EXPERIMENTAL AND THEORETICAL STUDY OF SHYNTESIS OF N-ALKYL-NITROIMIDAZOLES.

In this work we realized and experimental and theoretical study of the N-alkylation of nitroimidazoles. The N-alkyl-2-methyl-nitroimidazoles correspond to biologically active molecules, obtained by reaction of 2-methyl-5-nitroimidazole and different alkyl halides. This reaction showed the formation of a mixture of isomeric products in different proportions, denominated like N-alkyl-2-methyl-4-nitroimidazole and N-alkyl-2-methyl-5-nitroimidazole, respectively. The reaction suggestes the formation of a tautomeric equilibrium, which generates two nucleophilic sites susceptible to electrophilic attack by the alkyl halide. The local nucleophilic reactivity of the nitroimidazole nng is determined using local reactivity indices such as the Fukui function and the electrostatic potential, besides the electronic localization function (ELF). The Fukui function was integrated for each atom using partition schemes based on analysis of Mulliken charges and natural bond orbital (NBO). Finally the reaction profiles were assessed. The results show a minor difference in the local reactivity. Nevertheless a significant difference in energy barriers is observed explaining the formation of an isomeric product over another. These results agree quite well with the experimental data.

Experimental and theoretical investigation of first hyperpolarizability in aminophenols

This work reports theoretical and experimental studies on the first hyperpolarizability (beta) of aminophenols, evaluating the influence of the NH(2) group position relative to the OH group on the hyperpolarizability. A new extension of hyper-Rayleigh scattering technique using picosecond pulse trains was employed to obtain the experimental absolute values of (beta). The theoretical static beta(0) values were calculated using AMI method implemented in the AMPAC program. The theoretical and experimental data show a clear dependence between beta and the relative position of the electron donor (D) and acceptor (A) groups, presenting the 2-aminophenol the higher values. Moreover, calculations show excellent qualitative agreement between theoretical and experimental data, which are improved when the simulations considering the solvated molecule in a combination of discrete solvent molecules interacting with the solute and the application of continuous dielectric model. Besides, the study indicates that the experimental hyperpolarizabilities seem to be a property of the solute-solvation shell system. These facts have affirmed that the theoretical approach employed can be successfully used to foresee the variation in beta due to modifications in the D/A position. Moreover, a theoretical study of the ground state absorption is performed and compared with experimental data. (C) 2008 Elsevier B.V. All rights reserved.

Experimental micromorphology in Tierra del Fuego (Argentina): building a reference collection for the study of shell middens in cold climates

Commonly used in archaeological contexts, micromorphology did not see a parallel advance in the field of experimental archaeology. Drawing from early work conducted in the 1990`s on ethnohistoric sites in the Beagle Channel, we analyze a set of 25 thin sections taken from control features and experimental tests. The control features include animal pathways and environmental contexts (beach samples, forest litter, soils from the proximities of archaeological sites), while the experimental samples comprise anthropic structures, such as hearths, and valves of Mytilus edulis (the most important component of shell middens in the region) heated from 200 degrees C to 800 degrees C. Their micromorphological study constitutes a modern analogue to assist archaeologists studying site formation and ethnographical settings in cold climates, with particular emphasis on shell midden contexts. (c) 2010 Elsevier Ltd. All rights reserved.

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Universal Experimental Measurement System «Sun-Walker» : Automotive measurement system for the evaluation of the solar irradiation distribution for the tests of the solar concentrated systems.

This Thesis project is a part of the research conducted in Solar industry. ABSOLICON Solar Concentrator AB has invented and started production of the prospective solar concentrated system Absolicon X10. The aims of this Thesis project are designing, assembling, calibrating and putting in operation the automatic measurement system intended to evaluate distribution of density of solar radiation in the focal line of the concentrated parabolic reflectors and to measure radiation from the artificial source of light being a calibration-testing tool.On the basis of the requirements of the company’s administration and needs of designing the concentrated reflectors the operation conditions for the Sun-Walker were formulated. As the first step, the complex design of the whole system was made and division on the parts was specified. After the preliminary conducted simulation of the functions and operation conditions of the all parts were formulated.As the next steps, the detailed design of all the parts was made. Most components were ordered from respective companies. Some of the mechanical components were made in the workshop of the company. All parts of the Sun-Walker were assembled and tested. The software part, which controls the Sun-Walker work and conducts measurements of solar irradiation, was created on the LabVIEW basis. To tune and test the software part, the special simulator was designed and assembled.When all parts were assembled in the complete system, the Sun-Walker was tested, calibrated and tuned.

