Transformações químicas, caracterizações e estudo de modelagem molecular do clerodano bioativo trans-desidrocrotonina

In this work it were developed synthetic and theoretical studies for clerodane-type diterpenes obtained from Croton cajucara Benth which represents one of the most important medicinal plant of the Brazil amazon region. Specifically, the majoritary biocompound 19-nor-clerodane trans-dehydrocrotonin (t-DCTN) isolated from the bark of this Croton, was used as target molecule. Semi-synthetic derivatives were obtained from t-DCTN by using the followed synthetic procedures: 1) catalytic reduction with H2, 2) reduction using NaBH4 and 3) reduction using NaBH4/CeCl3. The semi-synthetic 19-nor-furan-clerodane alcohol-type derivatives were denominated such as t-CTN, tCTN-OL, t-CTN-OL, t-DCTN-OL, t-DCTN-OL, being all of them characterized by NMR. The furan-clerodane alcohol derivatives t-CTN-OL and tCTN-OL were obtained form the semi-synthetic t-CTN, which can be isolated from the bark of C. cajucara. A theoretical protocol (DFT/B3LYP) involving the prevision of geometric and magnetic properties such as bond length and angles, as well as chemical shifts and coupling constants, were developed for the target t-DCTN in which was correlated NMR theoretical data with structural data, with satisfactory correlation with NMR experimental data (coefficients ranging from 0.97 and 0.99) and X-ray diffraction data. This theoretical methodology was also validated for all semi-synthetic derivatives described in this work. In addition, topological data from the Quantum Theory of Atoms in Molecules (QTAIM) showed the presence of H-H and (C)O--H(C) intramolecular stabilized interactions types for t-DCTN e t-CTN, contributing to the understanding of the different reactivity of this clerodanes in the presence of NaBH4.

Modelos de condutividade térmica em rochas silicáticas, com ênfase em rochas da província Borborema, NE do Brasil

A practical approach to estimate rock thermal conductivities is to use rock models based just on the observed or expected rock mineral content. In this study, we evaluate the performances of the Krischer and Esdorn (KE), Hashin and Shtrikman (HS), classic Maxwell (CM), Maxwell-Wiener (MW), and geometric mean (GM) models in reproducing the measures of thermal conductivity of crystalline rocks.We used 1,105 samples of igneous and metamorphic rocks collected in outcroppings of the Borborema Province, Northeastern Brazil. Both thermal conductivity and petrographic modal analysis (percent volumes of quartz, K-feldspar, plagioclase, and sum of mafic minerals) were done. We divided the rocks into two groups: (a) igneous and ortho-derived (or meta-igneous) rocks and (b) metasedimentary rocks. The group of igneous and ortho-derived rocks (939 samples) covers most the lithologies de_ned in the Streckeisen diagram, with higher concentrations in the fields of granite, granodiorite, and tonalite. In the group of metasedimentary rocks (166 samples), it were sampled representative lithologies, usually of low to medium metamorphic grade. We treat the problem of reproducing the measured values of rock conductivity as an inverse problem where, besides the conductivity measurements, the volume fractions of the constituent minerals are known and the effective conductivities of the constituent minerals and model parameters are unknown. The key idea was to identify the model (and its associated estimates of effective mineral conductivities and parameters) that better reproduces the measures of rock conductivity. We evaluate the model performances by the quantity  that is equal to the percentage of number of rock samples which estimated conductivities honor the measured conductivities within the tolerance of 15%. In general, for all models, the performances were quite inferior for the metasedimentary rocks (34% <  < 65%) as compared with the igneous and ortho-derived rocks (51% <  < 70%). For igneous and ortho-derived rocks, all model performances were very similar ( = 70%), except the GM-model that presented a poor performance (51% <  < 65%); the KE and HS-models ( = 70%) were slightly superior than the CM and MW-models ( = 67%). The quartz content is the dominant factor in explaining the rock conductivity for igneous and ortho-derived rocks; in particular, using the MW-model the solution is in practice vi UFRN/CCET– Dissertação de mestrado the series association of the quartz content. On the other hand, for metasedimentary rocks, model performances were different and the performance of the KEmodel ( = 65%) was quite superior than the HS ( = 53%), CM (34% <  < 42%), MW ( = 40%), and GM (35% <  < 42%). The estimated effective mineral conductivities are stable for perturbations both in the rock conductivity measures and in the quartz volume fraction. The fact that the metasedimentary rocks are richer in platy-minerals explains partially the poor model performances, because both the high thermal anisotropy of biotite (one of the most common platy-mineral) and the difficulty in obtaining polished surfaces for measurement coupling when platyminerals are present. Independently of the rock type, both very low and very high values of rock conductivities are hardly explained by rock models based just on rock mineral content.

