Rheo-optical characterization of liquid crystalline acetoxypropylcellulose melt undergoing large shear flow and relaxation after flow cessation

The rheological and structural characteristics of acetoxypropylcellulose (APC) nematic melt are studied at shear rates ranging from 10 s(-1) to 1000 s(-1) which are relevant to extrusion based processes. APC shows a monotonic shear thinning behavior over the range of shear rates tested. The negative extrudate-swell shows a minimum when a critical shear rate (gamma) over dot(c) is reached. For shear rates smaller than (gamma) over dot(c), the flow-induced texture consists of two set of bands aligned parallel and normal to the flow direction. At shear rates larger than (gamma) over dot(c), the flow induced texture is reminiscent of a 2 fluids structure. Close to the shearing walls, domains elongated along the flow direction and stacked along the vorticity are imaged with POM, whereas SALS patterns indicate that the bulk of the sheared APC is made of elliptical domains oriented along the vorticity. No full nematic alignment is achieved at the largest shear rate tested. Below (gamma) over dot(c), the stress relaxation is described by a stretched exponential. Above (gamma) over dot(c), the stress relaxation is described by a fast and a slow process. The latter coincides with the growth of normal bands thicknesses, as the APC texture after flow cessation consists of two types of bands with parallel and normal orientations relative to the flow direction. Both bands thicknesses do not depend on the applied shear rate, in contrast to their orientation. (C) 2015 Elsevier Ltd. All rights reserved.

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Fluorescence Microscopy Imaging Denoising with Log-Euclidean Priors and Photobleaching Compensation

Fluorescent protein microscopy imaging is nowadays one of the most important tools in biomedical research. However, the resulting images present a low signal to noise ratio and a time intensity decay due to the photobleaching effect. This phenomenon is a consequence of the decreasing on the radiation emission efficiency of the tagging protein. This occurs because the fluorophore permanently loses its ability to fluoresce, due to photochemical reactions induced by the incident light. The Poisson multiplicative noise that corrupts these images, in addition with its quality degradation due to photobleaching, make long time biological observation processes very difficult. In this paper a denoising algorithm for Poisson data, where the photobleaching effect is explicitly taken into account, is described. The algorithm is designed in a Bayesian framework where the data fidelity term models the Poisson noise generation process as well as the exponential intensity decay caused by the photobleaching. The prior term is conceived with Gibbs priors and log-Euclidean potential functions, suitable to cope with the positivity constrained nature of the parameters to be estimated. Monte Carlo tests with synthetic data are presented to characterize the performance of the algorithm. One example with real data is included to illustrate its application.

From unthinned continent to ocean: The deep structure of the West Iberia passive continental margin at 38 degrees N

