Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer-Villiger Oxidation of Ketones

New rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

Self-Scheduling for energy and spinning reserve of wind/CSP plants by a MILP approach

This paper is on the self-scheduling for a power producer taking part in day-ahead joint energy and spinning reserve markets and aiming at a short-term coordination of wind power plants with concentrated solar power plants having thermal energy storage. The short-term coordination is formulated as a mixed-integer linear programming problem given as the maximization of profit subjected to technical operation constraints, including the ones related to a transmission line. Probability density functions are used to model the variability of the hourly wind speed and the solar irradiation in regard to a negative correlation. Case studies based on an Iberian Peninsula wind and concentrated solar power plants are presented, providing the optimal energy and spinning reserve for the short-term self-scheduling in order to unveil the coordination benefits and synergies between wind and solar resources. Results and sensitivity analysis are in favour of the coordination, showing an increase on profit, allowing for spinning reserve, reducing the need for curtailment, increasing the transmission line capacity factor. (C) 2014 Elsevier Ltd. All rights reserved.

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

Autonomic Activities in the Execution of Scientific Workflows: Evaluation of the AWARD Framework

Workflows have been successfully applied to express the decomposition of complex scientific applications. However the existing tools still lack adequate support to important aspects namely, decoupling the enactment engine from tasks specification, decentralizing the control of workflow activities allowing their tasks to run in distributed infrastructures, and supporting dynamic workflow reconfigurations. We present the AWARD (Autonomic Workflow Activities Reconfigurable and Dynamic) model of computation, based on Process Networks, where the workflow activities (AWA) are autonomic processes with independent control that can run in parallel on distributed infrastructures. Each AWA executes a task developed as a Java class with a generic interface allowing end-users to code their applications without low-level details. The data-driven coordination of AWA interactions is based on a shared tuple space that also enables dynamic workflow reconfiguration. For evaluation we describe experimental results of AWARD workflow executions in several application scenarios, mapped to the Amazon (Elastic Computing EC2) Cloud.

Sistemas de abastecimento de água e saneamento básico

O presente relatório de estágio enquadra-se no âmbito do Trabalho Final de Mestrado (TFM) do curso de Engenharia Civil, área de especialização de Hidráulica, do Instituto Superior de Engenharia de Lisboa, e baseia-se na temática dos sistemas de abastecimento de água e drenagem de águas residuais. O estágio, intitulado de “Sistemas de Abastecimento de Agua e Saneamento Básico”, decorreu numa empresa de consultaria de engenharia denominada ENGIDRO – Estudos de Engenharia, Lda., vocacionada para a realização de estudos e projectos na área de Hidráulica, com particular incidência na Hidráulica Urbana e Saneamento Básico. O estágio iniciou-se com um adequado enquadramento profissional na empresa e incidiu principalmente no desenvolvimento de trabalhos de concepção e dimensionamento, a nível de projectos de execução, de sistemas de abastecimento de água e de saneamento básico, para 21 localidades da província de Lunda Sul, em Angola, com prestação de serviços para o Governo Provincial de Lunda Sul – Direcção Provincial da Energia e Aguas, juntamente com empresa CENGA – Consultores de Engenharia de Angola, S.A. Na prestação de serviços à entidade contratante foram efectuados trabalhos de campo, que consistiram principalmente em reconhecimentos do terreno, levantamentos topográficos e recolha de informação relevante sobre elementos condicionantes dos projectos (origens e disponibilidades de água, natureza e declive dos terrenos, tipos de infra-estruturas locais) e trabalhos de gabinete para compilação e análise da informação recolhida na elaboração dos projectos de execução, incluindo pecas desenhadas (desenhos pormenorizados) e peças escritas (memórias descritivas e justificativas, medições e orçamentos). Sendo os projectos destinados a aglomerados populacionais pouco desenvolvidos e com carências e condicionantes de diversa ordem (falta de energia eléctrica, de acessos, de telecomunicações, de meios técnicos e materiais, entre outros), prestou-se especial atenção aos aspectos da concepção, privilegiando soluções de baixa tecnologia, mais fáceis de explorar e manter com os recursos locais disponíveis.

Prestação de serviços de assessoria e fiscalização da obra de "reabilitação das coberturas, acessibilidades e segurança da antiga escola Veiga Beirão - Palácio Valadares, em Lisboa"

