Avaliação da caracterização de lesões em mamografia com recurso a sistemas CAD (Computer-Aided Diagnosis)

Os sistemas Computer-Aided Diagnosis (CAD) auxiliam a deteção e diferenciação de lesões benignas e malignas, aumentando a performance no diagnóstico do cancro da mama. As lesões da mama estão fortemente correlacionadas com a forma do contorno: lesões benignas apresentam contornos regulares, enquanto as lesões malignas tendem a apresentar contornos irregulares. Desta forma, a utilização de medidas quantitativas, como a dimensão fractal (DF), pode ajudar na caracterização dos contornos regulares ou irregulares de uma lesão. O principal objetivo deste estudo é verificar se a utilização concomitante de 2 (ou mais) medidas de DF – uma tradicionalmente utilizada, a qual foi designada por “DF de contorno”; outra proposta por nós, designada por “DF de área” – e ainda 3 medidas obtidas a partir destas, por operações de dilatação/erosão e por normalização de uma das medidas anteriores, melhoram a capacidade de caracterização de acordo com a escala BIRADS (Breast Imaging Reporting and Data System) e o tipo de lesão. As medidas de DF (DF contorno e DF área) foram calculadas através da aplicação do método box-counting, diretamente em imagens de lesões segmentadas e após a aplicação de um algoritmo de dilatação/erosão. A última medida baseia-se na diferença normalizada entre as duas medidas DF de área antes e após a aplicação do algoritmo de dilatação/erosão. Os resultados demonstram que a medida DF de contorno é uma ferramenta útil na diferenciação de lesões, de acordo com a escala BIRADS e o tipo de lesão; no entanto, em algumas situações, ocorrem alguns erros. O uso combinado desta medida com as quatro medidas propostas pode melhorar a classificação das lesões.

Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method

QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5–110.0% with variation coefficients not exceeding 8%. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12– 1.90 ng/g wet weight (0.30–4.70 µg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 l 1.20 ng/g in horse mackerel to 14.6 ± 2.8 ng/ g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups.

Localização de páginas web do conceito ao processo

Conceitos como Globalização, Internacionalização, Localização e Tradução surgem, na realidade da indústria da língua, com uma grande interligação, mas com perspectivas nem sempre concordantes. O nosso trabalho analisa, por isso, as diferentes definições propostas dedicando especial atenção ao conceito de localização, uma vez que o nosso projecto analisa o processo de localização de uma página Web desenvolvido num contexto empresarial real. O nosso enfoque recai mais específicamente sobre a localização de páginas Web, objecto do nosso projecto, identificando não só as suas particularidades, como também os intervenientes e o tipo de competências necessárias para o desenvolvimento de um trabalho nesta área da tradução e as ferramentas disponíveis para o profissional da tradução/ localização, de que se destacam as freeware. O processo de localização impõe metas de qualidade exigentes, pelo que, partindo da definição do conceito de qualidade, analisamos o tipo de requisitos necessários a uma correcta definição de tarefas e objectivos no contexto da localização. Esta definição de conceitos e a análise do processo de localização suportaram, em seguida, o desenvolvimento do objecto do nosso projecto - o processo de localização da página Web da empresa Pinto & Cruz, ao mesmo tempo que permitiram uma prévia identificação de todos os passos a desenvolver e do tipo de dificuldades e problemas a enfrentar. Assim, e em função das condicionantes impostas pelo modelo de gestão da página, definimos um fluxo de trabalho, em que identificamos as diferentes fases e intervenientes, mediante a utilização de uma plataforma de trabalho disponibilizada pelo webmaster do sítio em questão. O processo seguido para a localização da página é descrito, as suas especificidades documentadas e as dúvidas e dificuldades identificadas. Pretendeu-se, com o desenvolvimento deste projecto e com a descrição feita sistematizar uma abordagem ao processo e alertar para o tipo de dificuldades inerentes à sua prossecução, sobretudo para quem se dispõem a fazê-lo pela primeira vez.

A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of -0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. -0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0x10-6 to 9.0x10-6 mol L-1; this corresponded to a detection limit of 3.5x10-8 mol L-1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.

