Synthesis, structural characterization and leishmanicidal activity evaluation of ferrocenyl N-heterocyclic compounds

Agência Financiadora: FCT - PTDC/QUI/72656/2006 ; SFRH/BPD/27454/2006; SFRH/BPD/44082/2008; SFRH/BPD/41138/2007

Benzo[c]thiophene chromophores linked to cationic Fe and Ru derivatives for NLO materials: synthesis characterization and quadratic hyperpolarizabilities

5-Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(5-C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5-[3-(thiophen-2-yl)benzo[c]thiophenyl]thiophene-2-carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyperpolarizabilities. The compounds were fully characterized by NMR, FTIR and UV/Vis spectroscopy and their electrochemical behaviour studied by cyclic voltammetry. Quadratic hyperpolarizabilities () were determined by hyper-Rayleigh scattering measurements at a fundamental wavelength of 1500 nm. Density functional theory calculations were employed to rationalize the second-order non-linear optical properties of these complexes.

Informal learning recognition through a cloud ecosystem

Learning and teaching processes, like all human activities, can be mediated through the use of tools. Information and communication technologies are now widespread within education. Their use in the daily life of teachers and learners affords engagement with educational activities at any place and time and not necessarily linked to an institution or a certificate. In the absence of formal certification, learning under these circumstances is known as informal learning. Despite the lack of certification, learning with technology in this way presents opportunities to gather information about and present new ways of exploiting an individual’s learning. Cloud technologies provide ways to achieve this through new architectures, methodologies, and workflows that facilitate semantic tagging, recognition, and acknowledgment of informal learning activities. The transparency and accessibility of cloud services mean that institutions and learners can exploit existing knowledge to their mutual benefit. The TRAILER project facilitates this aim by providing a technological framework using cloud services, a workflow, and a methodology. The services facilitate the exchange of information and knowledge associated with informal learning activities ranging from the use of social software through widgets, computer gaming, and remote laboratory experiments. Data from these activities are shared among institutions, learners, and workers. The project demonstrates the possibility of gathering information related to informal learning activities independently of the context or tools used to carry them out.

Preparação e análise estrutural de complexos de samário

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica - Ramo de Bioprocessos

Relatório de estágio na Empresa Biodroid Entertainment

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Redes de Comunicação e Multimédia

Casos especiais na avaliação de empresas

Mestrado em Controlo de Gestão e dos Negócios

Padrão epidemiológico das oclusopatias muito graves em adolescentes brasileiros

OBJETIVO: Descrever o padrão de distribuição das oclusopatias em adolescentes brasileiros e identificar fatores associados a esse agravo bucal. MÉTODOS: Foram analisados dados de 7.328 e 5.445 adolescentes de 12 e 15-19 anos, respectivamente, participantes da Pesquisa Nacional de Saúde Bucal (SBBrasil 2010). O desfecho foi oclusopatia muito grave segundo o índice de estética dental. As variáveis de exposição foram sexo, cor da pele, renda familiar mensal, número de bens, aglomeração no domicílio, cárie não tratada, perda dentária, uso, frequência e motivo da consulta odontológica. Foram conduzidas análises de regressão logística considerando a complexidade do desenho amostral, com base em modelo hierarquizado. RESULTADOS: Prevalência de oclusopatia muito grave foi observada em 6,5% e 9,1% nos jovens de 12 e 15-19 anos, respectivamente. Após análise ajustada, a chance do desfecho foi 1,59 (IC95% 1,08;2,34) vez maior nos pardos e pretos em relação aos brancos e 2,66 (IC95% 1,26;5,63) vezes maior dentre aqueles com perda de pelo menos um primeiro molar aos 12 anos. Jovens de 15-19 anos cuja renda familiar mensal foi de até R$ 1.500,00 (OR 2,69 [IC95% 1,62;4,47]) e aqueles que consultaram o dentista para tratamento (OR 2,59 [IC95% 2,55;4,34]) apresentaram maior chance de oclusopatia muito grave quando comparados aos de maior renda e que procuraram o dentista para prevenção. CONCLUSÕES: A distribuição das oclusopatias em adolescentes brasileiros segue o padrão de iniquidade social de outros agravos à saúde. Essas informações são úteis para a formulação de critérios relacionados tanto com a distribuição e provisão de recursos quanto com as prioridades de tratamento ortodôntico fundamentados no princípio da equidade da atenção à saúde bucal.

