Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Improving a Cluster Based Directional Channel Model in Realistic Macro-Cell Environment

In this paper a realistic directional channel model that is an extension of the COST 273 channel model is presented. The model uses a cluster of scatterers and visibility region generation based strategy with increased realism, due to the introduction of terrain and clutter information. New approaches for path-loss prediction and line of sight modeling are considered, affecting the cluster path gain model implementation. The new model was implemented using terrain, clutter, street and user mobility information for the city of Lisbon, Portugal. Some of the model's outputs are presented, mainly path loss and small/large-scale fading statistics.

Construção de obras de arte de médio vão através do método construtivo de viga de lançamento (V.L.)

O presente relatório de estágio enquadra-se no âmbito do Trabalho Final de Mestrado no curso de Engenharia Civil, perfil de Estruturas, do Instituto Superior de Engenharia de Lisboa. Desta forma, foi realizado um estágio na empresa Opway – Engenharia, com a duração de 16 semanas, com integração na Direcção Técnica e de Inovação desempenhando as funções de análise e acompanhamento de obras de arte especiais de médio vão. Pretende-se demonstrar, neste relatório, a grande especificidade deste tipo de construções quer ao nível do Dimensionamento como ao nível da Construção. Ao nível do processo de Dimensionamento são apresentados dois capítulos, um relativo ao projecto de alterações de uma Viga de Lançamento e outro relativo ao projecto de execução de um viaduto construído através deste tipo de cimbres. Desta forma, o Capítulo 2 aborda os principais factores a ter em consideração num caso de adaptação de um cimbre deste tipo, utilizado anteriormente num determinado tabuleiro, para um novo tabuleiro a realizar, com características necessariamente diferentes. Por sua vez, o Capítulo 5 prende-se com uma análise e descrição de um projecto de execução de um tabuleiro de um viaduto construído por este método construtivo. No âmbito de Construção, o Capítulo 3 aborda o método de funcionamento deste tipo de cimbres desde que chega ao local da empreitada, até à sua saída. O Capítulo 4 consiste numa avaliação de soluções para a construção de um tabuleiro, onde a solução inicial consistia na construção por avanços sucessivos enquanto que a solução variante, (adoptada), consiste na construção por lançamento incremental. Neste capítulo está demonstrada a variação de quantidades de materiais entre as duas soluções e consequentemente a sua tradução em valores monetários. Os casos de estudo, que serviram como base de trabalho, ao nível do acompanhamento da construção foram, o Viaduto ferroviário de alta velocidade “O Marco”, em Santiago de Compostela e o Viaduto sobre o Rio Águeda em Ciudad Rodrigo. Ao nível do aspecto de projecto, o caso em estudo foi do Viaduto sobre a Ribeira de Zacarias (V3), integrado na subconcessão do Douro Interior, Alfândega da Fé. Este relatório resulta da análise de documentos relativos aos diferentes tipos de projecto mencionados como também da oportunidade de realização de acompanhamento da construção deste tipo de obras de arte.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Modelo de especificação e controlo de execuções paralelas e distribuídas