Caracterização de células de lugar no hipocampo e de suas relações com oscilações do potencial de campo local

The main inputs to the hippocampus arise from the entorhinal cortex (EC) and form a loop involving the dentate gyrus, CA3 and CA1 hippocampal subfields and then back to EC. Since the discovery that the hippocampus is involved in memory formation in the 50's, this region and its circuitry have been extensively studied. Beyond memory, the hippocampus has also been found to play an important role in spatial navigation. In rats and mice, place cells show a close relation between firing rate and the animal position in a restricted area of the environment, the so-called place field. The firing of place cells peaks at the center of the place field and decreases when the animal moves away from it, suggesting the existence of a rate code for space. Nevertheless, many have described the emergence of hippocampal network oscillations of multiple frequencies depending on behavioral state, which are believed to be important for temporal coding. In particular, theta oscillations (5-12 Hz) exhibit a spatio-temporal relation with place cells known as phase precession, in which place cells consistently change the theta phase of spiking as the animal traverses the place field. Moreover, current theories state that CA1, the main output stream of the hippocampus, would interplay inputs from EC and CA3 through network oscillations of different frequencies, namely high gamma (60-100 Hz; HG) and low gamma (30-50 Hz; LG), respectively, which tend to be nested in different phases of the theta cycle. In the present dissertation we use a freely available online dataset to make extensive computational analyses aimed at reproducing classical and recent results about the activity of place cells in the hippocampus of freely moving rats. In particular, we revisit the debate of whether phase precession is due to changes in firing frequency or space alone, and conclude that the phenomenon cannot be explained by either factor independently but by their joint influence. We also perform novel analyses investigating further characteristics of place cells in relation to network oscillations. We show that the strength of theta modulation of spikes only marginally affects the spatial information content of place cells, while the mean spiking theta phase has no influence on spatial information. Further analyses reveal that place cells are also modulated by theta when they fire outside the place field. Moreover, we find that the firing of place cells within the theta cycle is modulated by HG and LG amplitude in both CA1 and EC, matching cross-frequency coupling results found at the local field potential level. Additionally, the phase-amplitude coupling in CA1 associated with spikes inside the place field is characterized by amplitude modulation in the 40-80 Hz range. We conclude that place cell firing is embedded in large network states reflected in local field potential oscillations and suggest that their activity might be seen as a dynamic state rather than a fixed property of the cell.

Regulador eletromagnético de frequência aplicado no controle de velocidade de geradores eólicos

The constant necessity for new sources of renewable energy is increasingly promoting the increase of investments in this area. Among other sources, the wind power has been becoming prominent. It is important to promote the search for the improvement of the technologies involved in the topologies of the wind turbines, seeking for alternatives which enhance the gotten performance, despite the irregularity of the wind speed. This study presents a new system for speed control, in this case applied to the wind turbines - the Electromagnetic Frequency Regulator (EFR). One of the most used devices in some topologies is the mechanical gearboxes which, along with a short service life, often represent sources of noise and defects. The EFR does not need these transmission boxes, representing a technological advancement, using for that an adapted induction machine, in which the stator becomes mobile, supportive to the axis of the turbine. In the topology used in this study, the EFR also allows us to leave out the usage of the eletronic converters to establish the coupling between the generator and the electrical grid. It also the reason why it provides the possibility of obtaining the generation in alternating current, with constant voltage and frequency, where there is no electrical grid. Responsable for the mechanical speed control of the generator, the EFR can be useful in other transmission systems in which the mechanical speed control output is the objective. In addition, the EFR operates through the combination of two inputs, a mechanical and other electrical. It multiplies the possibilities of application because it is able to synergistic coupling between different arrays of energy, and, for such reasons, it enables the various sources of energy involved to be uncoupled from the network, being the synchronous generator responsible for the system connection with the electrical grid, simplifying the control strategies on the power injected in it. Experimental and simulation results are presented through this study, about a wind turbine, validating the proposal related to the efficience in the speed control of the system for different wind conditions.

