Acompanhamento do reforço de potência Salamonde II

Tendo Portugal objetivos cada vez mais ambiciosos na utilização de energias renováveis, aliados às condicionantes socioeconómicas e ambientais existentes que têm dificultado a realização de novos investimentos em novos aproveitamentos, a EDP Gestão de Produção de Energia realizou estudos onde verificou que a realização de reforços de potência seria uma forma bastante atrativa de ultrapassar essas dificuldades e ao mesmo tempo responder às solicitações energéticas atuais. É neste âmbito que se insere o Reforço de Potência de Salamonde, Salamonde II. Este trabalho foi elaborado na sequência de um estágio realizado para elaboração do trabalho final de Mestrado em Engenharia Civil do ISEL, na área de especialização de Hidráulica, e tem como objetivo relacionar o conhecimento académico com os aspetos práticos do exercício profissional na área de construção dos órgãos e equipamentos de uma barragem. O conteúdo deste trabalho é composto pelos seguintes temas: i) um breve enquadramento da obra e definição dos objetivos do projeto, bem como uma descrição das características e processos construtivos utilizados nos diferentes órgãos do circuito hidráulico; ii) demonstração analítica das opções construtivas tomadas na execução do desvio provisório do Rio Mau, concluindo-se que este estava bem dimensionado; iii) estudo das precipitações máximas diárias, recorrendo à Lei de Gumbel, durante o período de estiagem, com o intuito de se estimar o caudal máximo que irá escoar no Rio Mau durante a execução do seu desvio definitivo, verificando que este ocorrerá no mês de setembro; iv) acompanhamento dos trabalhos de execução da ensecadeira de jusante recorrendo, em parte, a uma nova metodologia de betonagem, o BPCA (Betão com Prévia Colocação de Agregado) e também uma análise comparativa dos custos unitários dos diferentes processos construtivos utilizados, onde se evidenciou que esta técnica inovadora tem potencial, mas ainda carece de automatização de processos.

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.

Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.

Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite

The hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{eta(3)-HC(pz)(3)}] (Fe, pz = pyrazol-1-yl) immobilized on commercial (MOR) or desilicated (MOR-D) zeolite, catalyses the oxidation of cyclohexane with hydrogen peroxide to cyclohexanol and cyclohexanone, under mild conditions. MOR-D/Fe (desilicated zeolite supported [FeCl2{eta(3)-HC(pz)(3)}] complex) provides an outstanding catalytic activity (TON up to 2.90 x 10(3)) with the concomitant overall yield of 38%, and can be easy recovered and reused. The MOR or MOR-D supported hydrotris(pyrazol-1-yl)methane iron(II) complex (MOR/Fe and MOR-D/Fe, respectively) was characterized by X-ray powder diffraction, ICP-AES, and TEM studies as well as by IR spectroscopy and N-2 adsorption at -196 degrees C. The catalytic operational conditions (e.g., reaction time, type and amount of oxidant, presence of acid and type of solvent) were optimized. (C) 2013 Elsevier B.V. All rights reserved.

Synthesis of new Fe(II) and Ru(II) eta(5)-monocyclopentadienyl compounds showing significant second order NLO properties

A series of new ruthenium(II) complexes of the general formula [Ru(eta(5)-C5H5)(PP)(L)][PF6] (PP = DPPE or 2PPh(3), L = 4-butoxybenzonitrile or N-(3-cyanophenyl)formamide) and the binuclear iron(II) complex [Fe(eta(5)-C5H5)(PP)(mu-L)(PP)(eta(5)-C5H5)Fe][PF6](2) (L = (E)-2-(3-(4-nitrophenyl)allylidene)malononitrile, that has been also newly synthesized) have been prepared and studied to evaluate their potential in the second harmonic generation property. All the new compounds were fully characterized by NMR, IR and UV-Vis spectroscopies and their electrochemistry behaviour was studied by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of three of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at fundamental wavelength of 1500 nm and the calculated static beta(0) values are found to fall in the range 65-212 x 10(-30) esu. Compound presenting beta(0) = 212 x 10(-30) esu has revealed to be 1.2 times more efficient than urea standard in the second harmonic generation (SHG) property, measured in the solid state by Kurtz powder technique, using a Nd:YAG laser (1064 nm). (C) 2013 Elsevier B.V. All rights reserved.