Inquéritos populacionais como instrumentos de gestão e os modelos de atenção à saúde

O artigo faz uma breve sistematização dos modelos de atenção em saúde, enfatiza o papel do inquérito populacional como instrumento de gestão e analisa o caso específico da Pesquisa Nacional de Saúde Bucal (SBBrasil 2010), ressaltando a sua contribuição no processo de consolidação de modelos de atenção compatíveis com os princípios do Sistema Único de Saúde. Ainda que no plano legal o Sistema Único de Saúde corresponda a um modelo de atenção em saúde, no plano concreto das políticas públicas e das ações, o sistema dá origem a um modelo que resulta não de textos jurídicos nem de formulações teóricas, mas da práxis dos agentes envolvidos. Considerando que a gestão do cotidiano em saúde é um espaço privilegiado e prioritário para a produção e consolidação dos modelos de atenção à saúde, é necessário estimular e apoiar o desenvolvimento de competências técnicas e operacionais diferentes daquelas necessárias à gerência dos cuidados relacionados às demandas individuais.

Avanços e desafios à Política de Vigilância à Saúde Bucal no Brasil

Revisão crítica e integrativa, de caráter descritivo-discursivo, dedicada à explanação da política de vigilância à saúde bucal vigente atualmente no Brasil. Com base em uma apreciação crítica dos trabalhos nacionais e internacionais consultados sobre a temática da vigilância à saúde, examina-se a formulação de uma agenda política e científica em vigilância à saúde bucal, ancorada na institucionalidade do Sistema Único de Saúde. A efetivação da referida agenda é exemplificada com a apresentação da Pesquisa Nacional de Saúde Bucal (SBBrasil 2010). Uma síntese conclusiva é apresentada, buscando a convergência teórico-metodológica entre a identificação, por um lado, dos obstáculos e fragilidades ainda detectáveis na implementação da agenda e, por outro, no reconhecimento do seu mérito, discernível em expressivos avanços e conquistas já consolidados.

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

Determinants of using pacifier and bottle feeding

OBJECTIVE To analyze the factors associated with the use of pacifiers and/or bottle feeding in infants aged under one year.METHODS This is a cross-sectional study with 34,366 children and using data from the database of the 2nd Nationwide Survey of Breastfeeding Prevalence performed in the Brazilian capitals and Federal District in 2008. Cluster sampling was used. The questionnaire included questions about the use of artificial nipples in the last 24 hours. The analysis considered three outcomes: exclusive use of pacifier, exclusive use of bottle feeding, and use of artificial nipples (pacifier and bottle feeding). Prevalence ratios were obtained using Poisson regression with robust variance following a hierarchical model.RESULTS The following factors were associated with exclusive use of the pacifier: mother working outside the home, primiparity, child was not breastfed within the first hour, and child had consumed tea on the first day at home. The following factors were associated with exclusive use of bottle feeding: mother working outside the home, primiparity, low birth weight, child not breastfed within the first hour, and child had consumed milk formula and tea on the first day at home. The following factors were associated with use of artificial nipples (pacifier and bottle feeding): mother working outside the home, primiparity, cesarean delivery, the male gender, low birth weight, born in a hospital not accredited as “baby friendly”, required health baby monitoring in the Primary Health Care Unit (PR = 0.91), and child had consumed milk formula, water, or tea on the first day at home.CONCLUSIONS This study identified profiles of exclusive users of pacifiers, bottle feeding, and both. The provided information can guide preventive practices for child health.

Enabling Global Experiments With Interactive Reconfiguration And Steering By Multiple Users

In global scientific experiments with collaborative scenarios involving multinational teams there are big challenges related to data access, namely data movements are precluded to other regions or Clouds due to the constraints on latency costs, data privacy and data ownership. Furthermore, each site is processing local data sets using specialized algorithms and producing intermediate results that are helpful as inputs to applications running on remote sites. This paper shows how to model such collaborative scenarios as a scientific workflow implemented with AWARD (Autonomic Workflow Activities Reconfigurable and Dynamic), a decentralized framework offering a feasible solution to run the workflow activities on distributed data centers in different regions without the need of large data movements. The AWARD workflow activities are independently monitored and dynamically reconfigured and steering by different users, namely by hot-swapping the algorithms to enhance the computation results or by changing the workflow structure to support feedback dependencies where an activity receives feedback output from a successor activity. A real implementation of one practical scenario and its execution on multiple data centers of the Amazon Cloud is presented including experimental results with steering by multiple users.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Human-robot teamwork: a knowledge-based solution

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Electrotécnica e de Computadores

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.