences) and visualization types (2D, 3D). However, main effects were also analyzed.METHODS: The effect of emotional valence and visualization types and their interaction were analyzed through a 3x2 repeated measures ANOVA. Post-hoc t-tests were performed under a ROI-analysis approach. RESULTS: The results show increased brain activation for the 3D affective-inducing stimuli in comparison with the same stimuli in 2D scenarios, mostly in cortical and subcortical regions that are related to emotional processing, in addition to visual processing regions. CONCLUSIONS: This study has the potential of clarify brain mechanisms involved in the processing of emotional stimuli (scenarios’ valence) and their interaction with three-dimensionality.

Adhesively-bonded repair proposal for wood members damaged by horizontal shear using carbon-epoxy patches

In this work, a repair technique with adhesively bonded carbon-epoxy patches is proposed for wood members damaged by horizontal shear and under bending loads. This damage is characterized by horizontal crack growth near the neutral plane of the wood beam, normally originating from checks and shakes. The repair consists of adhesively bonded carbon-epoxy patches on the vertical side faces of the beam at the cracked region to block sliding between the beam arms. An experimental and numerical parametric analysis was performed on the patch length. The numerical analysis used the finite element method (FEM) and cohesive zone models (CZMs), with an inverse modelling technique for the characterization of the adhesive layer. Trapezoidal cohesive laws in each pure mode were used to account for the ductility of the adhesive used. To fully reproduce the tests, horizontal damage propagation within the wood beam was also simulated. A good correlation with the experiments was found. Regarding the effectiveness of the repair, for the conditions selected for this work, a full strength recovery was achieved for the bigger value of patch length tested.