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.

Lichens as biomonitors at indoor environments of primary schools

A biomonitoring study, using transplanted lichens Flavoparmelia caperata, was conducted to assess the indoor air quality in primary schools in urban (Lisbon) and rural (Ponte de Sor) Portuguese sites. The lichens exposure period occurred between April and June 2010 and two types of environments of the primary schools were studied: classrooms and outdoor/courtyard. Afterwards, the lichen samples were processed and analyzed by instrumental neutron activation analysis (INAA) to assess a total of 20 chemical elements. Accumulated elements in the exposed lichens were assessed and enrichment factors (EF) were determined. Indoor and outdoor biomonitoring results were compared to evaluate how biomonitors (as lichens) react at indoor environments and to assess the type of pollutants that are prevalent in those environments.

As imagens dos manuais escolares: representações mentais de professores e alunos relativamente à presença de imagens nos manuais escolares e à sua eficácia pedagógica

Sendo o manual escolar o recurso pedagógico mais utilizado por alunos e professores foi realizada uma investigação tendo por objectivo avaliar qualitativamente a forma comunicacional de um conjunto de manuais escolares do 2º ciclo do ensino básico1. A importância atribuída atualmente à imagem é patente nos manuais escolares, sob pretexto de se tornarem mais apelativos e mais eficazes. Tal como em outras áreas em que a quantidade de imagens acaba por se transformar em poluição visual porque o ser humano não tem capacidade para reagir, simultaneamente, a um demasiado número de estímulos, nas estratégias comunicacionais dos manuais escolares este problema deve ser acautelado porque delas depende a sua qualidade pedagógica. As investigações não comprovam que exista uma relação direta entre a presença de ilustrações num texto e o aumento da sua compreensão. Pelo contrário, há estudos que sugerem que muitas ilustrações falham como potenciadoras da aprendizagem. Neste sentido, da investigação referida, consta uma análise ao rácio imagem/texto e uma auscultação a dois grupos de amostra - professores e alunos – sobre alguns aspectos gerais relativos à presença e eficácia pedagógica das ilustrações dos manuais escolares. Destacamos que, no caso dos alunos, apesar do seu nível de literacia ter constituído um obstáculo ao tratamento das questões, optámos por apresentar as suas respostas.

A transição de aluno a professor: dificuldades e desafios

Dissertação apresentada à Escola Superior de Educação de Lisboa para a obtenção do Grau de Mestre em Ciências da Educação - especialidade Supervisão em Educação

A biosignal embedded system for physiological computing

Thesis submitted in the fulfilment of the requirements for the Degree of Master in Electronic and Telecomunications Engineering

Monitorization of alveolar deposited surface area of nanoparticles and ultrafine particles in different environments

Nanotechnology is an important emerging industry with a projected annual market of around one trillion dollars by 2015. It involves the control of atoms and molecules to create new materials with a variety of useful functions. Although there are advantages on the utilization of these nano-scale materials, questions related with its impact over the environment and human health must be addressed too, so that potential risks can be limited at early stages of development. At this time, occupational health risks associated with manufacturing and use of nanoparticles are not yet clearly understood. However, workers may be exposed to nanoparticles through inhalation at levels that can greatly exceed ambient concentrations. Current workplace exposure limits are based on particle mass, but this criteria could not be adequate in this case as nanoparticles are characterized by very large surface area, which has been pointed out as the distinctive characteristic that could even turn out an inert substance into another substance exhibiting very different interactions with biological fluids and cells. Therefore, it seems that, when assessing human exposure based on the mass concentration of particles, which is widely adopted for particles over 1 μm, would not work in this particular case. In fact, nanoparticles have far more surface area for the equivalent mass of larger particles, which increases the chance they may react with body tissues. Thus, it has been claimed that surface area should be used for nanoparticle exposure and dosing. As a result, assessing exposure based on the measurement of particle surface area is of increasing interest. It is well known that lung deposition is the most efficient way for airborne particles to enter the body and cause adverse health effects. If nanoparticles can deposit in the lung and remain there, have an active surface chemistry and interact with the body, then, there is potential for exposure. It was showed that surface area plays an important role in the toxicity of nanoparticles and this is the metric that best correlates with particle-induced adverse health effects. The potential for adverse health effects seems to be directly proportional to particle surface area. The objective of the study is to identify and validate methods and tools for measuring nanoparticles during production, manipulation and use of nanomaterials.

