A systematic procedure to enhance reproducibility of SWASV cycles in the determination of toxic metals in real samples

This work presents for the first time a systematic study on the optimization of the electrochemical cleaning time of a mercury film when it is used as a working electrode material in the analysis of toxic metals, such as Pb2+, used as model metal, in real samples by SWASV. The optimization study for the film’s cleaning time aimed at attaining a Pb2+ minimum value in the film after the re-oxidation step of the pre-concentrated metal, given the impossibility of complete removal of traces of the electroactive species from the film. This value was kept constant in each concentration range studied ensuring thus that all assays were performed in initial identical conditions. An assay performed on a synthetic sample was taken as reference. In it, given the absence of matrix effects, and after the electrochemical cleaning step, a direct proportionality was observed between the residual amounts of Pb2+ in the film (which for the cleaning time used was never completely removed) and Pb2+ concentration in the solution. This fact determined a high correlation between Pb2+ peak current and Pb2+ concentration which was not observed when real samples (tree leaves) were analyzed. This behavior may result from the presence of the interfering surfactants always present in real samples of complex matrix. Cleaning time optimization was performed for the following Pb2+ concentration ranges in the real samples of complex matrix: 0.006-0.020, 0.020-0.080, 0.060-0.200 and 0.100-0.600 ppb. As expected, in order to obtain identical levels of film’s cleaning efficiency, the need for longer cleaning times has been observed for higher concentrations. The optimized cleaning times for the concentration ranges under study were 120, 150, 180 e 300 s, respectively.

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.

Influência da longevidade da solução de Verhoeff na intensidade/especificidade das fibras elásticas, em material biológico de origem suína

As fibras elásticas são responsáveis pela elasticidade e flexibilidade dos tecidos. A técnica de Verhoeff é o método mais utilizado para demonstrar a presença destas fibras, corando-as de preto. A solução de Verhoeff é exclusivamente utilizada de um modo extemporâneo, no entanto, pela revisão da literatura verificou-se que a mesma poderia ter uma maior durabilidade. O presente estudo tem como principal objectivo determinar a longevidade da solução de Verhoeff. Utilizou-se material biológico de origem suína,fixado em formol neutro tamponado a 10% e incluído em parafina. Foi avaliado um total de 33 lâminas segundo critérios de intensidade e especificidade. Os resultados obtidos provam que o tempo tem influência sobre a referida solução, levando à perda de intensidade de coloração, não se tendo registado alterações significativas a nível de especificidade. Concluiu-se que a solução de Verhoeff pode não ser uma solução descartável, encontrando-se em perfeitas condições de utilização até às 48h de repouso.

Avaliação da exposição de crianças a material particulado em suspensão

Este trabalho teve como principal objectivo caracterizar a exposição de crianças a partículas atmosféricas e aos elementos químicos que as constituem. Pretendeu-se também determinar as fontes e processos que afectam os níveis e composição das partículas em suspensão no ar ambiente e no interior de salas de aula de escolas do 1º ciclo localizadas no centro de Lisboa. Os efeitos das partículas atmosféricas na saúde humana manifestam-se sobretudo ao nível do aparelho respiratório, dependendo da sua composição química, e principalmente da sua dimensão. As partículas inaláveis (PM10) podem depositar-se nas unidades funcionais do sistema respiratório. O PM2,5 podem atingir os alvéolos pulmonares e penetrar no sistema circulatório. As crianças são um dos principais grupos de risco, visto que os seus órgãos e tecidos ainda estão em desenvolvimento, ficando mais susceptíveis à exposição de partículas. A recolha de material particulado foi realizada no ar ambiente recorrendo a um colector PARTISOL e no interior e exterior das escolas usando amostradores GENT. A concentração total de partículas em suspensão foi determinada por gravimetria. A caracterização química da matéria particulada foi efectuada por Análise por Activação com Neutrões (INAA) para a determinação da concentração dos elementos e por Cromatografia Iónica para a quantificação de iões solúveis em água. Em 2007, a concentração média anual de PM2,5 no Centro de Lisboa foi de 18µg/m3. Através da Análise de Componentes Principais e Regressão Multilinear verificou-se que a massa das partículas da fracção fina resulta essencialmente da produção de aerossóis secundários (35%) de uma fonte de cálcio (28%) e da emissão de poluentes por veículos motorizados (23%). No interior das escolas verificou-se que as concentrações de partículas são mais elevadas comparativamente com o ambiente exterior, principalmente no PM2,5-10 (74µg/m3). A ressuspensão de partículas causada pelas actividades desempenhadas no interior das salas e a suspensão de poeiras do solo transportada pelas crianças, são as principais causas apontadas. O Ca é o elemento maioritário no interior das escolas. Os resultados obtidos neste trabalho não excederam os limites estabelecidos pela Legislação Portuguesa.

