Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

Evaluation of staining techniques on the results of micronucleus in exfoliated oral mucosa cells

Micronuclei (MN) in exfoliated epithelial cells are widely used as biomarkers of cancer risk in humans. MN are classified as biomarkers of the break age and loss of chromosomes. They are small, extra nuclear bodies that arise in dividing cells from centric chromosome/chromatid fragments or whole chromosomes/chromatids that lag behind in anaphase and are not included in the daughter nuclei in telophase. Buccal mucosa cells have been used in biomonitoring exposed populations because these cells are in the direct route of exposure to ingested pollutant, are capable of metabolizing proximate carcinogens to reactive chemicals, and are easily and rapidly collected by brushing the buccal mucosa. The objective of the present study was to further investigate if, and to what extent, different stains have an effect on the results of micronuclei studies in exfoliated cells. These techniques are: Papanicolaou (PAP), Modified Papanicolaou, May-Grünwald Giemsa (MGG), Giemsa, Harris’s Hematoxylin, Feulgen with Fast Green counterstain and Feulgen without counterstain.

Identification of tsunami-induced deposits using numerical modeling and rock magnetism techniques: A study case of the 1755 Lisbon tsunami in Algarve, Portugal

Storm- and tsunami-deposits are generated by similar depositional mechanisms making their discrimination hard to establish using classic sedimentologic methods. Here we propose an original approach to identify tsunami-induced deposits by combining numerical simulation and rock magnetism. To test our method, we investigate the tsunami deposit of the Boca do Rio estuary generated by the 1755 earthquake in Lisbon which is well described in the literature. We first test the 1755 tsunami scenario using a numerical inundation model to provide physical parameters for the tsunami wave. Then we use concentration (MS. SIRM) and grain size (chi(ARM), ARM, B1/2, ARM/SIRM) sensitive magnetic proxies coupled with SEM microscopy to unravel the magnetic mineralogy of the tsunami-induced deposit and its associated depositional mechanisms. In order to study the connection between the tsunami deposit and the different sedimentologic units present in the estuary, magnetic data were processed by multivariate statistical analyses. Our numerical simulation show a large inundation of the estuary with flow depths varying from 0.5 to 6 m and run up of similar to 7 m. Magnetic data show a dominance of paramagnetic minerals (quartz) mixed with lesser amount of ferromagnetic minerals, namely titanomagnetite and titanohematite both of a detrital origin and reworked from the underlying units. Multivariate statistical analyses indicate a better connection between the tsunami-induced deposit and a mixture of Units C and D. All these results point to a scenario where the energy released by the tsunami wave was strong enough to overtop and erode important amount of sand from the littoral dune and mixed it with reworked materials from underlying layers at least 1 m in depth. The method tested here represents an original and promising tool to identify tsunami-induced deposits in similar embayed beach environments.

Modification of MOR by desilication treatments: Structural, textural and acidic characterization

The effect of several desilication experimental parameters (base concentration, temperature and time) on the characteristics of MOR zeolite was studied. The samples were characterized by X-ray diffraction, Al-27 and Si-29 MAS-NMR, chemical analysis, and FTIR (framework vibration region). The textural characterization was made by N-2 adsorption and the acidity was evaluated by pyridine adsorption followed by FTIR and by the catalytic model reaction of n-heptane cracking. The alkaline treatments promoted the Si extraction from the zeolite framework, without considerable loss of crystallinity and, as it was envisaged, an important increase of the mesoporous structure was attained. A linear correlation between the number of framework Si per unit cell. N-Si and the asymmetric stretching wavenumber, nu(i), was observed. The acidity characterization shows that the desilicated samples exhibit practically the same acid properties than the parent HMOR zeolite. The optimum desilication conditions were those used to obtain sample M/0.2/85/2, i.e., sample treated with 0.2 M NaOH solution at 85 degrees C for 2 h.

Learning techniques for automatic email message tagging

A organização automática de mensagens de correio electrónico é um desafio actual na área da aprendizagem automática. O número excessivo de mensagens afecta cada vez mais utilizadores, especialmente os que usam o correio electrónico como ferramenta de comunicação e trabalho. Esta tese aborda o problema da organização automática de mensagens de correio electrónico propondo uma solução que tem como objectivo a etiquetagem automática de mensagens. A etiquetagem automática é feita com recurso às pastas de correio electrónico anteriormente criadas pelos utilizadores, tratando-as como etiquetas, e à sugestão de múltiplas etiquetas para cada mensagem (top-N). São estudadas várias técnicas de aprendizagem e os vários campos que compõe uma mensagem de correio electrónico são analisados de forma a determinar a sua adequação como elementos de classificação. O foco deste trabalho recai sobre os campos textuais (o assunto e o corpo das mensagens), estudando-se diferentes formas de representação, selecção de características e algoritmos de classificação. É ainda efectuada a avaliação dos campos de participantes através de algoritmos de classificação que os representam usando o modelo vectorial ou como um grafo. Os vários campos são combinados para classificação utilizando a técnica de combinação de classificadores Votação por Maioria. Os testes são efectuados com um subconjunto de mensagens de correio electrónico da Enron e um conjunto de dados privados disponibilizados pelo Institute for Systems and Technologies of Information, Control and Communication (INSTICC). Estes conjuntos são analisados de forma a perceber as características dos dados. A avaliação do sistema é realizada através da percentagem de acerto dos classificadores. Os resultados obtidos apresentam melhorias significativas em comparação com os trabalhos relacionados.

Controlo tolerante a falhas de um canal de rega

A presente dissertação pretende conceber e implementar um sistema de controlo tolerante a falhas, no canal experimental de rega da Universidade de Évora, utilizando um modelo implementado em MATLAB/SIMULINK®. Como forma de responder a este desafio, analisaram-se várias técnicas de diagnóstico de falhas, tendo-se optado por técnicas baseadas em redes neuronais para o desenvolvimento de um sistema de detecção e isolamento de falhas no canal de rega, sem ter em conta o tipo de sistema de controlo utilizado. As redes neuronais foram, assim, os processadores não lineares utilizados e mais aconselhados em situações onde exista uma abundância de dados do processo, porque aprendem por exemplos e são suportadas por teorias estatísticas e de optimização, focando não somente o processamento de sinais, como também expandindo os horizontes desse processamento. A ênfase dos modelos das redes neuronais está na sua dinâmica, na sua estabilidade e no seu comportamento. Portanto, o trabalho de investigação do qual resultou esta Dissertação teve como principais objectivos o desenvolvimento de modelos de redes neuronais que representassem da melhor forma a dinâmica do canal de rega, de modo a obter um sistema de detecção de falhas que faça uma comparação entre os valores obtidos nos modelos e no processo. Com esta diferença de valores, da qual resultará um resíduo, é possível desenvolver tanto o sistema de detecção como de isolamento de falhas baseados nas redes neuronais, possibilitando assim o desenvolvimento dum sistema de controlo tolerante a falhas, que engloba os módulos de detecção, de isolamento/diagnóstico e de reconfiguração do canal de rega. Em síntese, na Dissertação realizada desenvolveu-se um sistema que permite reconfigurar o processo em caso de ocorrência de falhas, melhorando significativamente o desempenho do canal de rega.

Reforço estrutural de uma edificação pombalina: acompanhamento em obra

Este trabalho Final de Mestrado consiste na elaboração de um relatório de estágio que reportará o acompanhamento por parte do discente de um reforço estrutural de uma edificação pombalina. Desta forma são definidas as principais características construtivas destas edificações, fazendo um enquadramento histórico-cultural e urbanístico do edifício alvo deste trabalho. Uma vez estudado um tipo de construção especial, são mencionados diversos sistemas e metodologias de reforço que se adequam às características singulares destas construções, ilustrando-se procedimentos e técnicas que normalmente são utilizadas na reabilitação. Procedeu-se ao relato dos trabalhos executados na obra, desde a demolição dos elementos degradados e dissonantes com esta tipologia construtiva, a um estudo mais pormenorizado ao solo de fundação encontrado na zona da edificação e soluções de fundação adoptadas. São descritas neste trabalho quais as medidas adoptadas no reforço da estrutura da edificação, evidenciando os procedimentos e técnicas aplicadas pela empresa. No final deste trabalho, foi efectuada uma modelação do edifício da Rua do Carmo num software de análise estrutural SAP 2000, com o objectivo de modelar de forma aproximada a real geometria do edifício e, através da introdução das variadas acções actuantes na estrutura, fazer determinadas considerações do comportamento da mesma face às solicitações impostas. Pretendeu-se ainda estabelecer uma relação entres os resultados obtidos e as técnicas de reforço utilizadas na reabilitação destes edifícios.

Identification of tsunami-induced deposits using numerical modeling and rock magnetism techniques: A study case of the 1755 Lisbon tsunami in Algarve, Portugal

Storm- and tsunami-deposits are generated by similar depositional mechanisms making their discrimination hard to establish using classic sedimentologic methods. Here we propose an original approach to identify tsunami-induced deposits by combining numerical simulation and rock magnetism. To test our method, we investigate the tsunami deposit of the Boca do Rio estuary generated by the 1755 earthquake in Lisbon which is well described in the literature. We first test the 1755 tsunami scenario using a numerical inundation model to provide physical parameters for the tsunami wave. Then we use concentration (MS. SIRM) and grain size (chi(ARM), ARM, B1/2, ARM/SIRM) sensitive magnetic proxies coupled with SEM microscopy to unravel the magnetic mineralogy of the tsunami-induced deposit and its associated depositional mechanisms. In order to study the connection between the tsunami deposit and the different sedimentologic units present in the estuary, magnetic data were processed by multivariate statistical analyses. Our numerical simulation show a large inundation of the estuary with flow depths varying from 0.5 to 6 m and run up of similar to 7 m. Magnetic data show a dominance of paramagnetic minerals (quartz) mixed with lesser amount of ferromagnetic minerals, namely titanomagnetite and titanohematite both of a detrital origin and reworked from the underlying units. Multivariate statistical analyses indicate a better connection between the tsunami-induced deposit and a mixture of Units C and D. All these results point to a scenario where the energy released by the tsunami wave was strong enough to overtop and erode important amount of sand from the littoral dune and mixed it with reworked materials from underlying layers at least 1 m in depth. The method tested here represents an original and promising tool to identify tsunami-induced deposits in similar embayed beach environments.