A New Method to Determine the Density and Water Absorption of Fine Recycled Aggregates

The construction industry keeps on demanding huge quantities of natural resources, mainly minerals for mortars and concrete production. The depletion of many quarries and environmental concerns about reducing the dumping of construction and demolition waste in quarries have led to an increase in the procuring and use of recycled aggregates from this type of waste. If they are to be incorporated in concrete and mortars it is essential to know their properties to guarantee the adequate performance of the end products, in both mechanical and durability-related terms. Existing regulated tests were developed for natural aggregates, however, and several problems arise when they are applied to recycled aggregates, especially fine recycled aggregates (FRA). This paper describes the main problems encountered with these tests and proposes an alternative method to determine the density and water absorption of FRA that removes them. The use of sodium hexametaphosphate solutions in the water absorption test has proven to improve its efficiency, minimizing cohesion between particles and helping to release entrained air.

Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction–headspace solid phase microextraction and gas chromatography–tandem mass spectrometry

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Regulação médica em emergência pela plataforma web: um estudo piloto

OBJETIVO: Descrever um sistema gestor de regulação médica em emergência baseado na rede mundial de computadores. MÉTODOS: O Sistema de Regulação de Urgências e Emergências foi desenvolvido segundo modelo evolutivo de software de prototipação. A comunicação entre os usuários e o sistema foi implementada utilizando tecnologias web; o sistema foi desenvolvido em personal home page (PHP) e o banco de dados, em MySQL. O protótipo foi baseado no processo de regulação médica da Divisão Regional de Saúde XIII do Estado de São Paulo e aplicado a 26 municípios dessa regional durante quatro semanas consecutivas em setembro de 2009. O sistema possibilitou a documentação das solicitações em ordem cronológica, sem permitir edição de dados já inseridos e garantindo o acesso hierarquizado e sigiloso às informações para cada participante do sistema. RESULTADOS: O sistema apresentou 100% de disponibilidade, confiabilidade e integridade da informação. Foram realizadas 1.046 solicitações ao sistema, das quais 703 (68%) foram completadas. Os solicitantes apresentaram 98% de adesão ao sistema na primeira semana de aplicação, e a adesão dos prestadores de serviço foi gradativa (37% na quarta semana). Os municípios mais próximos de Ribeirão Preto que não possuem prestadores de alta complexidade foram os que mais utilizaram o sistema. CONCLUSÕES: A regulação médica de solicitações de emergência pela rede mundial de computadores mostrou-se exeqüível e confiável, possibilitando a transparência do processo e acesso direto às informações por parte dos gestores. Possibilitou a construção de indicadores para monitorizar e aprimorar o processo, na perspectiva da criação de uma regulação semi-automatizada e de avanços na organização do sistema.

Multiresidue method for the determination of organophosphorus pesticides in still wine and fortified wine using solid-phase microextraction and gas chromatography – Tandem mass spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.

Control and comparison of the antioxidant capacity of beers

The purpose of the present work is to determine the antioxidant capacity (AC) of 27 commercial beers. The AC indicates the degree of protection of a certain organism against oxidative damage provoked by reactive oxygen and nitrogen species. Assays were carried out by the following methods: (i) total radical trapping antioxidant parameter (TRAP); (ii) trolox equivalent antioxidant capacity (TEAC); (iii) trolox equivalent antioxidant capacity (DPPH); (iv) ferric-ion reducing antioxidant parameter (FRAP); (v) cupric reducing antioxidant capacity (CUPRAC); (vi) oxygen radical absorbance capacity (ORAC). Ascorbic acid (AA), gallic acid (GA) and trolox (TR) were used as standards. All beers showed antioxidant power, but a wide range of ACs was observed. The effect of several factors upon these differences was studied. Statistical differences were found between ACs of beers of different colours. ORAC method provided always higher experimental ACs, of significant statistical differences to other assays.

Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Espetroscopia (1H) por ressonância magnética do disco intervertebral lombar no adulto e sua aplicação na rotina imagiológica

Objetivos – Demonstrar o potencial da espetroscopia (1H) por ressonância magnética na doença degenerativa discal lombar e defender a integração desta técnica na rotina clínico‑imagiológica para a precisa classificação da involução vs degenerescência dos discos L4‑L5 e L5‑S1 em doentes com lombalgia não relacionável com causa mecânica. Material e métodos – O estudo incluiu 102 discos intervertebrais lombares de 123 doentes. Foram estudados 61 discos de L4‑L5, 41 discos de L5‑S1 e 34 discos de D12‑L1. Utilizou‑se um sistema de ressonância magnética de 1,5 T e técnica monovoxel. Obtiveram‑se os rácios [Lac/Nacetyl] e [Nacetyl/(Lac+Lípidos)] e aplicou‑se a ressonância de lípidos para avaliar a bioquímica do disco com o fim de conhecer o estado de involução vs degenerescência que o suscetibilizam para a instabilidade e sobrecarga. Avaliou‑se o comportamento dos rácios e do teor lipídico dos discos L4‑L5‑S1 e as diferenças apresentadas em relação a D12‑L1. Foi também realizada a comparação entre os discos L4‑L5, L5‑S1 e D12‑L1 na ponderação T2 (T2W), segundo a classificação ajustada (1‑4) de Pfirrmann. Resultados – Verificou‑se que os rácios e o valor dos lípidos dos discos L4‑L5‑S1 apresentaram diferenças estatisticamente significativas quando relacionados com os discos D12‑L1. O rácio [Lac/Nacetyl] em L4‑L5‑S1 mostrou‑se aumentado em relação a D12‑L1 (p=0,033 para os discos com grau de involução [1+2] e p=0,004 para os discos com grau [3+4]). Estes resultados sugerem que a involução vs degenerescência dos discos nos graus mais elevados condiciona um decréscimo do pico do Lactato. O rácio [Nacetyl/(Lac+Lip)] discrimina os graus de involução [1+2] do [3+4] no nível L4‑L5, apresentando os valores dos rácios (média 0,65 e 0,5 respetivamente com p=0,04). O rácio médio de [Nacetyl/(Lac+Lip)] dos discos L4‑L5 foi 1,8 vezes mais elevado do que em D12‑L1. O espetro lipídico em L4‑L5‑S1 nos graus mais elevados não mostrou ter uma prevalência constante quanto às frequências de ressonância. Conclusão – A espetroscopia (1H) dos discos intervertebrais poderá ter aplicação na discriminação dos graus de involução vs degenerescência e representar um contributo semiológico importante em suplemento à ponderação T2 convencional. As ressonâncias de lípidos dos discos L4‑L5 e L5‑S1, involuídos ou degenerados, devem ser avaliadas em relação a D12‑L1, utilizando este valor como referência, pois este último é o nível considerado estável e com baixa probabilidade de degenerescência.

Effects of sulphurization time on Cu2ZnSnS4 absorbers and thin films solar cells obtained from metallic precursors

We report the results of a study of the sulphurization time effects on Cu2ZnSnS4 absorbers and thin film solar cells prepared from dc-sputtered tackedmetallic precursors. Three different time intervals, 10 min, 30min and 60 min, at maximum sulphurization temperature were considered. The effects of this parameter' change were studied both on the absorber layer properties and on the final solar cell performance. The composition, structure, morphology and thicknesses of the CZTS layers were analyzed. The electrical characterization of the absorber layer was carried out by measuring the transversal electrical resistance of the samples as a function of temperature. This study shows an increase of the conductivity activation energy from 10 meV to 54meV for increasing sulphurization time from 10min to 60min. The solar cells were built with the following structure: SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni:Al grid. Several ac response equivalent circuit models were tested to fit impedance measurements. The best results were used to extract the device series and shunt resistances and capacitances. Absorber layer's electronic properties were also determined using the Mott–Schottky method. The results show a decrease of the average acceptor doping density and built-in voltage, from 2.0 1017 cm−3 to 6.5 1015 cm−3 and from 0.71 V to 0.51 V, respectively, with increasing sulphurization time. These results also show an increase of the depletion region width from approximately 90 nm–250 nm.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.