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.

Assessment of fungal contamination in waste sorting and incineration: case study in Portugal

Organic waste is a rich substrate for microbial growth, and because of that, workers from waste industry are at higher risk of exposure to bioaerosols. This study aimed to assess fungal contamination in two plants handling solid waste management. Air samples from the two plants were collected through an impaction method. Surface samples were also collected by swabbing surfaces of the same indoor sites. All collected samples were incubated at 27◦C for 5 to 7 d. After lab processing and incubation of collected samples, quantitative and qualitative results were obtained with identification of the isolated fungal species. Air samples were also subjected to molecular methods by real-time polymerase chain reaction (RT PCR) using an impinger method to measure DNA of Aspergillus flavus complex and Stachybotrys chartarum. Assessment of particulate matter (PM) was also conducted with portable direct-reading equipment. Particles concentration measurement was performed at five different sizes (PM0.5; PM1; PM2.5; PM5; PM10). With respect to the waste sorting plant, three species more frequently isolated in air and surfaces were A. niger (73.9%; 66.1%), A. fumigatus (16%; 13.8%), and A. flavus (8.7%; 14.2%). In the incineration plant, the most prevalent species detected in air samples were Penicillium sp. (62.9%), A. fumigatus (18%), and A. flavus (6%), while the most frequently isolated in surface samples were Penicillium sp. (57.5%), A. fumigatus (22.3%) and A. niger (12.8%). Stachybotrys chartarum and other toxinogenic strains from A. flavus complex were not detected. The most common PM sizes obtained were the PM10 and PM5 (inhalable fraction). Since waste is the main internal fungal source in the analyzed settings, preventive and protective measures need to be maintained to avoid worker exposure to fungi and their metabolites.

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

Mestrado em Contabilidade e Gestão das Instituições Financeiras

Vertex component analysis: a fast algorithm to extract endmembers spectra from hyperspectral data

Chapter in Book Proceedings with Peer Review First Iberian Conference, IbPRIA 2003, Puerto de Andratx, Mallorca, Spain, JUne 4-6, 2003. Proceedings

Vertex component analysis: a fast algorithm to unmix hyperspectral data

Given a set of mixed spectral (multispectral or hyperspectral) vectors, linear spectral mixture analysis, or linear unmixing, aims at estimating the number of reference substances, also called endmembers, their spectral signatures, and their abundance fractions. This paper presents a new method for unsupervised endmember extraction from hyperspectral data, termed vertex component analysis (VCA). The algorithm exploits two facts: (1) the endmembers are the vertices of a simplex and (2) the affine transformation of a simplex is also a simplex. In a series of experiments using simulated and real data, the VCA algorithm competes with state-of-the-art methods, with a computational complexity between one and two orders of magnitude lower than the best available method.

Reabilitação energética de um edifício de índole cultural: Centro Cultural de Belém

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

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

Fast growing fungi: a problem to be solved to achieve characterization of occupational exposure to fungi in cork industry

Chrysonilia sitophila is a common mould in cork industry and has been identified as a cause of IgE sensitization and occupational asthma. This fungal species have a fast growth rate that may inhibit others species’ growth causing underestimated data from characterization of occupational fungal exposure. Aiming to ascertain occupational exposure to fungi in cork industry, were analyzed papers from 2000 about the best air sampling method, to obtain quantification and identification of all airborne culturable fungi, besides the ones that have fast-growing rates. Impaction method don’t allows the collection of a representative air volume, because even with some media that restricts the growth of the colonies, in environments with higher fungal load, such as cork industry, the counting of the colonies is very difficult. Otherwise, impinger method permits the collection of a representative air volume, since we can make dilution of the collected volume. Besides culture methods that allows fungal identification trough macro- and micro-morphology, growth features, thermotolerance and ecological data, we can apply molecular biology with the impinger method, to detect the presence of non-viable particles and potential mycotoxin producers’ strains, and also to detect mycotoxins presence with ELISA or HPLC. Selection of the best air sampling method in each setting is crucial to achieve characterization of occupational exposure to fungi. Information about the prevalent fungal species in each setting and also the eventual fungal load it’s needed for a criterious selection.

Occupational exposure to particulate matter in 2 Portuguese waste-sorting units

Objectives - This study intended to characterize work environment contamination by particles in 2 waste-sorting plants. Material and Methods - Particles were measured by portable direct-reading equipment. Besides mass concentration in different sizes, data related with the number of particles concentration were also obtained. Results - Both sorting units showed the same distribution concerning the 2 exposure metrics: particulate matter 5 (PM5) and particulate matter 10 (PM10) reached the highest levels and 0.3 μm was the fraction with a higher number of particles. Unit B showed higher (p < 0.05) levels for both exposure metrics. For instance, in unit B the PM10 size is 9-fold higher than in unit A. In unit A, particulate matter values obtained in pre-sorting and in the sequential sorting cabinet were higher without ventilation working. Conclusions - Workers from both waste-sorting plants are exposed to particles. Particle counting provided additional information that is of extreme value for analyzing the health effects of particles since higher values of particles concentration were obtained in the smallest fraction.

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)