Advanced side information creation techniques and framework for Wyner-Ziv video coding

Recently, several distributed video coding (DVC) solutions based on the distributed source coding (DSC) paradigm have appeared in the literature. Wyner-Ziv (WZ) video coding, a particular case of DVC where side information is made available at the decoder, enable to achieve a flexible distribution of the computational complexity between the encoder and decoder, promising to fulfill novel requirements from applications such as video surveillance, sensor networks and mobile camera phones. The quality of the side information at the decoder has a critical role in determining the WZ video coding rate-distortion (RD) performance, notably to raise it to a level as close as possible to the RD performance of standard predictive video coding schemes. Towards this target, efficient motion search algorithms for powerful frame interpolation are much needed at the decoder. In this paper, the RD performance of a Wyner-Ziv video codec is improved by using novel, advanced motion compensated frame interpolation techniques to generate the side information. The development of these type of side information estimators is a difficult problem in WZ video coding, especially because the decoder only has available some reference, decoded frames. Based on the regularization of the motion field, novel side information creation techniques are proposed in this paper along with a new frame interpolation framework able to generate higher quality side information at the decoder. To illustrate the RD performance improvements, this novel side information creation framework has been integrated in a transform domain turbo coding based Wyner-Ziv video codec. Experimental results show that the novel side information creation solution leads to better RD performance than available state-of-the-art side information estimators, with improvements up to 2 dB: moreover, it allows outperforming H.264/AVC Intra by up to 3 dB with a lower encoding complexity.

Information and investor behavior surrounding earnings announcements

Preliminary version

Ageing effects on the wettability behavior of laser textured silicon

In the present work we investigate the ageing of acid cleaned femtosecond laser textured < 100 > silicon surfaces. Changes in the surface structure and chemistry were analysed by Rutherford backscattering spectrometry (RBS) and X-ray photoelectron spectroscopy (XPS), in order to explain the variation with time of the water contact angles of the laser textured surfaces. It is shown that highly hydrophobic silicon surfaces are obtained immediately after laser texturing and cleaning with acid solutions (water contact angle >120 degrees). However these surfaces are not stable and ageing leads to a decrease of the water contact angle which reaches a value of 80 degrees. XPS analysis of the surfaces shows that the growth of the native oxide layer is most probably responsible for this behavior. (C) 2010 Elsevier B.V. All rights reserved.

Identification of tsunami-induced deposits using numerical modeling and rock magnetism techniques: Astudy case of the 1755 Lisbon tsunami in Algarve, Portugal (vol 182, pg 187, 2010)

Storm- and tsunami-deposits are generated by similar depositional mechanisms making their discrimination hard to establish using classic sedimentologic methods. Here we propose an original approach to identify tsunami-induced deposits by combining numerical simulation and rock magnetism. To test our method, we investigate the tsunami deposit of the Boca do Rio estuary generated by the 1755 earthquake in Lisbon which is well described in the literature. We first test the 1755 tsunami scenario using a numerical inundation model to provide physical parameters for the tsunami wave. Then we use concentration (MS. SIRM) and grain size (chi(ARM), ARM, B1/2, ARM/SIRM) sensitive magnetic proxies coupled with SEM microscopy to unravel the magnetic mineralogy of the tsunami-induced deposit and its associated depositional mechanisms. In order to study the connection between the tsunami deposit and the different sedimentologic units present in the estuary, magnetic data were processed by multivariate statistical analyses. Our numerical simulation show a large inundation of the estuary with flow depths varying from 0.5 to 6 m and run up of similar to 7 m. Magnetic data show a dominance of paramagnetic minerals (quartz) mixed with lesser amount of ferromagnetic minerals, namely titanomagnetite and titanohematite both of a detrital origin and reworked from the underlying units. Multivariate statistical analyses indicate a better connection between the tsunami-induced deposit and a mixture of Units C and D. All these results point to a scenario where the energy released by the tsunami wave was strong enough to overtop and erode important amount of sand from the littoral dune and mixed it with reworked materials from underlying layers at least 1 m in depth. The method tested here represents an original and promising tool to identify tsunami-induced deposits in similar embayed beach environments.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

Análogos do neuropéptido Y marcados com 99mTc para detecção de receptores Y1 expressos no cancro da mama

Mestrado em Medicina Nuclear. Área de especialização: Radiofarmácia.

Práticas de inclusão de alunos com perturbação do espectro do autismo no 1º Ciclo

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialidade Educação Especial – Problemas Cognitivos e Multideficiência