New p-i-n Si : H imager configuration for spatial resolution improvement

Amorphous glass/ZnO-Al/p(a-Si:H)/i(a-Si:H)/n(a-Si1-xCx:H)/Al imagers with different n-layer resistivities were produced by plasma enhanced chemical vapour deposition technique (PE-CVD). An image is projected onto the sensing element and leads to spatially confined depletion regions that can be readout by scanning the photodiode with a low-power modulated laser beam. The essence of the scheme is the analog readout, and the absence of semiconductor arrays or electrode potential manipulations to transfer the information coming from the transducer. The influence of the intensity of the optical image projected onto the sensor surface is correlated with the sensor output characteristics (sensitivity, linearity blooming, resolution and signal-to-noise ratio) are analysed for different material compositions (0.5 < x < 1). The results show that the responsivity and the spatial resolution are limited by the conductivity of the doped layers. An enhancement of one order of magnitude in the image intensity signal and on the spatial resolution are achieved at 0.2 mW cm(-2) light flux by decreasing the n-layer conductivity by the same amount. A physical model supported by electrical simulation gives insight into the image-sensing technique used.

Development of a biosensor for urea assay based on amidase inhibition, using an ion-selective electrode

A biosensor for urea has been developed based on the observation that urea is a powerful active-site inhibitor of amidase, which catalyzes the hydrolysis of amides such as acetamide to produce ammonia and the corresponding organic acid. Cell-free extract from Pseudomonas aeruginosa was the source of amidase (acylamide hydrolase, EC 3.5.1.4) which was immobilized on a polyethersulfone membrane in the presence of glutaraldehyde; anion-selective electrode for ammonium ions was used for biosensor development. Analysis of variance was used for optimization of the biosensorresponse and showed that 30 mu L of cell-free extract containing 7.47 mg protein mL(-1), 2 mu L of glutaraldehyde (5%, v/v) and 10 mu L of gelatin (15%, w/v) exhibited the highest response. Optimization of other parameters showed that pH 7.2 and 30 min incubation time were optimum for incubation ofmembranes in urea. The biosensor exhibited a linear response in the range of 4.0-10.0 mu M urea, a detection limit of 2.0 mu M for urea, a response timeof 20 s, a sensitivity of 58.245 % per mu M urea and a storage stability of over 4 months. It was successfully used for quantification of urea in samples such as wine and milk; recovery experiments were carried out which revealed an average substrate recovery of 94.9%. The urea analogs hydroxyurea, methylurea and thiourea inhibited amidase activity by about 90%, 10% and 0%, respectively, compared with urea inhibition.

Imunorreatividade em material histológico arquivado durante um, quatro e sete anos

Quando aplicada no âmbito da Anatomia Patológica, a imuno-histoquímica tem constituído um poderoso meio de identificação/caracterização de várias estruturas histológicas, permitindo delinear prognóstico e terapêutica para várias patologias. Tendo em conta que as amostras histológicas analisadas podem ser conservadas ao longo de vários anos, interessa avaliar a manutenção da antigenicidade ao longo do tempo, de forma a garantir a qualidade final da técnica quando aplicada em material de arquivo. Assim, o principal objetivo deste trabalho foi comparar a imunorreatividade do material histológico arquivado durante um, quatro e sete anos. Foi utilizado material histológico de próstata, pulmão e mama, no qual se procedeu à imunomarcação de citoqueratinas (Clones AE1/AE3), CD34 e proteína p63, por método de multímero/HRP no sistema Ventana BenchMark Ultra®. Foi realizado um ensaio com recuperação antigênica por alta temperatura (RAAT) e outro sem esta etapa. As imunomarcações (n=162) foram classificadas por três avaliadores independentes num escore quantitativo final (escala 0-100). O par média/desvio-padrão do escore final para os casos com sete anos foi de 69,06/19,05, para os casos com quatro anos foi de 66,47/20,73 e para os casos com um ano foi de 69,08/19,35, não se tendo encontrado diferenças estatisticamente significativas. Os casos sem RAAT obtiveram um par média/desvio-padrão de 54,90/17,00, enquanto os casos com RAAT obtiveram 81,50/11,60, o que revelou diferenças estatisticamente significativas (p=0,000). Para os casos em estudo conclui-se que o fator “tempo de arquivo” não está associado a alterações da imunorreatividade. A importância da RAAT na obtenção de imunomarcação de qualidade sai fortemente realçada. ABSTRACT - When applied within the framework of Pathology, immunohistochemistry has been a powerful means of identification/characterization of various histological structures, allowing to outline prognosis and therapy for various diseases. Given that the analyzed histological samples can be preserved for several years, it is interesting to assess the retention of antigenicity over time in order to ensure the quality of the final technique, when applied to stored material. Thus, the main objective of this study was to compare the immunoreactivity of the histological material archived for one, four and seven years. It was used histological material from prostate, lung and breast, in which it was performed the immunostaining of cytokeratins (clones AE1/AE3), CD34 and p63 protein by the method of multimer/HRP system on a Ventana BenchMark Ultra®. It was conducted a test with heat induced epitope retrieval (HIER) and another one without this step. The stained slides (n=162) were classified by three independent assessors using a quantitative score (scale 0-100). The pair mean/standard deviation of the score for cases with seven years was 69,06/19,05, for cases with four years was 66,47/20,73 and for cases with one year was 69,08/19,35, which did not revealed any statistically significant differences. The cases without HIER had a couple mean/standard deviation of 54.90/17.00 while the cases with HIER obtained 81.50/11.60, which revealed statistically significant differences (p=0.000). For this case study it was concluded that the factor archive period is not associated with changes in immunoreactivity. The importance of HIER in obtaining high quality immunostaining comes out strongly highlighted.