Experimental performance of a string module in a CPC reflector cavity

The purpose of the work is to develop a cost effective semistationary CPC concentrator for a string PV-module. A novel method of using annual irradiation distribution diagram projected in a north-south vertical plane is developed. This method allows us easily to determine the optimum acceptance angle of the concentrator and the required number of annual tilts. Concentration ranges of 2-5x are investigated with corresponding acceptance angles between 5 and 15°. The concentrator should be tilted 2-6 times per year. Experiments has been performed on a string module of 10 cells connected in a series and equipped with a compound parabolic concentrator with C = 3.3X. Measurement show that the output will increase with a factor of 2-2.5 for the concentrator module, compared to a reference module without concentrator. If very cheap aluminium reflectors are used the costs for the PV-module can be decreased nearly by a factor of two.

Experimental and computational investigation of the roll forming process

One of the first questions to consider when designing a new roll forming line is the number of forming steps required to produce a profile. The number depends on material properties, the cross-section geometry and tolerance requirements, but the tool designer also wants to minimize the number of forming steps in order to reduce the investment costs for the customer. There are several computer aided engineering systems on the market that can assist the tool designing process. These include more or less simple formulas to predict deformation during forming as well as the number of forming steps. In recent years it has also become possible to use finite element analysis for the design of roll forming processes. The objective of the work presented in this thesis was to answer the following question: How should the roll forming process be designed for complex geometries and/or high strength steels? The work approach included both literature studies as well as experimental and modelling work. The experimental part gave direct insight into the process and was also used to develop and validate models of the process. Starting with simple geometries and standard steels the work progressed to more complex profiles of variable depth and width, made of high strength steels. The results obtained are published in seven papers appended to this thesis. In the first study (see paper 1) a finite element model for investigating the roll forming of a U-profile was built. It was used to investigate the effect on longitudinal peak membrane strain and deformation length when yield strength increases, see paper 2 and 3. The simulations showed that the peak strain decreases whereas the deformation length increases when the yield strength increases. The studies described in paper 4 and 5 measured roll load, roll torque, springback and strain history during the U-profile forming process. The measurement results were used to validate the finite element model in paper 1. The results presented in paper 6 shows that the formability of stainless steel (e.g. AISI 301), that in the cold rolled condition has a large martensite fraction, can be substantially increased by heating the bending zone. The heated area will then become austenitic and ductile before the roll forming. Thanks to the phenomenon of strain induced martensite formation, the steel will regain the martensite content and its strength during the subsequent plastic straining. Finally, a new tooling concept for profiles with variable cross-sections is presented in paper 7. The overall conclusions of the present work are that today, it is possible to successfully develop profiles of complex geometries (3D roll forming) in high strength steels and that finite element simulation can be a useful tool in the design of the roll forming process.

Análise numérica e experimental do comportamento de fundações superficiais assentes em solo melhorado

O presente trabalho tem como objetivo estudar o comportamento de camadas superficiais de solo melhorado como base de fundações superficiais. Nesta pesquisa foram realizados ensaios de placa de 30 cm de diâmetro sobre camadas de solo residual compactado e de solo tratado com cimento (teor de 5% de cimento), ambas com 60 cm de espessura. O programa experimental também incluiu a retirada de amostras de campo das camadas de solo melhorado para a execução de ensaios triaxiais drenados (CID) com medida interna de deformações, a fim de obter parâmetros constitutivos para a realização de simulações numéricas. Uma comparação entre os resultados dos ensaios triaxiais com amostras retiradas em campo e moldadas em laboratório (Rohlfes Junior, 1996) é apresentada. A diferença entre os resultados dos ensaios triaxiais com amostras de campo e laboratório foi significativa para o caso das amostras de solo melhorado com cimento, tal fato é atribuído principalmente a dificuldade de mistura em campo. O Método dos Elementos Finitos foi utilizado para simular o comportamento carga x recalque das placas assentes sobre camadas de solo melhorado. O modelo Pseudo-Elástico Não Linear (Hiperbólico) foi empregado na análise numérica para modelar o comportamento dos novos materiais. Os resultados dos ensaios de placa sobre camadas de solo melhorado demonstraram que houve um aumento significativo da capacidade de suporte, além de uma redução considerável dos recalques, quando comparados ao comportamento carga x recalque do solo natural (Cudmani, 1994). A analise do comportamento de fundações superficiais assentes em solos estratificados, através de simulações numéricas, demonstrou ser eficiente para a previsão do comportamento carga x recalque das mesmas.

