970 resultados para theoretical basis


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Mestrado em Engenharia Civil – Ramo Tecnologia e Gestão das Construções

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Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

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In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV/mm, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.

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We discuss theoretical and phenomenological aspects of two-Higgs-doublet extensions of the Standard Model. In general, these extensions have scalar mediated flavour changing neutral currents which are strongly constrained by experiment. Various strategies are discussed to control these flavour changing scalar currents and their phenomenological consequences are analysed. In particular, scenarios with natural flavour conservation are investigated, including the so-called type I and type II models as well as lepton-specific and inert models. Type III models are then discussed, where scalar flavour changing neutral currents are present at tree level, but are suppressed by either a specific ansatz for the Yukawa couplings or by the introduction of family symmetries leading to a natural suppression mechanism. We also consider the phenomenology of charged scalars in these models. Next we turn to the role of symmetries in the scalar sector. We discuss the six symmetry-constrained scalar potentials and their extension into the fermion sector. The vacuum structure of the scalar potential is analysed, including a study of the vacuum stability conditions on the potential and the renormalization-group improvement of these conditions is also presented. The stability of the tree level minimum of the scalar potential in connection with electric charge conservation and its behaviour under CP is analysed. The question of CP violation is addressed in detail, including the cases of explicit CP violation and spontaneous CP violation. We present a detailed study of weak basis invariants which are odd under CP. These invariants allow for the possibility of studying the CP properties of any two-Higgs-doublet model in an arbitrary Higgs basis. A careful study of spontaneous CP violation is presented, including an analysis of the conditions which have to be satisfied in order for a vacuum to violate CP. We present minimal models of CP violation where the vacuum phase is sufficient to generate a complex CKM matrix, which is at present a requirement for any realistic model of spontaneous CP violation.

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This article aims to contribute to the discussion of long-term dependence, focusing on the behavior of the main Belgian stock index. Non-parametric analyzes of the general characteristics of temporal frequency show that daily returns are non-ergodic and non-stationary. Therefore, we use the rescaled-range analysis (R/S) and the detrended fluctuation analysis (DFA), under the fractional Brownian motion approach, and we found slight evidence of long-term dependence. These results refute the random walk hypothesis with i.i.d. increments, which is the basis of the EMH in its weak form, and call into question some theoretical modeling of asset pricing. Other more localized complementary study, to identify the evolution of the degree of dependence over time windows, showed that the index has become less persistent from 2010. This may mean a maturing market by the extension of the effects of current financial crisis.

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Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino no 1º e no 2º Ciclos do Ensino Básico

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

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

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The computations performed by the brain ultimately rely on the functional connectivity between neurons embedded in complex networks. It is well known that the neuronal connections, the synapses, are plastic, i.e. the contribution of each presynaptic neuron to the firing of a postsynaptic neuron can be independently adjusted. The modulation of effective synaptic strength can occur on time scales that range from tens or hundreds of milliseconds, to tens of minutes or hours, to days, and may involve pre- and/or post-synaptic modifications. The collection of these mechanisms is generally believed to underlie learning and memory and, hence, it is fundamental to understand their consequences in the behavior of neurons.(...)

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

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This paper addresses the topic of knowledge management in multinational companies (MNCs). Its purpose is to examine the role of expatriates in knowledge acquisition and transfer within MNCs. Specifically it focuses on knowledge acquisition and transfer from one MNC head office located in Germany to two Portuguese subsidiaries as a basis for competitive advantage in their Portuguese subsidiaries. A qualitative research methodology is used, specifically through an exploratory case study approach, which examines how international assignments are important for the role of expatriates In knowledge acquisition and transfer between foreign head offices and their Portuguese subsidiaries. The data were collected through semi structured interviews to 10 Portuguese repatriates from two Portuguese subsidiaries of one foreign MNC. The findings suggest that the reasons that lead to expatriating employees from Portuguese subsidiaries to foreign head offices are connected to (1) knowledge management strategies to development the subsidiary’s performance; (2) new skills and knowledge acquisition by future team leaders and business/product managers in Portuguese subsidiaries; (3) procuring knowledge, from agents in head office, to be disseminated amongst co-workers in Portuguese subsidiaries; (4) acquiring global management skills, impossible to acquire locally and; (5) developing global projects within MNC. Also our results show that knowledge acquisition and transfer from foreign head office, through subsidiaries’ expatriates, contributes directly to the Portuguese subsidiaries’ innovation, improved performance, competitive advantage and growth in the economic sectors in which they operate. Moreover, evidence reveals that expatriation is seen as a strategy to fulfil some of the main organisational objectives through their expatriates (e.g., create new products and business markets, develop and incorporate new organisational techniques and processes, integrate global teams within multinational corporation with a responsibility on the definition of global objectives). The results obtained suggest that expatriates have a central role in acquiring and transferring strategic knowledge from MNC head office to their subsidiaries located in Portugal. Based on the findings, the paper discusses in detail the main theoretical and managerial implications. Suggestions for further research are also presented. The study’s main limitation is the small size of the sample, but its findings and methodology are quite original and significant.

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Purpose – the aim of this paper is to analyse the diffusion and efficiency of ISO 9001 on different sectors of activity Design/methodology/approach – for that purpose, a holistic an integrative theoretical approach was based on the scope of the Contingency theory, the Institutional theory and the Resources-Based View (RBV). This theorethical perspective was used in a broad empirical study, using a qualitative and quantitative methodology, concerning Portuguese companies from different sectors of activity. Findings – according to the findings from both perspectives, a ranked combination of the named theoretical frame was constructed. Research limitations/implications – as to the analysis of the efficiency of ISO 9000, one of the limitations of this study lays in the consideration of just two sectors of activity, and another relates to its domestic geographical placement. Practical implications – this study used the ISO 9001 structure for the interviews and this has revealed very useful for the organizations to grasp the matters inquired. Originality/value – a relevant contribution to the state of art is achieved through the considered theoretical scope of analysis

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Trabalho de Projeto submetido à Escola Superior de Teatro e Cinema para cumprimento dos requisitos necessários à obtenção do grau de Mestre em TEATRO - especialização em Artes Performativas (Teatro-Música).

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When a pesticide is released into the environment, most of it is lost before it reaches its target. An effective way to reduce environmental losses of pesticides is by using controlled release technology. Microencapsulation becomes a promising technique for the production of controlled release agricultural formulations. In this work, the microencapsulation of chlorophenoxy herbicide MCPA with native b-cyclodextrin and its methyl and hydroxypropyl derivatives was investigated. The phase solubility study showed that both native and b-CD derivatives increased the water solubility of the herbicide and inclusion complexes are formed in a stoichiometric ratio of 1:1. The stability constants describing the extent of formation of the complexes have been determined by phase solubility studies. 1H NMR experiments were also accomplished for the prepared solid systems and the data gathered confirm the formation of the inclusion complexes. 1H NMR data obtained for the MCPA/CDs complexes disclosed noticeable proton shift displacements for OCH2 group and H6 aromatic proton of MCPA provided clear evidence of inclusion complexation process, suggesting that the phenyl moiety of the herbicide was included in the hydrophobic cavity of CDs. Free energy molecular mechanics calculations confirm all these findings. The gathered results can be regarded as an essential step to the development of controlled release agricultural formulations containing herbicide MCPA.

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Dissertation presented to obtain a Ph.D degree in Biology, speciality in Molecular Genetics, by Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia