Síntese de ligantes quirais pentacíclicos 1,5 e bicíclicos 1,3 di substituídos e suas aplicações como indutores quirais na reação de adição de dietilzinco ao bensaldeído

Neste trabalho foi observado um rearranjodiotrópico do composto quiral (+)-1 o que levou na sua racemização. Verificou-se que esse processoé termicamente permitido pela simetria dos orbitais de fronteira HOMO-LUMO. Posteriormente, constatou-se que o rearranjo não era somente governado pela temperatura, mas também pelas condições reacionais, respeitada a simetria de orbitais. A partir da obtenção dos precursores quirais (−)-40 e (−)-41 através de reação de transesterificação de (±)-40 com acetato de vinila catalisada pela lípase da Cândida rugosa, realizou-se a síntese de uma série de compostos quirais bicíclicos 1,3 di-substituídos, dióis e aminoálcoois. Estes bicíclicos quirais foram testados como indutores quirais na reação de adição enantioseletiva de dietilzinco ao benzaldeído. Observou-se, no caso dos aminoálcoois, que a posição do estereocentro C-O tem uma importância fundamental no processo, determinando o grau de enantioseletividade da reação. Sintetizou-se o aminoálcool (+)-63 o qual foi utilizado na redução enantioseletiva de cetonas pró-quirais através da síntese, in situ, de sua oxazaborolidina.

Novo formalismo semi-empírico para cálculos químico-quânticos

Realizou-se a dedução de um formalismo básico, útil para o desenvolvimento de novas implementações semi-empíricas, partindo de primeiros princípios. A abordagem utilizada é inspirada nos métodos da família HAM, e visa possibilitar o desenvolvimento de uma implementação semi-empírica de última geração que não esteja sujeita às di culdades que ocorrem com métodos da família ZDO. São apresentadas as expressões para a energia total e para os elementos da matriz de Fock segundo este formalismo básico. O emprego de expoentes variáveis nas funções de base (orbitais atômicos) é proposto e modelado com esquemas tipo HAM/3, HAM/4 e polinomial, tomando-se como referência resultados obtidos por cálculo ab initio. Além disso, uma contribuição para produção de conjuntos de dados de referência por cálculo ab initio é fornecida. Esta contribuição permite que sejam produzidos resultados de alto nível para energias eletrônicas a um custo computacional moderado, por meio da extrapola- ção da energia de correlação eletrônica em cálculos com bases correlation consistent de Dunning.

Vocalise com a vogal “i” nas tonalidades maior e menor

Módulo 7

Teoria da Ligação de Valência

O material apresenta as formas de ocorrência das ligações dos orbitais e a Teoria da Ligação de Valência com a mistura de orbitais. O objetivo é aprimorar o aprendizado do aluno por meio da visualização das ligações dos orbitais.

Teoria do Orbital Molecular (TOM)

O material aborda a Teoria do Orbital Molecular (TOM), ressaltando o conceito de energia e probabilidade. O objetivo é propiciar a compreensão da teoria através da visualização das ligações dos orbitais.

Potencialidades de cultivo de macroalgas no litoral do Rio Grande do Norte (NE, Brasil): uma perspectiva de integração de dados ambientais em sistemas de informação geográfica (SIG)

Since centuries ago, the Asians use seaweed as an important source of feeding and are their greatest world-wide consumers. The migration of these peoples for other countries, made the demand for seaweed to increase. This increasing demand prompted an industry with annual values of around US$ 6 billion. The algal biomass used for the industry is collected in natural reservoirs or cultivated. The market necessity for products of the seaweed base promotes an unsustainable exploration of the natural banks, compromising its associated biological balance. In this context, seaweed culture appears as a viable alternative to prevent the depletion of these natural supplies. Geographic Information Systems (GIS) provide space and produce information that can facilitate the evaluation of important physical and socio-economic characteristics for the planning of seaweed culture. This objective of this study is to identify potential coastal areas for seaweed culture in the state of Rio Grande do Norte, from the integration of social-environmental data in the SIG. In order to achieve this objective, a geo-referred database composed of geographical maps, nautical maps and orbital digital images was assembled; and a bank of attributes including physical and oceanographical variables (winds, chains, bathymetry, operational distance from the culture) and social and environmental factors (main income, experience with seaweed harvesting, demographic density, proximity of the sheltered coast and distance of the banks) was produced. In the modeling of the data, the integration of the space database with the bank of attributes for the attainment of the map of potentiality of seaweed culture was carried out. Of a total of 2,011 ha analyzed by the GIS for the culture of seaweed, around 34% or 682 ha were indicated as high potential, 55% or 1,101 ha as medium potential, and 11% or 228 ha as low potential. The good indices of potentiality obtained in the localities studied demonstrate that there are adequate conditions for the installation of seaweed culture in the state of Rio Grande do Norte