O desenvolvimento actual de aplicações paralelas com processamento intensivo (HPC - High Performance Computing) para alojamento em computadores organizados em Cluster baseia-se muito no modelo de passagem de mensagens, do qual é de realçar os esforços de definição de standards, por exemplo, MPI - Message - Passing Interface. Por outro lado, com a generalização do paradigma de programação orientado aos objectos para ambientes distribuídos (Java RMI, .NET Remoting), existe a possibilidade de considerar que a execução de uma aplicação, de processamento paralelo e intensivo, pode ser decomposta em vários fluxos de execução paralela, em que cada fluxo é constituído por uma ou mais tarefas executadas no contexto de objectos distribuídos. Normalmente, em ambientes baseados em objectos distribuídos, a especificação, controlo e sincronização dos vários fluxos de execução paralela, é realizada de forma explicita e codificada num programa principal (hard-coded), dificultando possíveis e necessárias modificações posteriores. No entanto, existem, neste contexto, trabalhos que propõem uma abordagem de decomposição, seguindo o paradigma de workflow com interacções entre as tarefas por, entre outras, data-flow, control-flow, finite - state - machine. Este trabalho consistiu em propor e explorar um modelo de execução, sincronização e controlo de múltiplas tarefas, que permita de forma flexível desenhar aplicações de processamento intensivo, tirando partido da execução paralela de tarefas em diferentes máquinas. O modelo proposto e consequente implementação, num protótipo experimental, permite: especificar aplicações usando fluxos de execução; submeter fluxos para execução e controlar e monitorizar a execução desses fluxos. As tarefas envolvidas nos fluxos de execução podem executar-se num conjunto de recursos distribuídos. As principais características a realçar no modelo proposto, são a expansibilidade e o desacoplamento entre as diferentes componentes envolvidas na execução dos fluxos de execução. São ainda descritos casos de teste que permitiram validar o modelo e o protótipo implementado. Tendo consciência da necessidade de continuar no futuro esta linha de investigação, este trabalho é um contributo para demonstrar que o paradigma de workflow é adequado para expressar e executar, de forma paralela e distribuída, aplicações complexas de processamento intensivo.

Atas do V Encontro do CIED - Escola e Comunidade

Esta publicação contém as comunicações apresentadas no V Encontro do CIED – Escola e Comunidade, nos dias 18 e 19 de novembro de 2011, na Escola Superior de Educação de Lisboa, Instituto Politécnico de Lisboa, organizado pelo CIED, com o apoio da Escola Superior de Educação de Lisboa

Effect of the number of shells on the pressure and energy of two-dimensional free bubble clusters

We have performed Surface Evolver simulations of two-dimensional hexagonal bubble clusters consisting of a central bubble of area lambda surrounded by s shells or layers of bubbles of unit area. Clusters of up to twenty layers have been simulated, with lambda varying between 0.01 and 100. In monodisperse clusters (i.e., for lambda = 1) [M.A. Fortes, F Morgan, M. Fatima Vaz, Philos. Mag. Lett. 87 (2007) 561] both the average pressure of the entire Cluster and the pressure in the central bubble are decreasing functions of s and approach 0.9306 for very large s, which is the pressure in a bubble of an infinite monodisperse honeycomb foam. Here we address the effect of changing the central bubble area lambda. For small lambda the pressure in the central bubble and the average pressure were both found to decrease with s, as in monodisperse clusters. However, for large,, the pressure in the central bubble and the average pressure increase with s. The average pressure of large clusters was found to be independent of lambda and to approach 0.9306 asymptotically. We have also determined the cluster surface energies given by the equation of equilibrium for the total energy in terms of the area and the pressure in each bubble. When the pressures in the bubbles are not available, an approximate equation derived by Vaz et al. [M. Fatima Vaz, M.A. Fortes, F. Graner, Philos. Mag. Lett. 82 (2002) 575] was shown to provide good estimations for the cluster energy provided the bubble area distribution is narrow. This approach does not take cluster topology into account. Using this approximate equation, we find a good correlation between Surface Evolver Simulations and the estimated Values of energies and pressures. (C) 2008 Elsevier B.V. All rights reserved.

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

The organ verses of Frei Jerónimo da Madre de Deus: Portuguese organ music in the time of D. João V

Contrastando com o importante legado dos mestres organistas portugueses dos séculos XVI e XVII, a música portuguesa para órgão pós-1700 parece quase inexistente (excluindo raros exemplos, como as quatro sonatas para órgão de Carlos Seixas). Seja devido à destruição causada pelo grande terramoto de Lisboa em 1755, ou a outras causas, a ausência de fontes é surpreendente, considerando os testemunhos de actividade musical durante aquele período. Este artigo lida com uma fonte até hoje relativamente ignorada: o manuscrito CLI/1-4 nº 7 da Biblioteca do Palácio Ducal de Vila Viçosa (Versos / Sobre o Canto Chão / Para Orgão / De Fr. Jeronimo da M.dre de DS.). Esta colecção de vinte versos para órgão de Jerónimo da Madre de Deus é, de longe, a maior obra portuguesa para órgão da primeira metade do século XVIII até hoje conhecida. Claramente pensadas para o órgão, estas curtas peças testemunham a transformação da escrita para tecla em Portugal durante o reinado de D. João V (nomeadamente através da absorção de influências italianas) e fornecem informações preciosas sobre o tipo de instrumento em que eram tocadas.

