24 resultados para Conjugação topológica


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Complex network analysis is a powerful tool into research of complex systems like brain networks. This work aims to describe the topological changes in neural functional connectivity networks of neocortex and hippocampus during slow-wave sleep (SWS) in animals submited to a novel experience exposure. Slow-wave sleep is an important sleep stage where occurs reverberations of electrical activities patterns of wakeness, playing a fundamental role in memory consolidation. Although its importance there s a lack of studies that characterize the topological dynamical of functional connectivity networks during that sleep stage. There s no studies that describe the topological modifications that novel exposure leads to this networks. We have observed that several topological properties have been modified after novel exposure and this modification remains for a long time. Major part of this changes in topological properties by novel exposure are related to fault tolerance

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In this thesis, we address two issues of broad conceptual and practical relevance in the study of complex networks. The first is associated with the topological characterization of networks while the second relates to dynamical processes that occur on top of them. Regarding the first line of study, we initially designed a model for networks growth where preferential attachment includes: (i) connectivity and (ii) homophily (links between sites with similar characteristics are more likely). From this, we observe that the competition between these two aspects leads to a heterogeneous pattern of connections with the topological properties of the network showing quite interesting results. In particular, we emphasize that there is a region where the characteristics of sites play an important role not only for the rate at which they get links, but also for the number of connections which occur between sites with similar and dissimilar characteristics. Finally, we investigate the spread of epidemics on the network topology developed, whereas its dissemination follows the rules of the contact process. Using Monte Carlo simulations, we show that the competition between states (infected/healthy) sites, induces a transition between an active phase (presence of sick) and an inactive (no sick). In this context, we estimate the critical point of the transition phase through the cumulant Binder and ratio between moments of the order parameter. Then, using finite size scaling analysis, we determine the critical exponents associated with this transition

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This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

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Chitin is the second most abundant polysaccharide in nature and its derivative chitosan has been widely studied due to its unique chemical and pharmacological properties. However, studies show that when this molecule is used as food, drug, etc. it tends to accumulate in renal tissue and promotes an increase in calcium excretion. Nevertheless, the effect of chitosan on the formation of calcium oxalate (OxCa) crystals has never been evaluated. The formation of kidney stones (urolithiasis) is the disease that most often affects the kidneys and the urinary system. In addition, this is a disease with high prevalence and recurrence. Many molecules with antioxidant activity have been shown to decrease the potential for in vitro OxCa crystals formation. Thus, the aim of this study was to evaluate the effect of low molecular weight chitosan and its derivatives conjugated to gallic acid (AG) as antioxidant and inhibitor of OxCa crystals formation. The physico-chemical analysis confirmed the identity of chitosan. This molecule was subjected to five antioxidant tests and showed an excellent copper chelating activity. However, chitosan did not show other significant antioxidant activity. When chitosan was subjected to in vitro crystal formation tests, it increased the number of OxCa monohydrate crystals, modified the morphology of the crystals, modified the proportions between populations of crystals in solution and increased the zeta potential of these crystals formed. Four molecules of chitosan conjugated with GA were obtained. The physico-chemical analysis confirmed that chitosan and AG were covalently bonded. However, the amount of GA liked to chitosan did not increase even when 10 times more GA was used in experiment. When these derivatives were subjected to antioxidant tests, all chitosan conjugates showed higher antioxidant potential than their precursors. However, they showed different activity between them, which indicating that the position where AG is conjugated is an important factor for chitosan-GA activity. When conjugated chitosans were submitted to in vitro crystal formation tests, a reduction in the crystals number was observed when compared with those formed in the presence of unconjugated chitosan. Chitosan has a strong capacity for inducing OxCa monohydrate crystal formation, as well as modify their morphology and zeta potential. Over all, the process of conjugating AG to chitosan led to an increase in antioxidant potential of this molecule and was also able to decrease its capacity of inducing in vitro crystal formation

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The aim of this work is to understand the morphological expression of ground occupation by the higher income population, by focusing on population distribution in accordance with income layers and demographical density, as well as topological accessibility (HILLIER and HANSON, 1984) resulting from the urban grid structure. It endeavors to identify a functional organizing principle regarding the intra-urban space of Natal capital city of the state of Rio Grande do Norte, the research focus. In order to achieve this, census data as well as syntactic data were utilized for mapping and spatial analysis of income patterns, topological accessibility and demographical density using Geographical Information System GIS. The organizing principle was named as the Form of Privilege, a pattern that concentrates or tends to concentrate wealth, topological accessibility and low demographical density. Attempting to assess its extent, beyond Natal, this principle was applied to other Brazilian northeastern capitals such as: Fortaleza, CE; Teresina, PI; Aracaju, SE; Recife, PE; and João Pessoa, PB. Findings point out that although the urban structures of these cities are not immune to the Form of Privilege, Natal is emblematic of this phenomenon, a fact that demonstrates the perverse character of its spatial process, which historically creates privileged areas within the city, by means of the appropriation of accessibility as well as of the many urban benesses that are related to it by higher income groups at the expense of the major part of the population, which though being the people mostly in need of the benefits originating from the urban form are excluded from them