The crustal and lithospheric mantle structure at the south segment of the west Iberian margin was investigated along a 370 km long seismic transect. The transect goes from unthinned continental crust onshore to oceanic crust, crossing the ocean-continent transition (OCT) zone. The wide-angle data set includes recordings from 6 OBSs and 2 inland seismic stations. Kinematic and dynamic modeling provided a 2D velocity model that proved to be consistent with the modeled free-air anomaly data. The interpretation of coincident multi-channel near-vertical and wide-angle reflection data sets allowed the identification of four main crustal domains: (i) continental (east of 9.4 degrees W); (ii) continental thinning (9.4 degrees W-9.7 degrees W): (iii) transitional (9.7 degrees W-similar to 10.5 degrees W); and (iv) oceanic (west of similar to 10.5 degrees W). In the continental domain the complete crustal section of slightly thinned continental crust is present. The upper (UCC, 5.1-6.0 km/s) and the lower continental crust (LCC, 6.9-7.2 km/s) are seismically reflective and have intermediate to low P-wave velocity gradients. The middle continental crust (MCC, 6.35-6.45 km/s) is generally unreflective with low velocity gradient. The main thinning of the continental crust occurs in the thinning domain by attenuation of the UCC and the LCC. Major thinning of the MCC starts to the west of the LCC pinchout point, where it rests directly upon the mantle. In the thinning domain the Moho slope is at least 13 degrees and the continental crust thickness decreases seaward from 22 to 11 km over a similar to 35 km distance, stretched by a factor of 1.5 to 3. In the oceanic domain a two-layer high-gradient igneous crust (5.3-6.0 km/s; 6.5-7.4 km/s) was modeled. The intra-crustal interface correlates with prominent mid-basement, 10-15 km long reflections in the multi-channel seismic profile. Strong secondary reflected PmP phases require a first order discontinuity at the Moho. The sedimentary cover can be as thick as 5 km and the igneous crustal thickness varies from 4 to 11 km in the west, where the profile reaches the Madeira-Tore Rise. In the transitional domain the crust has a complex structure that varies both horizontally and vertically. Beneath the continental slope it includes exhumed continental crust (6.15-6.45 km/s). Strong diffractions were modeled to originate at the lower interface of this layer. The western segment of this transitional domain is highly reflective at all levels, probably due to dykes and sills, according to the high apparent susceptibility and density modeled at this location. Sub-Moho mantle velocity is found to be 8.0 km/s, but velocities smaller than 8.0 km/s confined to short segments are not excluded by the data. Strong P-wave wide-angle reflections are modeled to originate at depth of 20 km within the lithospheric mantle, under the eastern segment of the oceanic domain, or even deeper at the transitional domain, suggesting a layered structure for the lithospheric mantle. Both interface depths and velocities of the continental section are in good agreement to the conjugate Newfoundland margin. A similar to 40 km wide OCT having a geophysical signature distinct from the OCT to the north favors a two pulse continental breakup.

Quantificação da difusão na ressonância magnética da mama: ADC e Kurtosis

Mestrado em Radiações Aplicadas às Tecnologias da Saúde. Área de especialização: Ressonância Magnética