Modelagem molecular na caracterização eletrônica de oligopeptídeos e na descrição quântica da interação fármaco-receptor

In this dissertation, the theoretical principles governing the molecular modeling were applied for electronic characterization of oligopeptide α3 and its variants (5Q, 7Q)-α3, as well as in the quantum description of the interaction of the aminoglycoside hygromycin B and the 30S subunit of bacterial ribosome. In the first study, the linear and neutral dipeptides which make up the mentioned oligopeptides were modeled and then optimized for a structure of lower potential energy and appropriate dihedral angles. In this case, three subsequent geometric optimization processes, based on classical Newtonian theory, the semi-empirical and density functional theory (DFT), explore the energy landscape of each dipeptide during the search of ideal minimum energy structures. Finally, great conformers were described about its electrostatic potential, ionization energy (amino acids), and frontier molecular orbitals and hopping term. From the hopping terms described in this study, it was possible in subsequent studies to characterize the charge transport propertie of these peptides models. It envisioned a new biosensor technology capable of diagnosing amyloid diseases, related to an accumulation of misshapen proteins, based on the conductivity displayed by proteins of the patient. In a second step of this dissertation, a study carried out by quantum molecular modeling of the interaction energy of an antibiotic ribosomal aminoglicosídico on your receiver. It is known that the hygromycin B (hygB) is an aminoglycoside antibiotic that affects ribosomal translocation by direct interaction with the small subunit of the bacterial ribosome (30S), specifically with nucleotides in helix 44 of the 16S ribosomal RNA (16S rRNA). Due to strong electrostatic character of this connection, it was proposed an energetic investigation of the binding mechanism of this complex using different values of dielectric constants (ε = 0, 4, 10, 20 and 40), which have been widely used to study the electrostatic properties of biomolecules. For this, increasing radii centered on the hygB centroid were measured from the 30S-hygB crystal structure (1HNZ.pdb), and only the individual interaction energy of each enclosed nucleotide was determined for quantum calculations using molecular fractionation with conjugate caps (MFCC) strategy. It was noticed that the dielectric constants underestimated the energies of individual interactions, allowing the convergence state is achieved quickly. But only for ε = 40, the total binding energy of drug-receptor interaction is stabilized at r = 18A, which provided an appropriate binding pocket because it encompassed the main residues that interact more strongly with the hygB - C1403, C1404, G1405, A1493, G1494, U1495, U1498 and C1496. Thus, the dielectric constant ≈ 40 is ideal for the treatment of systems with many electrical charges. By comparing the individual binding energies of 16S rRNA nucleotides with the experimental tests that determine the minimum inhibitory concentration (MIC) of hygB, it is believed that those residues with high binding values generated bacterial resistance to the drug when mutated. With the same reasoning, since those with low interaction energy do not influence effectively the affinity of the hygB in its binding site, there is no loss of effectiveness if they were replaced.

Classificação de imagens de ambientes coralinos: uma abordagem empregando uma combinação de classificadores e máquina de vetor de suporte

The use of the maps obtained from remote sensing orbital images submitted to digital processing became fundamental to optimize conservation and monitoring actions of the coral reefs. However, the accuracy reached in the mapping of submerged areas is limited by variation of the water column that degrades the signal received by the orbital sensor and introduces errors in the final result of the classification. The limited capacity of the traditional methods based on conventional statistical techniques to solve the problems related to the inter-classes took the search of alternative strategies in the area of the Computational Intelligence. In this work an ensemble classifiers was built based on the combination of Support Vector Machines and Minimum Distance Classifier with the objective of classifying remotely sensed images of coral reefs ecosystem. The system is composed by three stages, through which the progressive refinement of the classification process happens. The patterns that received an ambiguous classification in a certain stage of the process were revalued in the subsequent stage. The prediction non ambiguous for all the data happened through the reduction or elimination of the false positive. The images were classified into five bottom-types: deep water; under-water corals; inter-tidal corals; algal and sandy bottom. The highest overall accuracy (89%) was obtained from SVM with polynomial kernel. The accuracy of the classified image was compared through the use of error matrix to the results obtained by the application of other classification methods based on a single classifier (neural network and the k-means algorithm). In the final, the comparison of results achieved demonstrated the potential of the ensemble classifiers as a tool of classification of images from submerged areas subject to the noise caused by atmospheric effects and the water column