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This study intends to enhance the existing knowledge concerning the patterns of the uses of space for low cost housing in Parnamirim, Rio Grande do Norte, Brazil, by way of comparative morphological studies in spatial arrangements and articulations regarding three distinct, however inter-related, sets of social housing: (1) a development comprising 21 self-built houses erected on public routes and illegal plots within a tract of land originally designed to be an industrial development: (2) architect-designed houses built by the public authority in order to accommodate the previous 21 (plus a few additions) families occupying the self-built dwellings, and (3) modifications performed by dwellers on a total of those 24 houses built by the public authority after an occupation period of one year. The predominant uses of each room within the self-built and modified houses were represented in ground plan, based on empirical observation, surveys with dwellers and the use of analytical procedures of morphologic analysis of nature predominantly geometric (specific) and topology (space syntax analysis). A scale of priorities was identified in relation to the uses of each room, its geometrical arrangement (adjacency, front/back relations etc), and underlying structures (connectivity, depth and spatial integration) in order to establish congruencies and non-congruencies between a social-cultural order embedded in the self-built domestic space and the design logic contained in the houses offered by official agencies. The comparative analysis points towards the convivial existence of two tendencies: one that seems to reinforce a design logic inasmuch as the additions and modifications performed by the dwellers do not alter but even emphasize the original configuration of the designed houses, and another one in which those patterns are subverted in accordance with a logic which, to a lesser or greater degree, coincides with that of the self-built dwellings

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This study focuses on the building ensemble of Avenida Roberto Freire, a main road in Natal, Brazil, as a material expression of the confluence of various factors among which the following may be emphasized: high level of accessibility due to urban spatial re-structuring and the growth of the real estate market, in view of the increasing number of consumers, who arrived in Natal within the last decades. The intense urban modification process that has been going on in Natal since at least the 1980s, has engendered the formation of long axial lines which express the expansion dynamics and some of the forces subjacent to it. Avenida Roberto Freire has been an iconic example of an urban thoroughfare where architecture becomes primarily a communication support that can be perceived by fast moving passers-by, what brings it close to the venturian concept of strip (Venturi at al, 1972). The building types that line the road not only respond to the dynamics in process but also contribute to intensify it, as they house a variety of uses which attract people and generate more movement. The dynamics is further strengthened by the action of the real estate business which benefits from the increase of highly accessible locations, and from the private and public investments and incentives to tourism that aim to insert this city into the globalized world. Although the intention of reconstituting part of the history of density increase on this avenue in a diachronical perspective was attempted within the limits of the available references and documentation, the central contribution of this study is to understand the relations between topological accessibility and the typological nature of the building ensemble. By observing the synchronic morphological frame resulting from the spatial configuration analysis pertinent to this avenue (cf. Hillier and Hanson,1984) and the inventory and classification of the building ensemble there existing, this study aims to understand how architecture responds to accessibility in view of the real estate pressure, boosted by a cosmopolitanizing process brought about by the continuous flow of foreign and Brazilian arrivals as visitors, temporary or permanent residents

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This study reviews the spatial configuration from the road network of an urban compound formed by the cities of Crato, Juazeiro do Norte and Barbalha (the Crajubar - core of the Cariri metropolitan region, in the State of Ceará, Brazil), in order to establish nexus (or relations) between different levels of accessibility and the formation/ transformation and specialization of centralities in local and metropolitan scales. Stemming from the Social Logic of Space theoretical and operational apparatus, the study explores modeling possibilities (with axial lines, segments and lines of continuity) which is then confronted to empirical observations concerning movement flows and land use, within a Geographic Information System database. At different scales of analysis, the results suggest evidences of continuity were found in the permanence of intra-urban centres and sub-centres within each town, whereas evidences of change pointed out to the formation of a new centrality of metropolitan magnitude in the neighbourhood referred to as the Triângulo, in the municipality of Juazeiro, where high levels of topological accessibility coincides with the appearance of new business buildings as well as with the emergence of urban equipment of a scale more adequate to meet a regional demand

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Assuming that the form of a building shell and its content the spatial form are distinct dimensions of architecture - however indivisible and interdependent -, this study focus, in the light of the Social Logic of Space (HILLIER; HANSON, 1984), on the intrinsic properties through which domestic space was structured in a sample of single-family dwellings built in João Pessoa (PB) during the 1970s - when the vocabulary of modern architecture still prevailed in Brazil though sharing the urban scene with other architectural trends -, in order to investigate regularities or divergences underlying their conception. These dwellings were originally classified (ARAÚJO, 2010a) in five categories defined according to the form of their building shells and to their prevailing construction techniques: (1) Brazilian modern legacy (considered as truly Brazilian modern style); (2) Paulista architecture (that refers to the modern production of São Paulo, Brazil, from the 1950s through the 1970s); (3) experiences of rationalization and prefabrication ; (4) experiences of adaptation to the climate (referring to a design strongly influenced by the hot and humid climate of North-eastern Brazil); and (5) hybrid (to account for a kind of stylistic hybridism that includes formal attributes, which evoke our colonial past). This study aims to determine, through the analyses of nineteen cases that represent each category, whether this taxonomy corresponds to distinct modes of spatial configuration. This research therefore proposes an approach to the classification of domestic architecture based on topological properties. The dwellings spatial organization was represented, quantified and analyzed, their spatial properties explored in consonance with one another and with the literature. Results pointed out that there is no evidence of a reciprocal relationship between the formal look of the built shells and their respective spatial structures