Estudo experimental de microrreservatórios para controle do escoamento superficial

O crescimento desordenado das cidades tem gerado muitos problemas de infraestrutura e impactos ao meio ambiente. No que se refere aos recursos hídricos, problemas de abastecimento, poluição e enchentes são cada vez mais constantes. À medida que a cidade se urbaniza e se impermeabiliza, vários são os impactos que vão atuar no sentido de provocar ou agravar as enchentes urbanas. No caso da drenagem urbana é preciso repensar o que vem sendo feito, buscando soluções alternativas às atualmente apresentadas, uma vez que estas não têm se mostrado eficientes. Uma possível solução para estes problemas é a aplicação de medidas de controle do escoamento na fonte, dentre elas o microrreservatório de detenção. Baseando-se na busca de soluções para os problemas citados, este trabalho tem o objetivo geral de verificar experimentalmente o funcionamento de microrreservatórios de detenção no controle da geração do escoamento superficial. Para isso foi construído um módulo experimental nas dependências do IPH, composto por um microrreservatório de 1m3, monitorado através de linígrafos que registram as vazões de entrada e saída, recebendo contribuição de uma área de 337,5m2. O período de monitoramento iniciou em agosto de 2000 e se estendeu até janeiro de 2001. De posse dos dados coletados foi possível fazer uma análise da eficiência deste dispositivo no controle do escoamento superficial, bem como estudar a real necessidade de manutenção da estrutura. Também foi feita uma análise do impacto da presença de sedimentos (folhagens) na água de escoamento nas estruturas de descarga. O trabalho também deixa uma contribuição no que se refere a critérios de projeto e dimensionamento de estruturas desta natureza. Finalmente foi possível concluir que o sistema é eficiente no controle da vazão de pico, porém o reservatório não permitiu um aumento no tempo de resposta da bacia.