Flavored asymmetries for type II seesaw leptogenesis

A novel contribution to the leptonic CP asymmetries in type II seesaw leptogenesis scenarios is obtained for the cases in which flavor effects are relevant for the dynamics of leptogenesis. In the so-called flavored leptogenesis regime, the interference between the tree-level amplitude of the scalar triplet decaying into two leptons and the one-loop wave function correction with leptons in the loop, leads to a new nonvanishing CP asymmetry contribution. The latter conserves total lepton number but violates lepton flavor. Cases in which this novel contribution may be dominant in the generation of the baryon asymmetry are briefly discussed.

Impactos do projecto solvência II nos sistemas de governance das seguradoras portuguesas

Mestrado em Contabilidade e Gestão das Instituições Financeiras

Study of Annealed Indium Tin Oxide-Films prepared by RF Reactive Magnetron Sputtering

Tin doped indium oxide (ITO) films were deposited on glass substrates by rf reactive magnetron sputtering using a metallic alloy target (In-Sn, 90-10). The post-deposition annealing has been done for ITO films in air and the effect of annealing temperature on the electrical, optical and structural properties of ITO films was studied. It has been found that the increase of the annealing temperature will improve the film electrical properties. The resistivity of as deposited film is about 1.3 x 10(-1) Omega*cm and decreases down to 6.9 x 10(-3) Omega*cm as the annealing temperature is increased up to 500 degrees C. In addition, the annealing will also increase the film surface roughness which can improve the efficiency of amorphous silicon solar cells by increasing the amount of light trapping.

Prática de ensino supervisionada II: a sequência didática como estratégia para escrita de textos no 1º ano de escolaridade

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1º e 2º CEB

O Reinado de Isabel II e a relação com os média

A Rainha Isabel II, que completou oitenta e quatro anos em Abril de 2010, conta actualmente com cinquenta e sete anos de reinado, um longo período que tem sido caracterizado pela mediatização das formas simbólicas. Utilizamos a expressão “formas simbólicas” de acordo com o significado que lhe é atribuído por John Thompson, devendo-se entender por tal um amplo conjunto de “acções e falas, imagens e textos, que são produzidos por sujeitos e reconhecidos por eles e outros como construtos significativos.” (1998: 79)

Atas do II Encontro de Mestrados em Educação e Ensino da Escola Superior de Educação de Lisboa

Na continuidade da publicação das Atas do I Encontro dos Mestrados em Educação da ESELx (1.º EME), realizado em 2013, a publicação dos artigos reunidos neste volume de atas, submetidos a revisão científica anónima, pretende tornar acessível, a um público mais vasto e diversificado, as comunicações apresentadas no II Encontro dos Mestrados em Educação e Ensino da ESELx (2.º EME), que decorreu na Escola Superior de Educação de Lisboa, no dia 8 de março de 2014. O Encontro foi dinamizado pela Comissão Coordenadora de Mestrados, instância do Conselho Técnico-Científico, em colaboração com o Centro Interdisciplinar de Estudos Educacionais – CIED, em que se inscrevem os projetos e programas de investigação desenvolvidos na ESELx. Prevendo-se que venha a ter, futuramente, uma periodicidade bianual, o Encontro dos Mestrados em Educação e Ensino da ESELx tem como objetivos centrais divulgar a investigação produzida no âmbito dos vários Mestrados na ESELx, e simultaneamente, constituir-se como um fórum de discussão, não só dos resultados obtidos, mas também das diversas abordagens metodológicas adotadas. Com este II Encontro de Mestrados, pretendeu-se ampliar a divulgação da investigação desenvolvida na ESELx, ao contemplar, quer a formação de natureza pós-profissional, no âmbito de mestrados dirigidos a profissionais em educação já no terreno, quer a formação inicial desses profissionais, no âmbito dos mestrados que habilitam para a docência nos contextos da Educação Pré-Escolar e do Ensino Básico (1.º e 2.º Ciclos). Este Encontro inaugura, como foi referido, a apresentação dos trabalhos desenvolvidos pelos estudantes do Mestrado em Educação Pré-Escolar, realizados no âmbito da Prática Profissional Supervisionada nos contextos de creche e jardim de infância. Neste âmbito as nove comunicações apresentadas enquadram-se numa discussão mais ampla sobre a formação de educadores/as de infância na academia portuguesa, que tem vindo a considerar a necessidade de densificar, entre outros objetivos, uma formação que dê corpo, considere e promova o desenvolvimento de uma atitude de natureza investigativa e reflexiva do/no exercício da profissão. Considerando que a investigação possa ser também entendida numa dimensão social e cultural, envolvida com o contexto em que está inserida, a apresentação oral e escrita dos trabalhos desenvolvidos configurou-se como uma oportunidade de divulgação de processos de saber compartilhado, o que, em fim último, caracteriza a própria função pedagógica da investigação no exercício da profissão docente. Os dezassete artigos, situados no contexto dos mestrados pós-profissionalização, abrangem áreas diferenciadas, tais como a intervenção precoce, o teatro, as artes plásticas, a educação matemática, a supervisão e a didática da língua portuguesa. Os percursos metodológicos privilegiados contemplam as abordagens de natureza qualitativa, quantitativa, e ainda abordagens mistas. Alguns dos estudos desenvolvidos adotaram o design de estudo de caso e outros de investigação-ação.A grande diversidade de temas, domínios e abordagens apresentados faz desta publicação um pertinente recurso para apoio epistemológico e metodológico aos estudantes inseridos em processos investigativos diversificados e, ainda, um contributo para a divulgação de conhecimento no âmbito da educação e do ensino, no contexto da realidade educativa portuguesa.

Experimental Study And Evaluation Of Paper-Based Inkjet Electrodes For ECG Signal Acquisition

Applications involving biosignals, such as Electrocardiography (ECG), are becoming more pervasive with the extension towards non-intrusive scenarios helping targeting ambulatory healthcare monitoring, emotion assessment, among many others. In this study we introduce a new type of silver/silver chloride (Ag/AgCl) electrodes based on a paper substrate and produced using an inkjet printing technique. This type of electrodes can increase the potential applications of biosignal acquisition technologies for everyday life use, given that there are several advantages, such as cost reduction and easier recycling, resultant from the approach explored in our work. We performed a comparison study to assess the quality of this new electrode type, in which ECG data was collected with three types of Ag/AgCl electrodes: i) gelled; ii) dry iii) paper-based inkjet printed. We also compared the performance of each electrode when acquired using a professional-grade gold standard device, and a low cost platform. Experimental results showed that data acquired using our proposed inkjet printed electrode is highly correlated with data obtained through conventional electrodes. Moreover, the electrodes are robust to high-end and low-end data acquisition devices. Copyright © 2014 SCITEPRESS - Science and Technology Publications. All rights reserved.

Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applications

[CoCl(-Cl)(Hpz(Ph))(3)](2) (1) and [CoCl2(Hpz(Ph))(4)] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))(3) and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible (CoCoIII)-Co-II oxidations and (CoCoI)-Co-II reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). Insitu X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co-III site. Complex 2 showed low invitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.

Dinuclear Mn (II,II) complexes: magnetic properties and microwave assisted oxidation of alcohols

A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.

Insights into the mechanims underlyng the antiproliferative potential of a Co(II) coordination compound bearing 1,10-Phenanthroline-5,6-Dione: DNA and protein interaction studies

The very high antiproliferative activity of [Co(Cl)(H2O)(phendione)(2)][BF4] (phendione is 1,10-phenanthroline-5,6-dione) against three human tumor cell lines (half-maximal inhibitory concentration below 1 mu M) and its slight selectivity for the colorectal tumor cell line compared with healthy human fibroblasts led us to explore the mechanisms of action underlying this promising antitumor potential. As previously shown by our group, this complex induces cell cycle arrest in S phase and subsequent cell death by apoptosis and it also reduces the expression of proteins typically upregulated in tumors. In the present work, we demonstrate that [Co(Cl)(phendione)(2)(H2O)][BF4] (1) does not reduce the viability of nontumorigenic breast epithelial cells by more than 85 % at 1 mu M, (2) promotes the upregulation of proapoptotic Bax and cell-cycle-related p21, and (3) induces release of lactate dehydrogenase, which is partially reversed by ursodeoxycholic acid. DNA interaction studies were performed to uncover the genotoxicity of the complex and demonstrate that even though it displays K (b) (+/- A standard error of the mean) of (3.48 +/- A 0.03) x 10(5) M-1 and is able to produce double-strand breaks in a concentration-dependent manner, it does not exert any clastogenic effect ex vivo, ruling out DNA as a major cellular target for the complex. Steady-state and time-resolved fluorescence spectroscopy studies are indicative of a strong and specific interaction of the complex with human serum albumin, involving one binding site, at a distance of approximately 1.5 nm for the Trp214 indole side chain with log K (b) similar to 4.7, thus suggesting that this complex can be efficiently transported by albumin in the blood plasma.