Analysis of land use and occupancy in permanent preservation areas according to the hydrography of Ribeirão Água Fria - Bofete, SP - Brazil

Os conflitos de uso são determinados pelas ocupações inadequadas do solo, como é o caso de ocupação do solo dentro de áreas de preservação permanente. O presente trabalho teve como objetivos determinar as classes de uso do solo e se há conflitos dentro de áreas de preservação permanente ao longo da rede de drenagem da microbacia do Ribeirão Água Fria, município de Bofete (SP). Situa-se geograficamente entre as coordenadas: 48°09'30 a 48°18'30 de longitude WGr., 22°58'30 a 23°04'30 de latitude sul com uma área de 15.242,84 ha. O mapa de uso do solo foi elaborado por meio da interpretação diretamente na tela do computador de imagem digital de satélite. Nos dados orbitais, a área de estudo está inserida no quadrante A, da imagem TM/Landsat-5, órbita 220, ponto 76, passagem de 8/09/2007. O Sistema de Informação Geográfica empregado foi o Cartalinx. As áreas de conflito da microbacia foram obtidas a partir do cruzamento entre os mapas de uso do solo e de APPs. Os resultados permitiram concluir que mais da metade da área (51,09%) está ocupada por pastagens, reflexo de solos arenosos e de baixa fertilidade. Constatou-se, ainda, que apesar de quase metade da microbacia estar coberta com algum tipo de vegetação (48,78% de mata natural/reflorestamento), possui aproximadamente um terço das áreas de preservação permanente utilizadas inadequadamente por pastagens (88,15%), reflorestamento (10,42%) e solo exposto (1,43%), totalizando 343,07 ha de áreas conflitantes em um total de 993,26 ha de APPs.

Estimativa da evapotranspiração espacial em uma região semiárida utilizando sensoriamento remoto

With the need to deploy management and monitoring systems of natural resources in areas susceptible to environmental degradation, as is the case of semiarid regions, several works have been developed in order to find effective models and technically and economically viable. Therefore, this study aimed to estimate the daily actual evapotranspiration (ETr) through the application of the Surface Energy Balance Algorithm for Land (SEBAL), from remote sensing products, in a semiarid region, Seridó of the Rio Grande do Norte, and do the validation of these estimates using ETr values obtained by the Penman-Monteith (standard method of the Food and Agriculture Organization-FAO). The SEBAL is based on energy balance method, which allows obtaining the vertical latent heat flux (LE) with orbital images and, consequently, of the evapotranspiration through the difference of flows, also vertical, of heat in the soil (G), sensitive heat (H) and radiation balance (Rn). The study area includes the surrounding areas of the Dourado reservoir, located in the Currais Novos/RN city. For the implementation of the algorithm were used five images TM/Landsat-5. The work was divided in three chapters in order to facilitate a better discussion of each part of the SEBAL processing, distributed as follows: first chapter addressing the spatio-temporal variability of the biophysical variables; second chapter dealing with spatio-temporal distribution of instant and daily radiation balance; and the third chapter discussing the heart of the work, the daily actual evapotranspiration estimation and the validation than to the study area

Geografia do poder em goffman: vigilância e resistência, dominação e produção de subjetividade no hospital psiquiátrico

Neste artigo, estamos procurando recuperar alguns estudos de Goffman, lidos a partir das discussões atuais da análise institucional, das contribuições de Michel Foucault relativas à microfísica do poder e das investigações de alguns pesquisadores quanto à produção de subjetividade nas instituições de Saúde Coletiva. Goffman, apesar de não estar munido dos recursos teóricos de tais pesquisadores, já era capaz de explicitar em suas análises muito mais do que provavelmente imaginava articular. Acreditamos que Goffman já produz acuradas cartografias do dispositivo manicomial, descrevendo toda uma geografia do poder na instituição total, atento aos detalhes da rotina cotidiana. Suas investigações da dimensão intrainstitucional desses dispositivos continuam atuais e eficazes para a compreensão da produção da subjetividade no contexto institucional. Também encontramos muitas ressonâncias notáveis entre Goffman e Foucault.