Um estudo sobre a variabilidade do vento no nordeste do Brasil através de métodos estatísticos e via modelos dinâmicos de meso e micro escala

The objective of this study was to determine the seasonal and interannual variability and calculate the trends of wind speed in NEB and then validate the mesoscale numerical model for after engage with the microscale numerical model in order to get the wind resource at some locations in the NEB. For this we use two data sets of wind speed (weather stations and anemometric towers) and two dynamic models; one of mesoscale and another of microscale. We use statistical tools to evaluate and validate the data obtained. The simulations of the dynamic mesoscale model were made using data assimilation methods (Newtonian Relaxation and Kalman filter). The main results show: (i) Five homogeneous groups of wind speed in the NEB with higher values in winter and spring and with lower in summer and fall; (ii) The interannual variability of the wind speed in some groups stood out with higher values; (iii) The large-scale circulation modified by the El Niño and La Niña intensified wind speed for the groups with higher values; (iv) The trend analysis showed more significant negative values for G3, G4 and G5 in all seasons and in the annual average; (v) The performance of dynamic mesoscale model showed smaller errors in the locations Paracuru and São João and major errors were observed in Triunfo; (vi) Application of the Kalman filter significantly reduce the systematic errors shown in the simulations of the dynamic mesoscale model; (vii) The wind resource indicate that Paracuru and Triunfo are favorable areas for the generation of energy, and the coupling technique after validation showed better results for Paracuru. We conclude that the objective was achieved, making it possible to identify trends in homogeneous groups of wind behavior, and to evaluate the quality of both simulations with the dynamic model of mesoscale and microscale to answer questions as necessary before planning research projects in Wind-Energy area in the NEB

Contribuições para estratégia de controle aplicada à geração fotovoltaica interconectada à rede elétrica

Generation systems, using renewable sources, are becoming increasingly popular due to the need for increased use of electricity. Currently, renewables sources have a role to cooperate with conventional generation, due to the system limitation in delivering the required power, the need for reduction of unwanted effects from sources that use fossil fuels (pollution) and the difficulty of building new transmission and/or distribution lines. This cooperation takes place through distributed generation. Therefore, this work proposes a control strategy for the interconnection of a PV (Photovoltaic) system generation distributed with a three-phase power grid through a connection filter the type LCL. The compensation of power quality at point of common coupling (PCC) is performed ensuring that the mains supply or consume only active power and that his currents have low distorcion. Unlike traditional techniques which require schemes for harmonic detection, the technique performs the harmonic compensation without the use of this schemes, controlling the output currents of the system in an indirect way. So that there is effective control of the DC (Direct Current) bus voltage is used the robust controller mode dual DSMPI (Dual-Sliding Mode-Proportional Integral), that behaves as a sliding mode controller SM-PI (Sliding Mode-Proportional Integral) during the transition and like a conventional PI (Proportional Integral) in the steady-state. For control of current is used to repetitive control strategy, which are used double sequence controllers (DSC) tuned to the fundamental component, the fifth and seventh harmonic. The output phase current are aligned with the phase angle of the utility voltage vector obtained from the use of a SRF-PLL (Synchronous Reference Frame Phase-Locked-Loop). In order to obtain the maximum power from the PV array is used a MPPT (Maximum Power Point Tracking) algorithm without the need for adding sensors. Experimental results are presented to demonstrate the effectiveness of the proposed control system.

