Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h−1), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1–3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved.

Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Modelos de supervisão/regulação bancária: enquadramento internacional e desenvolvimentos mais recentes

Mestrado em Contabilidade e Análise Financeira

Auditoria dos sistemas de informação das instituições financeiras

Mestrado em Contabilidade e Gestão das Instituições Financeiras

Avaliação e optimização operacional: estudo do terminal de contentores de Alcântara

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica - Ramo Manutenção e Produção

Síntese e caracterização de redes metalo-orgânicas de fármacos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Formulação editorial de uma colecção de aventuras: a colecção Salgari da livraria Romano Torres

Este artigo explora os caminhos múltiplos e, por vezes, ínvios através dos quais se tece o trabalho editorial na construção de uma colecção de livros. Esse trabalho encontra-se socialmente inscrito num contexto em que se articulam e interligam, frequentemente em tensão, lógicas e actores até exteriores à editora, formando um processo que molda a cultura impressa. O caso estudado é o da colecção Salgari, editada pela Livraria Romano Torres, editora portuguesa que publica esta série de literatura de aventuras durante mais de sete décadas.

A fraude no Fundo Social Europeu

Mestrado em Auditoria

Teatro e igualdade de género : uma intervenção social e artística : relatório de estágio

O presente Relatório de Estágio tem como objecto de pesquisa a concepção e monitorização de duas Oficinas de Teatro dirigidas a dois grupos de mulheres constituídos, respectivamente, por estudantes universitárias e desempregadas. O estágio realizou-se entre Novembro/2013 e Junho/2014 na Quarta Parede - Associação de Artes Performativas da Covilhã e inseriu-se nos Empowerment Labs, laboratórios formativos que cruzam artes performativas e ciências sociais na reflexão e intervenção sobre a igualdade de género com foco no desemprego feminino. Este relatório expõe os três momentos do processo do estágio: pesquisa de referenciais teórico-práticos, concepção e monitorização das Oficinas de Teatro e reflexão a partir da prática laboratorial. Na pesquisa de referenciais, essencial para delinear a metodologia operacional e o programa de conteúdos, explorei dimensões como o feminismo e a igualdade de género, e procurei compreender de que forma o empowerment, a pedagogia de Paulo Freire e as metodologias do teatro aplicado serviam os objectivos do meu trabalho. A realização das oficinas foi o momento de experimentar as metodologias e o programa delineado. Tendo a igualdade de género como temática unificadora, o empowerment através da arte como objectivo maior e o teatro aplicado como base metodológica, as oficinas inserem-se nos processos de educação não-formal aplicados ao incremento de recursos intelectuais, emocionais, sociais, expressivos e criativos e, neste caso específico, à ampliação da consciência de género. Neste sentido, as oficinas desenvolveram uma abordagem metodológica processual, participativa e multidisciplinar, orientada para a pesquisa performativa, primeiro de uma dramaturgia individual, depois de uma dramaturgia do colectivo e, por fim, de uma dramaturgia orientada para a igualdade de género. O conceito de “dramaturgia” surge aqui no sentido metodológico do pachwork (trabalho com retalhos) e do sampling (recolha e transformação de materiais), relevante sobretudo na última fase, dedicada à construção colectiva de um exercício performativo apresentado publicamente.

Estudo comparativo da estrutura de betão armado de um edifício dimensionada segunda a actual regulamentação nacional e os eurocódigos estruturais

Dissertação para obtenção do grau de Mestre em Engenharia Civil - Ramo de Estruturas

Inconstância, ausência e paradoxo na política para o livro no Estado Novo português

Neste artigo procura-se entender a dúplice forma como o Estado Novo em Portugal lidou com o livro como objecto de acção política. As tentativas de enquadrar o livro como alvo de promoção no sentido de um apoio efectivo e da adopção de medidas correctivas das disfunções do mercado, próprias de uma matriz contemporânea e aberta de sistemas políticos e sociais desenvolvidos, nunca terão verdadeiramente existido durante o período autocrático. Com efeito, desde o seu começo até meados da década de 1950 o regime hesitou entre fórmulas – isoladas – de suporte à edição e à leitura, que não pôde ou não quis consolidar, e opções tendentes a conseguir arregimentar agentes do livro (sobretudo editores e autores) à nunca concretizada literatura oficial do Estado Novo, e que obedecesse aos seus pressupostos. O caminho trilhado parece ter sido, a partir de dado momento, essencialmente o da repressão ao livro, pautando o poder a sua actuação pela ausência de propostas de fomento do mercado editorial e livreiro como as que se verificaram noutros contextos nacionais, inclusive ditatoriais.

BITalino: a novel hardware framework for physiological computing

Physical computing has spun a true global revolution in the way in which the digital interfaces with the real world. From bicycle jackets with turn signal lights to twitter-controlled christmas trees, the Do-it-Yourself (DiY) hardware movement has been driving endless innovations and stimulating an age of creative engineering. This ongoing (r)evolution has been led by popular electronics platforms such as the Arduino, the Lilypad, or the Raspberry Pi, however, these are not designed taking into account the specific requirements of biosignal acquisition. To date, the physiological computing community has been severely lacking a parallel to that found in the DiY electronics realm, especially in what concerns suitable hardware frameworks. In this paper, we build on previous work developed within our group, focusing on an all-in-one, low-cost, and modular biosignal acquisition hardware platform, that makes it quicker and easier to build biomedical devices. We describe the main design considerations, experimental evaluation and circuit characterization results, together with the results from a usability study performed with volunteers from multiple target user groups, namely health sciences and electrical, biomedical, and computer engineering. Copyright © 2014 SCITEPRESS - Science and Technology Publications. All rights reserved.

Data analytics in the cloud with flexible mapreduced workflows

Data analytic applications are characterized by large data sets that are subject to a series of processing phases. Some of these phases are executed sequentially but others can be executed concurrently or in parallel on clusters, grids or clouds. The MapReduce programming model has been applied to process large data sets in cluster and cloud environments. For developing an application using MapReduce there is a need to install/configure/access specific frameworks such as Apache Hadoop or Elastic MapReduce in Amazon Cloud. It would be desirable to provide more flexibility in adjusting such configurations according to the application characteristics. Furthermore the composition of the multiple phases of a data analytic application requires the specification of all the phases and their orchestration. The original MapReduce model and environment lacks flexible support for such configuration and composition. Recognizing that scientific workflows have been successfully applied to modeling complex applications, this paper describes our experiments on implementing MapReduce as subworkflows in the AWARD framework (Autonomic Workflow Activities Reconfigurable and Dynamic). A text mining data analytic application is modeled as a complex workflow with multiple phases, where individual workflow nodes support MapReduce computations. As in typical MapReduce environments, the end user only needs to define the application algorithms for input data processing and for the map and reduce functions. In the paper we present experimental results when using the AWARD framework to execute MapReduce workflows deployed over multiple Amazon EC2 (Elastic Compute Cloud) instances.