Quantificação por imagem ponderada em difusão (DWI) das lesões tumorais da mama

Introdução – A técnica de Difusão por Ressonância Magnética (RM), ao avaliar o movimento das moléculas de água nos tecidos, permite inferir sobre a arquitetura dos mesmos, em particular relativamente à celularidade, volume celular e permeabilidade das membranas. O Coeficiente de Difusão Aparente (ADC) é um parâmetro quantificável da imagem ponderada em difusão (DWI). A sua análise poderá fornecer informação clínica adicional sobre estas lesões, sobretudo em relação à sua caracterização histológica. Objetivos – Caracterizar e diferenciar tipos e alguns subtipos de lesões mamárias através da análise do ADC. Metodologia – 20 Mulheres com 23 lesões mamárias foram submetidas a RM mamária: 3 lesões benignas (3 Fibroadenomas-FA) e 20 malignas (16 Carcinomas Ductais Invasivos-CDI, 2 Carcinomas Ductais In Situ-CDIS e 2 Carcinomas Invasivos Lobulares-CLI). Num equipamento 1.5T aplicou-se uma sequência de Difusão (b=0,50,250,500,750,1000 s/mm2). Obteve-se o ADC através do ajuste exponencial da intensidade de sinal das lesões em função do valor de b, fazendo-se corresponder os valores de ADC à respetiva caracterização histológica e posterior comparação com a literatura. Resultados e Discussão – As lesões malignas apresentaram ADCs significativamente (p=0,014) inferiores [(0,94±0,22)x10-3 mm2/s] aos das benignas [(1,43±0,25)x10-3 mm2/s]. A justificação pode residir no aumento da celularidade e consequente restrição da Difusão que se observa nas lesões malignas. Os CDI apresentaram ADCs baixos [(0,88±0,17)x10-3 mm2/s], enquanto que os CDIS apresentaram ADCs mais elevados [(1,33±0,29)x10-3 mm2/s]. Estes resultados estão de acordo com o facto dos CDIS estarem limitados aos ductos mamários, mantendo-se menos alterada a estrutura do tecido adjacente e resultando numa menor restrição à difusão que nos CDI. Verificaram-se diferenças significativas entre FA e CDI (p=0,010) e entre CDI e CDIS (p=0,049). Conclusões – O ADC possibilita a diferenciação entre lesões mamárias benignas e malignas, bem como entre alguns tipos histológicos. O desenvolvimento deste conceito pode representar um avanço no papel da RM na avaliação destas neoplasias. ABSTRACT - Introduction – The Magnetic Resonance (MR) diffusion technique measures the movement of water molecules in tissues. Therefore, it provides useful information about tissue architecture, specially regarding tissue cellularity, cell volume and membrane permeability. The quantification of diffusion weighted imaging (DWI) data is done by measuring the so-called. Apparent Diffusion Coefficient (ADC). This parameter provides additional clinical information about breast lesions, and potentially allows for in-vivo histological characterization. Purpose – To characterize and differentiate breast lesions through ADC analysis. Methodology – The study comprised 20 women, with 23 breast lesions: 3 benign lesions - 3 Fibroadenomas (FA); and 20 malignant - 16 Invasive Ductal Carcinomas (CDI), 2 Ductal Carcinomas In Situ (CDIS), 2 Invasive Lobular Carcinoma (CLI). On a 1.5T equipment a diffusion-weighted sequence with 6 b-values (b=0,50,250,500,750,1000 s/mm2) was used to examine the patients. ADC was obtained by fitting an exponential to data of lesion signal intensity vs. b values. A correspondence of ADC values to histological lesion characterization was done and finally, the results were comparison with the literature. Results and Discussion – Malignant lesions showed inferior ADCs significantly (p=0.014) lower ((0.94±0.22)x10-3 mm2/s) than the benign lesions ((1.43±0.25)x10-3 mm2/s). This may be associated to increasead cellularity in malignant lesions, which result in higher tissue restriction to diffusion. CDI showed low ADC values ((0.88±0.17)x10-3 mm2/s), while the CDIS showed higher ADCs ((1.33±0.29)x10-3 mm2/s). These results agree with the fact that CDIS are limited to mammary ducts, maintaining a less altered neighboring tissue structure, which results in a lower restriction to diffusion than observed in CDI. Significant differences between FA and CDI (p=0.010) and between CDI and CDIS (p=0.049) were observed. Conclusion – The ADC parameter is able to differentiate between malignant and benign breast lesions, as well as between some histological types.

Estudo e desenvolvimento de um sensor de chuva piezoelétrico para automóveis

A presença de sistemas eletrónicos nos veículos automóveis tem vindo a aumentar de forma considerável nos últimos 30 anos, tornando possível o aumento dos padrões de eficiência, segurança e conforto dos mesmos. Os sistemas de acionamento automático dos limpa-para-brisas, baseados em sensores de chuva óticos, têm registado um crescimento quase exponencial nos últimos 10 a 15 anos; no ano 2000, apenas 5 % dos veículos novos produzidos na Europa estavam equipados com este sistema, hoje é um equipamento amplamente difundido na oferta automóvel existente. O presente trabalho consistiu no estudo de uma solução para deteção de chuva em veículos automóveis com a aplicação de um sensor piezoelétrico, tendo em vista a obtenção de uma solução mais versátil e aplicável em vários pontos do veículo. As reduzidas dimensões, a elevada sensibilidade do sensor e a facilidade de aplicação nas superfícies de ensaio foram fatores que motivaram a escolha deste tipo de equipamento como elemento sensorial. As hipóteses definidas para o procedimento laboratorial basearam-se nas conclusões obtidas em estudos anteriormente desenvolvidos no campo dos sensores de chuva para automóveis e nas capacidades dos materiais piezoelétricos para medição de pluviosidade. Os sensores foram instalados sob as superfícies do veículo que apresentavam, simultaneamente, uma maior exposição à pluviosidade, quando este está em movimento, e um menor risco de sofrer danos. Os resultados obtidos permitiram concluir que a utilização deste tipo de sensores permite detetar elevados níveis de pluviosidade e em superfícies com considerável capacidade de deformação elástica. A sua implementação futura em veículos automóveis exige mais algum trabalho de melhoria dos processos de fixação dos sensores e do condicionamento de sinal utilizados.