Anisotropia magnética em nanofilmes com assimetria cristalográfica

This Thesis comprises a theoretical study about the influence of the magnetocrystalline anisotropy on the static and dynamic magnetic properties of nanofilms: monolayers and trilayers coupled through the bilinear and biquadratic exchange fields, for situations in which the systems are grown in unusual [hkl] asymmetric directions. Using a theory based on a realistic phenomenological model for description of nanometric systems, we consider the total free magnetic energy including the Zeeman interaction, cubic and uniaxial anisotropies, demagnetizing and surface anysotropy energies, as well as the exchange terms. Numerical calculations are conducted by minimizing the total magnetic energy from the determination of equilibrium static configurations. We consider experimental parameters found in the literature to illustrate our results for Fe/Cr/Fe trilayer systems. In particular, a total of six different magnetic scenarios are analyzed for three regimens of exchange fields and the [211] and [321] asymmetric growth directions. After numerically minimize the total energy, we use the equilibrium configurations to calculate magnetization and magnetoresistance curves with the respective magnetic phases and corresponding critical fields. These results are also used to establish the boundary for occurrence of saturated states. Within the context of the spin waves, we solve the equation of motion for these systems in order to find the respective associated dispersion relations. The results show similar magnetization and magnetoresistance curves for both [211] and [321] growth scenarios, including an equivalent magnetic transition behavior. However, the combination of those peculiar symmetries and influence of the exchange energies results in attractive properties, including the generation of magnetic states as a function of the asymmetric degree imposed in the [hkl] growth orientations. There is also an increasing incompatibility between the values of saturation fields of magnetization and magnetoresistance for the cases in which a magnetic field acts along intermediate cubic anisotropic axes, particularly in the situations where the bilinear and biquadratic exchange fields are comparable. The dispersion relations and static results are consistent, the corresponding magnetic states are also present in both acoustic and optical modes. Furthermore, Goldstone excitations are also observed for that particular cases of a magnetic field acting in the intermediate axes, an effect related to transitions of second order and to the spontaneous symmetry breaking imposed by the combination of the biquadratic energy with the cubic and uniaxial anisotropies.

Processamento Inteligente de Sinais de Pressão e Temperatura Adquiridos Através de Sensores Permanentes em Poços de Petróleo

Originally aimed at operational objectives, the continuous measurement of well bottomhole pressure and temperature, recorded by permanent downhole gauges (PDG), finds vast applicability in reservoir management. It contributes for the monitoring of well performance and makes it possible to estimate reservoir parameters on the long term. However, notwithstanding its unquestionable value, data from PDG is characterized by a large noise content. Moreover, the presence of outliers within valid signal measurements seems to be a major problem as well. In this work, the initial treatment of PDG signals is addressed, based on curve smoothing, self-organizing maps and the discrete wavelet transform. Additionally, a system based on the coupling of fuzzy clustering with feed-forward neural networks is proposed for transient detection. The obtained results were considered quite satisfactory for offshore wells and matched real requisites for utilization

Projeto, construção e análise de um prototipo vibracional em escala de bancada aplicável ao tratamento de água de produção de petróleo bruto, mediante inovadora operação híbrida de adsorção e auto-flotação

A self-flotator vibrational prototype electromechanical drive for treatment of oil and water emulsion or like emulsion is presented and evaluated. Oil production and refining to obtain derivatives is carried out under arrangements technically referred to as on-shore and off-shore, ie, on the continent and in the sea. In Brazil 80 % of the petroleum production is taken at sea and area of deployment and it cost scale are worrisome. It is associated, oily water production on a large scale, carrier 95% of the potential pollutant of activity whose final destination is the environment medium, terrestrial or maritime. Although diversified set of techniques and water treatment systems are in use or research, we propose an innovative system that operates in a sustainable way without chemical additives, for the good of the ecosystem. Labyrinth adsor-bent is used in metal spirals, and laboratory scale flow. Equipment and process patents are claimed. Treatments were performed at different flow rates and bands often monitored with control systems, some built, other bought for this purpose. Measurements of the levels of oil and grease (OGC) of efluents treaty remained within the range of legal framework under test conditions. Adsorbents were weighed before and after treatment for obtaining oil impregna-tion, the performance goal of vibratory action and treatment as a whole. Treatment technolo-gies in course are referenced, to compare performance, qualitatively and quantitatively. The vibration energy consumption is faced with and without conventional flotation and self-flotation. There are good prospects for the proposed, especially in reducing the residence time, by capillary action system. The impregnation dimensionless parameter was created and confronted with consecrated dimensionless parameters, on the vibrational version, such as Weber number and Froude number in quadratic form, referred to as vibrational criticality. Re-sults suggest limits to the vibration intensity