Cluster de volatilidade no mercado de taxas de câmbio USD/GBP

Mestrado em Controlo de Gestão e dos Negócios

On the choice of posittioning and cluster size for fixed relay stations in a LTE network

The long term evolution (LTE) is one of the latest standards in the mobile communications market. To achieve its performance, LTE networks use several techniques, such as multi-carrier technique, multiple-input-multiple-output and cooperative communications. Inside cooperative communications, this paper focuses on the fixed relaying technique, presenting a way for determining the best position to deploy the relay station (RS), from a set of empirical good solutions, and also to quantify the associated performance gain using different cluster size configurations. The best RS position was obtained through realistic simulations, which set it as the middle of the cell's circumference arc. Additionally, it also confirmed that network's performance is improved when the number of RSs is increased. It was possible to conclude that, for each deployed RS, the percentage of area served by an RS increases about 10 %. Furthermore, the mean data rate in the cell has been increased by approximately 60 % through the use of RSs. Finally, a given scenario with a larger number of RSs, can experience the same performance as an equivalent scenario without RSs, but with higher reuse distance. This conduces to a compromise solution between RS installation and cluster size, in order to maximize capacity, as well as performance.

Intraplate seismicity across the Cape Verde swell: a contribution from a temporary seismic network

We present an analysis and characterization of the regional seismicity recorded by a temporary broadband seismic network deployed in the Cape Verde archipelago between November 2007 and September 2008. The detection of earthquakes was based on spectrograms, allowing the discrimination from low-frequency volcanic signals, resulting in 358 events of which 265 were located, the magnitudes usually being smaller than 3. For the location, a new 1-D P-velocity model was derived for the region showing a crust consistent with an oceanic crustal structure. The seismicity is located mostly offshore the westernmost and geologically youngest areas of the archipelago, near the islands of Santo Antao and Sao Vicente in the NW and Brava and Fogo in the SW. The SW cluster has a lower occurrence rate and corresponds to seismicity concentrated mainly along an alignment between Brava and the Cadamosto seamount presenting normal faulting mechanisms. The existence of the NW cluster, located offshore SW of Santo Antao, was so far unknown and concentrates around a recently recognized submarine cone field; this cluster presents focal depths extending from the crust to the upper mantle and suggests volcanic unrest No evident temporal behaviour could be perceived, although the events tend to occur in bursts of activity lasting a few days. In this recording period, no significant activity was detected at Fogo volcano, the most active volcanic edifice in Cape Verde. The seismicity characteristics point mainly to a volcanic origin. The correlation of the recorded seismicity with active volcanic structures agrees with the tendency for a westward migration of volcanic activity in the archipelago as indicated by the geologic record. (C) 2014 Elsevier B.V. All rights reserved.

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.

Laser-induced diffusion decomposition in Fe-V thin-film alloys

We investigate the origin of ferromagnetism induced in thin-film (similar to 20 nm) Fe-V alloys by their irradiation with subpicosecond laser pulses. We find with Rutherford backscattering that the magnetic modifications follow a thermally stimulated process of diffusion decomposition, with formation of a-few-nm-thick Fe enriched layer inside the film. Surprisingly, similar transformations in the samples were also found after their long-time (similar to 10(3) s) thermal annealing. However, the laser action provides much higher diffusion coefficients (similar to 4 orders of magnitude) than those obtained under standard heat treatments. We get a hint that this ultrafast diffusion decomposition occurs in the metallic glassy state achievable in laser-quenched samples. This vitrification is thought to be a prerequisite for the laser-induced onset of ferromagnetism that we observe. 2014 Elsevier B.V. All rights reserved.