Real-time rheology of actively growing bacteria

The population growth of a Staphylococcus aureus culture, an active colloidal system of spherical cells, was followed by rheological measurements, under steady-state and oscillatory shear flows. We observed a rich viscoelastic behavior as a consequence of the bacteria activity, namely, of their multiplication and density-dependent aggregation properties. In the early stages of growth (lag and exponential phases), the viscosity increases by about a factor of 20, presenting several drops and full recoveries. This allows us to evoke the existence of a percolation phenomenon. Remarkably, as the bacteria reach their late phase of development, in which the population stabilizes, the viscosity returns close to its initial value. Most probably, this is caused by a change in the bacteria physiological activity and in particular, by the decrease of their adhesion properties. The viscous and elastic moduli exhibit power-law behaviors compatible with the "soft glassy materials" model, whose exponents are dependent on the bacteria growth stage. DOI: 10.1103/PhysRevE.87.030701.

Caracterização bidimensional de um canal rádio Wimax

Com o crescimento previsível e exponencial das redes de comunicações móveis motivado pela mobilidade, flexibilidade e também comodidade do utilizador levam a que este se torne na fatia mais importante do mundo das telecomunicações dos dias que correm. Assim é importante estudar e caracterizar canais rádio para as mais diversas gamas de frequências utilizadas nas mais variadas tecnologias. O objectivo principal desta dissertação de Mestrado é caracterizar um canal rádio para a tecnologia sem fios Worldwide Inter-operability for Microwave Access (Wimax para as frequências de 3,5 GHz e 5 GHz) actualmente vista pela comunidade científica como a tecnologia sem fios com maiores perspectivas de sucesso. Para tal, determinaram-se o Perfil de Atraso de Potência (PAP) e também a Potência em Função da Distância (PFD) recorrendo ao método computacional de simulação Finite-Difference Time-Domain (FDTD). De forma a estudar e caracterizar o canal rádio, em termos de desvanecimento relativo ao espalhamento de atraso, usaram-se dois métodos alternativos que têm como entrada o PAP. Para caracterizar o canal quanto ao desvanecimento baseado em espalhamento de Doppler, recorreu-se também a duas técnicas alternativas tendo como entrada o PFD. Em ambas as situações os dois métodos alternativos convergiram para os mesmos resultados. A caracterização é feita em dois cenários diferentes: um em que consideramos que a maioria dos obstáculos são condutores eléctricos perfeitos (CEP) e que passaremos a designar Cenário PEC, e um segundo cenário em que os obstáculos têm propriedades electromagnéticas diferentes, e que passará a ser designado por Cenário MIX. Em ambos os cenários de análise concluiu-se que o canal é plano, lento e sem ISI.

Abordagem à previsão do preço de energia elétrica via métodos de suavização exponencial

Dissertação para a obtenção do grau de Mestre em Engenharia Electrotécnica Ramo de Energia

Observação e controlo da segurança estrutural de barragens de betão: utilização integrada de modelos numéricos e de modelos de separação de efeitos

Dissertação de Natureza Científica elabora da no âmbito do protocolo de cooperação entre o ISEL e o LNEC para obtenção do grau de Mestre em Engenharia Civil

SGBD de alta escalabilidade com suporte a dados georreferenciados

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Informática e de Computadores

Critérios de projecto de um data centre

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Previsão de curto prazo do consumo de energia elétrica

Dissertação para a obtenção do grau de Mestre em Engenharia Electrotécnica - Ramo de Energia

Metaheuristic approach to the Holt-Winters optimal short term load forecast

Electricity short-term load forecast is very important for the operation of power systems. In this work a classical exponential smoothing model, the Holt-Winters with double seasonality was used to test for accurate predictions applied to the Portuguese demand time series. Some metaheuristic algorithms for the optimal selection of the smoothing parameters of the Holt-Winters forecast function were used and the results after testing in the time series showed little differences among methods, so the use of the simple local search algorithms is recommended as they are easier to implement.