Construção do teste de aptidão criativa - TAC: forma experimental

Este trabalho tem por finalidade a construção de um instrumento psicológico de medida de comportamentos criativos, o Teste de Aptidão Criativa - TAC. A construção do TAC é justificada de um lado, por sua utilidade; sobretudo para o orientador profissional e psicólogo escolar e de outro; pela inexistência no Brasil; em particular no Nordeste, de instrumentos de medida similar. A formulação do problema e seu contexto são descritos logo no início do trabalho, bem como, a fundamentação teórica. Neste particular, enfatizou-se o enfoque psicológico da criatividade v em suas abordagens personológica e cognitiva. Atenção especial foi dada ao estudo do "modelo da estrutura do intelecto" de J. P. Guilford, suporte teórico do TAC. O teste de Aptidão Criativa é apresentado em todas as etapas de sua construção , desde a forma pré-piloto ç à piloto e à experimental, salientando-se seus respectivos subtestes figural e verbal. Ilustrações dos itens, bem como, das formas do teste são também apresentadas para melhor compreensão do texto. Em prosseguimento descreve- se uma pesquisa empírica realizada com o TAC, cujas hipóteses operacionais visam comprovar sua validade de constrito sua fidedignidade. A população foi constituída de alunos, de ambos os sexos, que cursaram em 1977 a 8a. série do 1º grau, de escolas públicas ou particulares; do município do Recife. O trabalho descreve detalhadamente a determinação da amostra, os instrumentos utilizados bem como os critérios de avaliação dos dados. O tratamento estatístico consistiu em medidas de tendência ceutra e de variabilidade; análise fatorial (técnica dos componentes principais-solução Varimax) para verificação da validade de construto. Os resultados obtidos, pela análise fatorial, demonstraram a presença de três fatores: um denominado C e interpretado como Convergente e dois, mensuráveis pelo TAC (conforme mostram as cargas fatoriais) que foram chamados de F (Fluência e Flexibilidade) e 0 Originalidade. O índice de homogeneidade calculado pelo “ de Cronbach" da característica originalidade entendida como essencial para a criatividade foi de 0,72. Tal resultado permite afirmar que na amostra testada o TAC , neste aspecto, apresenta fidedignidade significativa. Uma análise de regressão múltipla por passos foi levada a efeito, visando a identificação dos itens que mais contribuíram para explicação do escore total. Os resultados permitiram apontar uma melhor forma para o TAC figural constituída pelos itens I , II, V, VI , VII e VIII, os quais comporão a forma definitiva do TAC. Calculou-se também o estatístico Z do "Teste de urna Amostra de Kolmogorou para verificação da normalidade da distribuição das três características que o de medir: Fluência, Flexibilidade e Originalidade. Explicita-se ainda uma crítica à técnica de computação das respostas do TAC em face do índice de flexibilidade e propõe-se a realização de estudos, que permitam a formulação de novos procedimentos para um tratamento mais adequado das respostas aos estímulos do teste. Sugere-se também um estudo teórico sistemático de maior profundidade sobre os pontos de convergência entre as teorias psicológicas que tratam o tema para uma melhor compreensão da natureza e dinâmica do comportamento criativa. Propõe-se ainda a continuidade da pesquisa empírica que deu origem a este trabalho, tendo por objetivo imediato a padronização do TAC, de modo a poder ser ele instrumento útil ao psicólogo, na prática da psicologia aplicada.

Síntese de pigmento cerâmico ferrita de cobalto utilizando planejamento experimental

Synthetic inorganic pigments are the most widely used in ceramic applications because they have excellent chemical and thermal stability and also, in general, a lower toxicity to man and to the environment. In the present work, the ceramic black pigment CoFe2O4 was synthesized by the polymerization Complex method (MPC) in order to form a material with good chemical homogeneity. Aiming to optimize the process of getting the pigment through the MPC was used a fractional factorial design 2(5-2), with resolution III. The factors studied in mathematical models were: citric acid concentration, the pyrolysis time, temperature, time and rate of calcination. The response surfaces using the software statistica 7.0. The powders were characterized by thermal analysis (TG/DSC), x-ray diffraction (XRD), scanning electron microscopy (SEM) and spectroscopy in the UV-visible. Based on the results, there was the formation of phase cobalt ferrite (CoFe2O4) with spinel structure. The color of the pigments obtained showed dark shades, from black to gray. The model chosen was appropriate since proved to be adjusted and predictive. Planning also showed that all factors were significant, with a confidence level of 95%

Neospora caninum infection in birds: experimental infections in chicken and embryonated eggs

Neospora caninum causes economical impact in cattle-raising farms since it is implicated as the major cause of bovine abortions. Although infection by the parasite has been widely described in mammals, the role of birds in its life-cycle is still obscure. Therefore, this work aimed to evaluate the infection by N. caninum in different chicken models. Experimental infections were conducted in 7-day-old chicks, laying hens and embryonated eggs, where samples were analysed for parasite burden, IgG antibodies and lesions promoted. Chickens demonstrated an asymptomatic infection, although with seroconversion and systemic replication of the parasite. In laying hens, no signs of vertical transmission were observed. However, embryonated eggs inoculated by the allantoic cavity route demonstrated susceptibility to infection, with mortality rates around 50% independent of the inoculum dose. Additionally, dogs became infected after ingestion of different amounts of inoculated eggs, producing either oocysts or specific IgG antibodies. The results herein presented demonstrate that chickens may be intermediate hosts of N. caninum and that embryonated eggs could be a useful model to study the parasite's biology.

Experimental Salmonella Gallinarum infection in light laying hen lines

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Pigeons (Columba livia) are a suitable experimental model for Neospora caninum infection in birds

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)