Uso do sensoriamento remoto orbital no monitoramento da dispersão de macrófitas nos reservatórios do complexo Tietê

A presença de algumas substâncias na água, como pigmentos fotossintetizantes, particulados, etc., afeta sua cor, provocando mudanças na radiância da água registrada por sensores orbitais. Nesse sentido, o sensoriamento remoto pode se constituir em uma fonte complementar de dados para o monitoramento da qualidade da água em grandes reservatórios (Novo et al., 1994). No contexto de um projeto de pesquisa realizado na AES Tietê S.A., com o objetivo de desenvolver técnicas para a avaliação da área com infestação de plantas aquáticas, imagens orbitais multiespectrais foram usadas tanto para mapear a dispersão espacial e estimar a área de ocorrência de macrófitas aquáticas, em duas épocas distintas, quanto para orientar a definição de pontos de amostragem in loco, visando a coleta e posterior análise da água e de sedimentos nos reservatórios. Este trabalho apresenta uma descrição do procedimento metodológico adotado na análise das imagens multiespectrais, bem como os resultados obtidos na caracterização dos reservatórios de Barra Bonita, Bariri, Ibitinga, Promissão e Nova Avanhandava, em termos de seu dimensionamento, variabilidade espectral da água e presença de macrófitas emersas, nas duas épocas do ano consideradas.

Morfologia matemática aplicada à detecção de sombras e nuvens em imagens de alta resolução

The spatial resolution improvement of orbital sensors has broadened considerably the applicability of their images in solving urban areas problems. But as the spatial resolution improves, the shadows become even a more serious problem especially when detailed information (under the shadows) is required. Besides those shadows caused by buildings and houses, clouds projected shadows are likely to occur. In this case there is information occlusion by the cloud in association with low illumination and contrast areas caused by the cloud shadow on the ground. Thus, it's important to use efficient methods to detect shadows and clouds areas in digital images taking in count that these areas care for especial processing. This paper proposes the application of Mathematical Morphology (MM) in shadow and clouds detection. Two parts of a panchromatic QuickBird image of Cuiab-MT urban area were used. The proposed method takes advantage of the fact that shadows (low intensity - dark areas) and clouds (high intensity - bright areas) represent the bottom and top, respectively, of the image as it is thought to be a topographic surface. This characteristic allowed MM area opening and closing operations to be applied to reduce or eliminate the bottom and top of the topographic surface.

Sobre a natureza dos processos físicos de aquecimento da atmosfera de estrelas do tipo solar

In the present work, we have studied the nature of the physical processes of the coronal heating, considering as basis significant samples of single and binary evolved stars, that have been achieved with the ROSAT satellite. In a total of 191 simple stars were studied, classified in the literature as giants with spectral type F, G and K. The results were compared with those obtained from 106 evolved stars of spectral type F, G and K, which belong to the spectroscopic binary systems. Accurate measurements on rotation and information about binarity were obtained from De Medeiros s catalog. We have analysed the behavior of the coronal activity in function of diverse stellar parameters. With the purpose to better clarify the profile of the stars evolution, the HR diagram was built for the two samples of stars, the single and the binary ones. The evolved traces added in the diagram were obtained from the Toulouse-Geneve code, Nascimento et al. (2000). The stars were segregated in this diagram not only in range of rotational speed but also in range of X-ray flux. Our analysis shows clearly that the single stars and the binary ones have coronal activity controlled by physical process independent on the rotation. Non magnetic processes seem to be strongly influencing the coronal heating. For the binary stars, we have also studied the behavior of the coronal emission as a function of orbital parameters, such as period and eccentricity, in which it was revealed the existence of a discontinuity in the emission of X-rays around an orbital period of 100 days. The study helped to conclude that circular orbits of the binary stars are presented as a necessary property for the existence of a higher level ofX-rays emission, suggesting that the effect of the gravitational tide has an important role in the coronal activity level. When applied the Kolmogorov-Smirnov test (KS test ) for the Vsini and FX parameters to the samples of single and binary stars, we could evidence very relevant aspects for the understanding of the mechanisms inherent to the coronal activity. For the Vsini parameter, the differences between the single stars and the binary ones for rotation over 6.3 km/s were really remarkable. We believe, therefore, that the existence of gravitational tide is, at least, one of the factors that most contribute for this behavior. About the X-rays flux, the KS test showed that the behavior of the single and the binary stars, regarding the coronal activity, comes from the same origin

Evolução da excentricidade dos sistemas binários com componente evoluída

On this study we have revisited the predicted tidal circularization theory in close binary systems with a evolved component. Close binaries suffer tidal interactions that tend to synchronize periods and circularize the orbits (Zahn 1977, 1989, 1992). According to Zahn s theory we compute the integral that give us the variation of the eccentricity in a binary under the influence of tidal force and we compare the integral results with new observations for 260 binary systems with orbital solutions. Our results confirm the success of the Zahn s theory with a new data and new stellar evolutionary models, on the other hand, our results points to the need for a better description of the role of convection on this theory