O presente relatório diz respeito a um estágio de natureza profissional realizado com o objectivo de constituir Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil no perfil de Edificações, do Instituto Superior de Engenharia de Lisboa. O estágio subordinado ao tema “Prestação de serviços de Assessoria, Fiscalização e Coordenação de Segurança da Obra de REABILITAÇÃO DAS COBERTURAS, ACESSIBILIDADES E SEGURANÇA DA ANTIGA ESCOLA VEIGA BEIRÃO – PALÁCIO VALADARES, EM LISBOA”, decorreu na Pengest – Planeamento, Engenharia e Gestão, S.A., empresa vocacionada para a prestação de serviços de Assessoria, Gestão, Coordenação e Fiscalização de Obras, sector no qual possui vasta e diversificada experiência, e reconhecidos mérito e competência. O objectivo da empreitada é o de recuperação deste imóvel, intervenção necessária à instalação no local da Exposição “República e Ensino” enquadrada no âmbito das Comemorações do Centenário da República. A empreitada foi adjudicada ao Empreiteiro Teixeira Duarte, S.A, pelo valor de €998.072,76. O prazo é de 4,5 meses prevendo-se a conclusão para 18 de Março de 2010. Embora a proposta de estágio tenha decorrido no início de 2010, no âmbito do tema que viria a ser proposto e de forma a integrar a Estagiária numa empresa em pleno funcionamento, o estágio teve início aquando do início da empreitada, em Novembro de 2009. Exceptuando os trabalhos de montagem da grua-torre e dos andaimes para a cobertura provisória, que decorreram antes da consignação, foi acompanhado todo o processo de Fiscalização. A Estagiária participou na análise do Plano de Trabalhos, nas vistorias às fracções autónomas e edifícios adjacentes, nas visitas à obra e na elaboração de relatórios mensais. Acompanhou os procedimentos da Pengest no Controlo do Planeamento, da Qualidade e Financeiro. Em relação à Coordenação de Segurança em obra, por ser um tema tão vasto e específico, teve acesso aos relatórios, não tendo efectivamente participado nas actividades desenvolvidas sobre esta matéria. Sob a co-orientação da Eng.ª Isabel Vicente, responsável da Fiscalização e orientação do Eng.º José Pedro Fernandes do ISEL, a estagiária desenvolveu este estágio de forma proveitosa, sempre com o auxílio de uma equipa experiente em Gestão e Fiscalização.

DRhoGEF2 regulates cellular tension and cell pulsations in the Amnioserosa during Drosophila dorsal closure

Coordination of apical constriction in epithelial sheets is a fundamental process during embryogenesis. Here, we show that DRhoGEF2 is a key regulator of apical pulsation and constriction of amnioserosal cells during Drosophila dorsal closure. Amnioserosal cells mutant for DRhoGEF2 exhibit a consistent decrease in amnioserosa pulsations whereas overexpression of DRhoGEF2 in this tissue leads to an increase in the contraction time of pulsations. We probed the physical properties of the amnioserosa to show that the average tension in DRhoGEF2 mutant cells is lower than wild-type and that overexpression of DRhoGEF2 results in a tissue that is more solid-like than wild-type. We also observe that in the DRhoGEF2 overexpressing cells there is a dramatic increase of apical actomyosin coalescence that can contribute to the generation of more contractile forces, leading to amnioserosal cells with smaller apical surface than wild-type. Conversely, in DRhoGEF2 mutants, the apical actomyosin coalescence is impaired. These results identify DRhoGEF2 as an upstream regulator of the actomyosin contractile machinery that drives amnioserosa cells pulsations and apical constriction.

O desenvolvimento profissional docente: a função supervisiva do coordenador de ano do 1º ciclo

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação, especialidade de Supervisão em Educação

Estudo sobre o efeito de contágio nos mercados financeiros de acções: aplicação aos índices de acções europeus, americanos, asiáticos e brasileiro no período de Janeiro de 1996 a Junho de 2009 e no sub-período da crise subprime

Mestrado em Contabilidade

A supervisão nas estruturas intermédias do 1º ciclo: as coordenações de ano

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção do grau de mestre em Ciências da Educação, especialidade em Supervisão em Educação

Autonomic workflow activities: the award framework

Workflows have been successfully applied to express the decomposition of complex scientific applications. This has motivated many initiatives that have been developing scientific workflow tools. However the existing tools still lack adequate support to important aspects namely, decoupling the enactment engine from workflow tasks specification, decentralizing the control of workflow activities, and allowing their tasks to run autonomous in distributed infrastructures, for instance on Clouds. Furthermore many workflow tools only support the execution of Direct Acyclic Graphs (DAG) without the concept of iterations, where activities are executed millions of iterations during long periods of time and supporting dynamic workflow reconfigurations after certain iteration. We present the AWARD (Autonomic Workflow Activities Reconfigurable and Dynamic) model of computation, based on the Process Networks model, where the workflow activities (AWA) are autonomic processes with independent control that can run in parallel on distributed infrastructures, e. g. on Clouds. Each AWA executes a Task developed as a Java class that implements a generic interface allowing end-users to code their applications without concerns for low-level details. The data-driven coordination of AWA interactions is based on a shared tuple space that also enables support to dynamic workflow reconfiguration and monitoring of the execution of workflows. We describe how AWARD supports dynamic reconfiguration and discuss typical workflow reconfiguration scenarios. For evaluation we describe experimental results of AWARD workflow executions in several application scenarios, mapped to a small dedicated cluster and the Amazon (Elastic Computing EC2) Cloud.

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Gestão de projetos audiovisuais: a experiência na RTP

Relatório de estágio apresentado à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Audiovisual e Multimédia.

A gestão e coordenação de projecto e obra: considerações gerais sobre duas abordagens em casos concretos

Trabalho de Projecto Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil