Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

On the monoids of transformations that preserve the order and a uniform partition

In this article we consider the monoid O(mxn) of all order-preserving full transformations on a chain with mn elements that preserve a uniformm-partition and its submonoids O(mxn)(+) and O(mxn)(-) of all extensive transformations and of all co-extensive transformations, respectively. We determine their ranks and construct a bilateral semidirect product decomposition of O(mxn) in terms of O(mxn)(-) and O(mxn)(+).

Smart Electric Vehicle Charging System

In this work is proposed the design of a system to create and handle Electric Vehicles (EV) charging procedures, based on intelligent process. Due to the electrical power distribution network limitation and absence of smart meter devices, Electric Vehicles charging should be performed in a balanced way, taking into account past experience, weather information based on data mining, and simulation approaches. In order to allow information exchange and to help user mobility, it was also created a mobile application to assist the EV driver on these processes. This proposed Smart ElectricVehicle Charging System uses Vehicle-to-Grid (V2G) technology, in order to connect Electric Vehicles and also renewable energy sources to Smart Grids (SG). This system also explores the new paradigm of Electrical Markets (EM), with deregulation of electricity production and use, in order to obtain the best conditions for commercializing electrical energy.

Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

The influence of curing conditions on the mechanical performance of concrete made with recycled concrete waste

Research on the use of Construction and Demolition Waste (CDW) as recycled aggregate (in particular crushed concrete) for the production of new concrete has by now established the feasibility of this environmentally-friendly use of otherwise harmful waste. However, contrary to conventional concrete (CC), no large applications of concrete made with recycled concrete have been made and there is still a lack of knowledge in some areas of production and performance of recycled aggregate concrete (RAC). One issue concerns curing conditions: these greatly affect the performance of concrete made on site and some potential users of RAC wonder how RAC is affected by far-from-ideal curing conditions. This paper shows the main results of experiments to determine the influence of different curing conditions on the mechanical performance of concrete made with coarse recycled aggregate from crushed concrete. The properties analyzed include compressive strength, splitting tensile strength, modulus of elasticity, and abrasion resistance. The general conclusion in terms of mechanical performance is that RAC is affected by curing conditions roughly in the same way as CC. (C) 2011 Elsevier Ltd. All rights reserved.

Wind turbines equipped with fractional-order controllers: Stress on the mechanical drive train due to a converter control malfunction

This paper is on variable-speed wind turbines with permanent magnet synchronous generator (PMSG). Three different drive train mass models and three different topologies for the power-electronic converters are considered. The three different topologies considered are respectively a matrix, a two-level and a multilevel converter. A novel control strategy, based on fractional-order controllers, is proposed for the wind turbines. Simulation results are presented to illustrate the behaviour of the wind turbines during a converter control malfunction, considering the fractional-order controllers. Finally, conclusions are duly drawn. Copyright (C) 2010 John Wiley & Sons, Ltd.

Estudo dos indicadores de qualidade e de risco na interaça o mãe-filho(a)

O presente estudo tem como principal objetivo identificar na interação mãe- bebés de 3 meses, indicadores de risco e de qualidade e, consequentemente, criar um guião que ajude os profissionais a identificar esses mesmos indicadores. Para o efeito observámos 30 díades mãe-filho(a) em jogo livre distribuídas em dois grupos: 1) 12 díades sem condições assinaláveis de risco e 2) 18 díades em risco socioeconómico. O comportamento interativo dos bebés e das mães foi avaliado através do Child-Adult Relashionship Experimental, designado pela autora de CARE-Index (Crittenden, 2003). Os comportamentos maternos e infantis foram cotados de acordo com os 7 aspetos do comportamento diádico: Expressão Facial, Expressão Verbal, Posição e Contato Corporal, Afetividade, Reciprocidade, Diretividade e Escolha da Atividade. Os resultados do nosso estudo revelam que as díades mãe-filho(a) sem condições assinaláveis de risco apresentam interações mais positivas, recíprocas e ajustadas à idade das crianças do que as díades sujeitas a condições de risco e que o comportamento materno sensível e responsivo surge associado ao comportamento cooperativo infantil e negativamente correlacionado com a dificuldade infantil, enquanto que uma postura controladora, diretiva ou punitiva da mãe surge positivamente correlacionada com a submissão e evitamento infantil. Por fim, encontramos associados a comportamentos maternos sensíveis uma variabilidade de comportamentos infantis desde satisfação, coerção, procura de proximidade ou evitamento. Na discussão dos resultados apresentamos um script dos indicadores de qualidade e de risco do comportamento materno. - Abstract This study main goal was to study mother-infant quality of interaction in dyads with 3 months babies. Moreover, our goal was to explore maternal and infant key behaviors that shape the quality of the interaction in order to organize a script that helps professionals to identify these critical interactive behaviors. To this end we observed 30 mother-child dyads (a) in free play interaction divided into two groups: 1) 12 dyads without any known risk condition and 2) 18 dyads at socioeconomic risk. The interactive behavior of infants and mothers was assessed using the Child-Adult Relationship Experimental, designated by the author of CARE-Index (Crittenden, 2003). The maternal and infant behaviors were rated according to seven aspects of dyadic behavior: Facial Expression, Verbal Expression, Position and Contact Body, Affection, Reciprocity, Directivity and Choice of Activity. Findings indicate that mother-child dyads without know risk conditions are more likely to present positive interactions, reciprocal and age-adjusted than dyads at risk. The sensitive and responsive maternal behavior emerges associated with children's cooperative behavior and negatively correlated with infant difficultness, while a controlling or punitive maternal behavior is positively correlated with infant compliance and avoidance. Finally, sensitive maternal behaviors were associated with a variability of child behaviors, from satisfaction, coercion, avoidance or proximity search. In the results discussion we present a script of the quality and risks indicators of maternal behavior.

Será que as empresas portuguesas seguem a pecking order na escolha das alternativas de financiamento?

Mestrado em Contabilidade e Análise Financeira

A educação de adultos: um novo desafio organizacional na escola pública

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação Especialização em Administração Escolar

Validação da eficácia dos procedimentos de limpeza, no equipamento de fabrico e embalagem, na indústria farmacêutica

Na indústria farmacêutica, a limpeza dos equipamentos e superfícies é muito importante no processo de fabrico/embalagem dos produtos farmacêuticos. Possíveis resíduos contaminantes devem ser removidos dos equipamentos e das superfícies envolvidas no processo. De acordo com as Boas Práticas de Fabrico (GMP), os procedimentos de limpeza e os métodos analíticos usados para determinar as quantidades de resíduos devem ser validados. O método analítico combinado com o método de amostragem utilizado na colheita de amostras deve ser sujeito a um ensaio de “recovery”. Neste trabalho apresenta-se uma estratégia inovadora para a validação de limpeza de formas farmacêuticas semi-sólidas. Propõe-se o uso de um método de amostragem que consiste na colheita direta de amostra após o seu fabrico, sendo a análise de resíduos feita directamente nesta amostra. Os produtos escolhidos para a avaliação da estratégia foram dois medicamentos dermatológicos, apresentados na forma de pomada e produzidos numa unidade de fabrico de vários produtos, pela Schering Plough Farma/ Merck Sharp & Dohme (Cacém, Portugal). Como métodos analíticos para a quantificação dos resíduos, utilizaram-se métodos validados por via espectrofotométrica (HPLC), usados na análise do produto acabado. A validação de limpeza foi avaliada através da análise de uma quantidade conhecida de pomada (produto B (*)), usando o método de análise da pomada fabricada anteriormente (produto A (*)), de modo a verificar-se a existência ou não de agente de limpeza e substâncias ativas deixadas após a limpeza do produto A, e vice-versa. As concentrações residuais das substâncias ativas e do agente de limpeza encontradas após a limpeza foram nulas, ou seja, inferiores ao limite de deteção (LOD), sendo que o critério de aceitação da limpeza utilizado foi de 6,4 x 10-4 mg/g para a substância ativa 1 (*); 1,0 x 10-2 mg/g para a substância ativa 2 (*); 1,0 x 10-3 mg/g para a substância ativa 3 (*) e de 10 ppm para o agente de limpeza. No ensaio de “recovery”, obtiveram-se resultados acima de 70% para todas as substâncias ativas e para o agente de limpeza nas duas pomadas. Antes de se proceder a este ensaio de “recovery”, houve a necessidade de ajustar as condições cromatográficas dos métodos analíticos de ambos os produtos e do agente de limpeza, por forma a obter-se valores da conformidade do sistema (fator de tailling e de resolução) de acordo com as especificações. A precisão dos resultados, reportada como desvio padrão relativo (RSD), deu abaixo de 2,0%, excepto nos ensaios que envolvem a substância ativa 3, cuja especificação é inferior a 10,0%. Os resultados obtidos demonstraram que os procedimentos de limpeza usados na unidade de fabrico em causa são eficazes, eliminando assim a existência de contaminação cruzada.

Determination of stresses around a cylindrical single pile caused by horizontal movements of soils with the finitive element method

This study was carried out with the aim of modeling in 2D, in plain strain, the movement of a soft cohesive soil around a pile, in order to enable the determination of stresses resulting along the pile, per unit length. The problem in study fits into the large deformations problem and can be due to landslide, be close of depth excavations, to be near of zones where big loads are applied in the soil, etc. In this study is used an constitutive Elasto-Plastic model with the failure criterion of Mohr-Coulomb to model the soil behavior. The analysis is developed considering the soil in undrained conditions. To the modeling is used the finite element program PLAXIS, which use the Updated Lagrangian - Finite Element Method (UL-FEM). In this work, special attention is given to the soil-pile interaction, where is presented with some detail the formulation of the interface elements and some studies for a better understand of his behavior. It is developed a 2-D model that simulates the effect of depth allowing the study of his influence in the stress distribution around the pile. The results obtained give an important base about how behaves the movement of the soil around a pile, about how work the finite element program PLAXIS and how is the stress distribution around the pile. The analysis demonstrate that the soil-structure interaction modeled with the UL-FEM and interface elements is more appropriate to small deformations problems.

Manutenção preventiva de um edifício hospitalar

Os Hospitais, equipamentos de interesse público, são edifícios cujos desempenho e disponibilidade das suas instalações e equipamentos podem comprometer a prestação de cuidados de saúde, pelo que nestes estabelecimentos, a Manutenção Preventiva assume um papel relevante. Nesse sentido, pretendeu-se nesta dissertação definir uma estratégia específica que permita efectuar o planeamento da manutenção preventiva de um edifício hospitalar, enquanto infraestrutura para desenvolvimento da actividade clínica. Para tal, foi efectuada uma pesquisa bibliográfica, com a qual se identificaram conceitos de manutenção e requisitos a serem tidos em conta na manutenção de edifícios hospitalares. Foi efectuada uma caracterização genérica do objecto de manutenção, limitada no âmbito desta dissertação às principais componentes dos sistemas de construção e das instalações de águas e esgotos, que podem integrar um edifício hospitalar actual, atendendo às especificações e recomendações técnicas vigentes para este tipo de edifícios. Foram identificados os objectivos e requisitos de manutenção nestes edifícios, estabelecidos pelas condições de funcionamento pretendidas, pelos critérios de durabilidade exigidos pelo Dono de Obra, pelo nível de desempenho funcional requerido para as suas componentes e pelo grau de operacionalidade imposto nas suas diferentes unidades funcionais. Tendo em consideração que a criticidade de uma componente não depende só do contexto operacional da área funcional em se insere mas também das consequências que o seu estado de funcionamento pode acarretar para a unidade funcional. Foi exemplificada a análise dos modos de falha, sua criticidade e seus efeitos para hierarquização do risco associado nas componentes estudadas. As fichas exemplificativas dos planos de manutenção preventiva, que se apresentam no âmbito desta dissertação para algumas componentes básicas, integram acções e procedimentos que derivam de uma análise aos seus modos de falha e seus efeitos, bem como de recomendações técnicas exigências da regulamentação em vigor.

Exposição a partículas e eventuais efeitos sobre a saúde

Mestrado em Segurança e Higiene do Trabalho.

Commercial agents portfolio optimization in electricity markets

As it is well known, competitive electricity markets require new computing tools for power companies that operate in retail markets in order to enhance the management of its energy resources. During the last years there has been an increase of the renewable penetration into the micro-generation which begins to co-exist with the other existing power generation, giving rise to a new type of consumers. This paper develops a methodology to be applied to the management of the all the aggregators. The aggregator establishes bilateral contracts with its clients where the energy purchased and selling conditions are negotiated not only in terms of prices but also for other conditions that allow more flexibility in the way generation and consumption is addressed. The aggregator agent needs a tool to support the decision making in order to compose and select its customers' portfolio in an optimal way, for a given level of profitability and risk.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.