Estudo teórico de intermediários tetraédricos acidez / basicidade e estereosseletividade enzimáticos

The present work aimed first, the theoretical study of tetrahedral intermediate stability formed from carbonyl addition reactions using the second (MP2) and third (MP3) order Møller–Plesset perturbation theory. Linear correlations between electronic energy difference of reactions with Wiberg Indexes and C-O bond lengths were obtained, and was observed that the stability of adducts formed depends directly of electronic density involved between these atoms. The knowing of electronic parameters of these structures has an important hole due to the large use on reactions that in his course forms this tetrahedral intermediate. Employing the ONIOM (B3LYP:AMBER) methodology, was evaluated the stereoselectivity of a enzymatic reaction between CAL B enzyme and a long chain ester. In this study, were obtained the electronic energies of ground state and intermediate state of transesterification rate-determing step from two possible proquirals faces Re and Si. The objective was study the enantioselectivity of CAL B and rationalizes it using quantum theory of atoms in molecules (QTAIM). A theoretical study employing inorganic compounds was performed using ab initio CBS-QB3 method aiming to find a link between thermodynamic and equilibrium involving acids and bases. The results observed showed an excellent relationship between difference in Gibbs free energy, ΔG of acid dissociation reaction and ΔG of hydrolysis reaction of the corresponding conjugate base. It was also observed, a relationship between ΔG of hydrolysis reaction of conjugate acids and their corresponding atomic radius showing that stability plays an important role in hydrolysis reactions. The importance of solvation in acid/base behavior when compared to theoretical and experimental ΔG´s also was evaluated.

Cenário da produção acadêmica em história da matemática no ensino de matemática: uma análise reflexiva das teses e dissertações (1990-2010)

This research aims to make a reflective analysis about the academic production originated in the stricto sensu post graduation programs in the country, produced in the period of 1990 to 2010, in the field of History of Mathematics, especifically on works about the History of Mathematics in Mathematics education and that present pedagogical proposals that make use of the History of Mathematics in order to teach Mathematics. Defending the thesis that the researches on mathematics education with goals turned to the use of didactic proposals related to the history of mathematic that take in consideration the coherency between epistemological aspects inherent to mathematics history and anthological elements materialized on the conceptions of mathematics and mathematics history and of apprenticeship (implicitly or explicitly exposed) may originate significant contribution to the field of history of mathematics on education. Among these, nine were Master’s Degree dissertations and five PHD’s theses. The reflective analysis was accomplished from two matrixes; one from theoretical nature and the other, ontologic nature, elaborated from the pretexts of Sanches Gamboa, about the epistemological analysis from academic production in the field of Mathematics Education and the following theoretical perspectives in the field of History of Mathematics Education, that are: linear evolutionary theory, structural construtivist operative, evolutionary discontinuous, historical and socialcultural investigation and the use of activities estimulating the usage of verbal and nonverbal expressions. These perspectives were based on the works of Miguel and Miorim, Mendes and Radford. As results, we have detected some established dissonances between the categories related to theoretical and ontologic levels and the pedagogical proposal presented in these researches. On the other hand, we have discovered works that are able to establish consonances between the theoretical and ontological elements and the presented pedagogical proposal. These works carry significative contributions to the field of History of Mathematics applied to Mathematics pedagogical practice, inclusively presenting significative theoretical elements to the production of knowledge recognized as scientific in the Mathematics field

Origem física das curvas sigmoidais respiratórias pressão-volume: recrutamento alveolar e elasticidade não-linear

An important unsolved problem in medical science concerns the physical origin of the sigmoidal shape of pressure volume curves of healthy (and some unhealthy) lungs. Such difficulties are expected because the lung, which is the most important structure in the respiratory system, is extremely complex. Its rheological properties are unknown and seem to depend on phenomena occurring from the alveolar scale up to the thoracic scale. Conventional wisdom holds that linear response, i.e., Hooke s law, together with alveolar overdistention, play a dominant role in respiration, but such assumptions cannot explainthe crucial empirical sigmoidal shape of the curves. In this doctorate thesis, we propose an alternative theory to solve this problem, based on the alveolar recruitment together with the nonlinear elasticity of the alveoli. This theory suggests that recruitment may be the predominant factor shaping these curves in the entire range of pressures normally employed in experiments. The proposed model correctly predicts the observed sigmoidal pressure volume curves, allowing us to discuss adequately the importance of this result, as well as its implications for medical practice

Identificação não linear usando uma rede fuzzy wavelet neural network modificada

In last decades, neural networks have been established as a major tool for the identification of nonlinear systems. Among the various types of networks used in identification, one that can be highlighted is the wavelet neural network (WNN). This network combines the characteristics of wavelet multiresolution theory with learning ability and generalization of neural networks usually, providing more accurate models than those ones obtained by traditional networks. An extension of WNN networks is to combine the neuro-fuzzy ANFIS (Adaptive Network Based Fuzzy Inference System) structure with wavelets, leading to generate the Fuzzy Wavelet Neural Network - FWNN structure. This network is very similar to ANFIS networks, with the difference that traditional polynomials present in consequent of this network are replaced by WNN networks. This paper proposes the identification of nonlinear dynamical systems from a network FWNN modified. In the proposed structure, functions only wavelets are used in the consequent. Thus, it is possible to obtain a simplification of the structure, reducing the number of adjustable parameters of the network. To evaluate the performance of network FWNN with this modification, an analysis of network performance is made, verifying advantages, disadvantages and cost effectiveness when compared to other existing FWNN structures in literature. The evaluations are carried out via the identification of two simulated systems traditionally found in the literature and a real nonlinear system, consisting of a nonlinear multi section tank. Finally, the network is used to infer values of temperature and humidity inside of a neonatal incubator. The execution of such analyzes is based on various criteria, like: mean squared error, number of training epochs, number of adjustable parameters, the variation of the mean square error, among others. The results found show the generalization ability of the modified structure, despite the simplification performed

Termodinâmica de um gás de fótons no contexto de eletrodinâmicas não-lineares

The objective of this dissertation is the development of a general formalism to analyze the thermodynamical properties of a photon gas under the context of nonlinear electrodynamics (NLED). To this end it is obtained, through the systematic analysis of Maxwell s electromagnetism (EM) properties, the general dependence of the Lagrangian that describes this kind of theories. From this Lagrangian and in the background of classical field theory, we derive the general dispersion relation that photons must obey in terms of a background field and the NLED properties. It is important to note that, in order to achieve this result, an aproximation has been made in order to allow the separation of the total electromagnetic field into a strong background electromagnetic field and a perturbation. Once the dispersion relation is in hand, the usual Bose-Einstein statistical procedure is followed through which the thermodynamical properties, energy density and pressure relations are obtained. An important result of this work is the fact that equation of state remains identical to the one obtained under EM. Then, two examples are made where the thermodynamic properties are explicitly derived in the context of two NLED, Born-Infelds and a quadratic approximation. The choice of the first one is due to the vast appearance in literature and, the second one, because it is a first order approximation of a large class of NLED. Ultimately, both are chosen because of their simplicity. Finally, the results are compared to EM and interpreted, suggesting possible tests to verify the internal consistency of NLED and motivating further developement into the formalism s quantum case