A Técnica de Dança Clássica na Performance Contemporânea : desenvolvimento de competências técnicas e artísticas, nos alunos dos últimos anos da Academia de Dança Contemporânea de Setúbal, visando a sua entrada no meio artístico profissional

Relatório Final de Estágio apresentado à Escola Superior de Dança com vista à obtenção do grau de Mestre em Ensino de Dança.

Public relations, satisfaction and commitment

The importance of the organizational relationship (senior managers) with an internal public (employees) is the main focus of this research, aiming to understand how this relationship differs between the different publics. Nowadays, the relevance attributed by Public Relations to this relationship is crucial. The main purpose is to identify two consistent models to measure the impact of an organizational relationship on the internal public. The second purpose is to identify how the internal public react to this organizational relationship, namely by gender. The research was conducted in nine Portuguese companies with a sample of 1.244 subjects in order to study the context of the relationship and validate the identified models. The results show the gender stereotypes in the relationship in these companies and that the organizational relationship has an impact on organizational commitment with a consistent model that highlights the impact of Public Relations on a company's productivity.

Tecnologias de apoio e multideficiência: recursos mediadores da aprendizagem e da inclusão

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção do grau de Mestre em Ensino Especial – ramo de Problemas de Cognição e Multideficiência

Contributo do ipad® para o desenvolvimento e aprendizagem de uma criança com limitações motoras e sensoriais

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Educação Especial – ramo de Problemas de Cognição e Multideficiência

Relatório de estágio

Resumo I (Prática Pedagógica) - O Estágio do Ensino Especializado realizado no presente ano lectivo foi elaborado na Academia de Música de Lisboa em três turmas. Vários foram os desafios encontrados no decorrer do ano lectivo, como por exemplo a instabilidade das turmas, a falta do quadro na sala em algumas aulas e a pouca experiência anterior na área de docência. A realização deste estágio permitiu experimentar actividades e estratégias aprendidas nas disciplinas do mestrado e estimulou uma atitude de reflexão regular sobre as escolhas pedagógicas elaboradas e sobre a resposta dos alunos. Também o feedback dos professores da Unidade Curricular de Didáctica do Ensino Especializado foi essencial na consciencialização de aspectos que teriam que ser mudados na minha abordagem do ensino: fazer actividades mais formativas e menos avaliativas, dar mais feedback, não avançar para outro nível enquanto uma tarefa ainda não estiver consolidada, não modificar as instruções tão rapidamente, ter cuidado com a apresentação visual das células rítmicas e pensar em soluções para quando os alunos estão cansados. Foi também importante reflectir sobre os planos de aula realizados ao longo do ano e sobre o que não seria realizado da mesma forma, nomeadamente na introdução de células rítmicas, introdução de funções harmónicas e cadências. Durante este ano foi feito um esforço para melhorar estes aspectos, no entanto ainda não foi possível implementar todas as mudanças. De qualquer modo, esta reflexão é um bom ponto de partida para o planeamento do próximo ano e um exemplo da atitude que deve acompanhar-me durante toda a minha actividade enquanto docente.

Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

Tri-and hexa-cyanoethyl functionalized 17-(L-1) and 42-membered (L-2) macrocyclic compounds were obtained by [1 + 1] (for L-1) or [2 + 2] (for L-2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metalorganic coordination polymers [Ag-2(NO3)(2)L-1](n) (2) and {[Ag2L2](NO3)(2)}(n) (3). The complexes were characterized by elemental analysis, H-1 NMR, C-13 NMR, IR spectroscopies, and ESI-MS; moreover, L-2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N-4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1 kappa N-3:kappa O-2,2 kappa N,3 kappa N,4 kappa N (in 2) or 1 kappa N-3,2 kappa N-3,3 kappa N,4 kappa N fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.

Desenvolvimento de métodos de análise físico-química em águas usando um analisador multiparamétrico AQUAKEM

Trabalho Final de mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).