Multilayer Architectures Based on a-SiC:H Material: Tunable Wavelength Filters in Optical Processing Devices

The characteristics of tunable wavelength filters based on a-SiC:H multilayered stacked pin cells are studied both theoretically and experimentally. The optical transducers were produced by PECVD and tested for a proper fine tuning of the cyan and yellow fluorescent proteins emission. The active device consists of a p-i'(a-SiC:H)-n/p-i(a-Si:H)-n heterostructures sandwiched between two transparent contacts. Experimental data on spectral response analysis, current-voltage characteristics and color and transmission rate discrimination are reported. Cyan and yellow fluorescent input channels were transmitted together, each one with a specific transmission rate and different intensities. The multiplexed optical signal was analyzed by reading out, under positive and negative applied voltages, the generated photocurrents. Results show that the optimized optical transducer has the capability of combining the transient fluorescent signals onto a single output signal without losing any specificity (color and intensity). It acts as a voltage controlled optical filter: when the applied voltages are chosen appropriately the transducer can select separately the cyan and yellow channel emissions (wavelength and frequency) and also to quantify their relative intensities. A theoretical analysis supported by a numerical simulation is presented.

Juntas mecânicas em material compósito

O âmbito da presente tese é o estudo de juntas mecânicas em material compósito realizado com fibra de vidro. Os materiais compósitos são a solução procurada pela generalidade dos sectores da indústria, devido essencialmente à sua grande capacidade estrutural e à sua resistência mecânica específica, ou seja, a resistência mecânica versus peso ser em geral maior que nas ligações metálicas. O estudo efectuado neste trabalho é referente à delaminação presente na furação de materiais compósitos, sendo esta um dos problemas de maior gravidade, existente quando se realiza a furação do material. Este problema influência a integridade estrutural do material bem como a sua fiabilidade a longo prazo. Foram usados dois métodos de furação, o primeiro conhecido por furação convencional e o segundo habitualmente designado método KTH ou por furação orbital. Foi feita uma comparação entre estes dois métodos e verificado qual deles apresenta menor delaminação em torno do furo e melhor qualidade de furo. Conclui-se que a furação orbital apresenta uma delaminação inferior relativamente à furação convencional, e que esta é preferível para a realização de furação em material compósito.

Electrodeposition and characterization of nickel–copper metallic foams for application as electrodes for supercapacitors

Nickel-copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm(-2)) the nickel-copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel-copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge-discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni-Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge-discharge data and the best value (105 F g(-1) at 1 mA cm(-2)) was obtained for nickel-copper foams deposited at 1.8 A cm(-2) for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm(-2).

Aço em varão para betão armado: caracterização do material e enquadramento atual

Dissertação para obtenção do grau de Mestre em Engenharia Civil

Unstabilized rammed Earth: characterization of material collected from old constructions in South Portugal and comparison to normative requirements

Unstabilized rammed earth is a recyclable, economical, and eco-friendly building material, used in the past and still applied today. Traditionally, its use was based on a long empirical knowledge of the local materials. Because this knowledge was mostly lost or is no longer sufficient, in many countries normative documents have been produced to allow the assessment of rammed earth soils. With the aim of contributing for a refining of these normative requirements, this article presents a research work that included: (i) collection of Unstabilized rammed earth samples from six constructions in Portugal; (ii) a literature survey of normative and complementary documents to identify the most mentioned key-properties, the test procedures and the corresponding threshold limits; and (iii) a discussion of the test procedures and of the thresholds limits in the light of the experimental results. The analyzed properties are the particle size distribution, maximum particle size, plasticity, compaction, linear shrinkage, organic content, and salt content. The work highlights the advantages of taking into account the characteristics of existing constructions as a basis for the establishment and further refining of consistent threshold values. In particular, it shows that it is essential to adjust the requirements to the specificities of local materials.

Electrodeposition and characterization of nikel-copper metallic foams for application as electrodes for supercapacitors

Nickel-copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm(-2)) the nickel-copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel-copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge-discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni-Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge-discharge data and the best value (105 F g(-1) at 1 mA cm(-2)) was obtained for nickel-copper foams deposited at 1.8 A cm(-2) for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm(-2).

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This article reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160 degrees C and 24 h. A band gap of 3.06 +/- 0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 min of irradiation of a 10 ppm dye aqueous solution and 1 g L-1 of TNS catalyst.

Via algaliada versus mudança de bitola dos eixos do material circulante

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil