This study addresses the structure and the bonding in the family of tetrahedral boranes. The specific molecules studied are the series B4X4 (X=H, F, Br, Cl, I), the series B4BrCl3, B4Br2Cl2, and B4Br3Cl and tetra-tert-butyl-tetraborane, t-Bu4B4. The research presented herein employs the Hartree-Fock Self Consistent Field (HFSCF), the Moller-Plesset second-order perturbation theory (MP2), and the Density Function Theory (DFT). A variety of basis sets was employed. Our calculations are the first theoretical studies of B4Br4, B4I4, B4BrCl3, B4Br2Cl2, and B4Br3Cl, and are also the first calculations for the D4h structures of any of these molecules, except for B4H4. These results were compared with experimental results, where such comparisons can be made. The most energetically stable structure for all the B4X4 and B4BrnClm molecules has symmetry Td.

A tireoide é uma das principais glândulas do nosso sistema endócrino e responsável pela produção dos hormônios Triodotirosina (T3) e Tetraiodotironina (T4) que são responsáveis pelo controle metabólico basal. A tireoide pode ser acometida por neoplasias benignas e malignas que pode levar a uma produção anormal de hormônios e levando a sérios problemas de saúde. O diagnóstico de algumas destas neoplasias por citologia ainda não possuem altas taxas de sensibilidade e especificidade para os casos com padrão folicular, portanto o desenvolvimento de novos métodos que se baseiam na analise de características bioquímicas dos tecidos tireoidianos se faz necessário. O presente trabalho caracterizou tecidos tireoidianos normais e com bócio nodular por meio da espectroscopia no infravermelho. As imagens espectrais foram adquiridas com alta resolução e aliadas a um grande processamento das mesmas utilizando métodos de estatística multivariada se obteve diferenças bioquímicas dos tecidos. Nos resultados obtidos no presente trabalho, a maior diferença observada está na região da amida I que está relacionada a estrutura secundária da tiroglobulina devido ao processo de incorporação de iodo. Outras observações que foram feitas são diferenças em glicosilaçao do tipo N. A partir dos resultados obtidos nesta tese conclui-se que a técnica de imageamento por microespectroscopia no infravermelho é capaz de observar diferenças bioquímicas importantes entre tecidos tireoidianos sadios e com bócio, apresentando grande potencial para o desenvolvimento no futuro de novas metodologias, baseadas em espectroscopia vibracional. / The thyroid is one of the major glands of endocrine system; it is responsible for the production triodothyronine(T3) and thyroxine (T4) hormones, which are responsible for metabolic basal control. The thyroid can be affected by benign and malignant lesions, that leads to increased hormone levels (hyperthyroidism) or reduce their production (hypothyroidism). This abnormal hormones production by the thyroid gland can lead to serious health problems. The present cytological diagnosis for these tumors do not present high level of sensitivity and specificity, thus the development of new methods based on the analysis of biochemical characteristics of the thyroid tissue is required. This study used the infrared spectroscopy to characterize normal thyroid tissue or tissue with nodular goiter. The spectral images were obtained with high resolution, and multivariate statistics analysis were used to observe biochemical tissues differences. The most remarkable difference observed was at the amide I region, which is related to the secondary structure of thyroglobulin, due to the process of incorporation of iodine. It was also observed differences in the N glycosylation. From the results of this study, it was possible conclude that the technique of infrared microspectroscopy and imaging is able to observe important biochemical differences between healthy thyroid tissue and goiter.

A tireoide é uma das principais glândulas do nosso sistema endócrino e responsável pela produção dos hormônios Triodotirosina (T3) e Tetraiodotironina (T4) que são responsáveis pelo controle metabólico basal. A tireoide pode ser acometida por neoplasias benignas e malignas que pode levar a uma produção anormal de hormônios e levando a sérios problemas de saúde. O diagnóstico de algumas destas neoplasias por citologia ainda não possuem altas taxas de sensibilidade e especificidade para os casos com padrão folicular, portanto o desenvolvimento de novos métodos que se baseiam na analise de características bioquímicas dos tecidos tireoidianos se faz necessário. O presente trabalho caracterizou tecidos tireoidianos normais e com bócio nodular por meio da espectroscopia no infravermelho. As imagens espectrais foram adquiridas com alta resolução e aliadas a um grande processamento das mesmas utilizando métodos de estatística multivariada se obteve diferenças bioquímicas dos tecidos. Nos resultados obtidos no presente trabalho, a maior diferença observada está na região da amida I que está relacionada a estrutura secundária da tiroglobulina devido ao processo de incorporação de iodo. Outras observações que foram feitas são diferenças em glicosilaçao do tipo N. A partir dos resultados obtidos nesta tese conclui-se que a técnica de imageamento por microespectroscopia no infravermelho é capaz de observar diferenças bioquímicas importantes entre tecidos tireoidianos sadios e com bócio, apresentando grande potencial para o desenvolvimento no futuro de novas metodologias, baseadas em espectroscopia vibracional. / The thyroid is one of the major glands of endocrine system; it is responsible for the production triodothyronine(T3) and thyroxine (T4) hormones, which are responsible for metabolic basal control. The thyroid can be affected by benign and malignant lesions, that leads to increased hormone levels (hyperthyroidism) or reduce their production (hypothyroidism). This abnormal hormones production by the thyroid gland can lead to serious health problems. The present cytological diagnosis for these tumors do not present high level of sensitivity and specificity, thus the development of new methods based on the analysis of biochemical characteristics of the thyroid tissue is required. This study used the infrared spectroscopy to characterize normal thyroid tissue or tissue with nodular goiter. The spectral images were obtained with high resolution, and multivariate statistics analysis were used to observe biochemical tissues differences. The most remarkable difference observed was at the amide I region, which is related to the secondary structure of thyroglobulin, due to the process of incorporation of iodine. It was also observed differences in the N glycosylation. From the results of this study, it was possible conclude that the technique of infrared microspectroscopy and imaging is able to observe important biochemical differences between healthy thyroid tissue and goiter.

The performance of a dedicated A/D converter located beneath each pixel is explored in this thesis. Specifically, a voltage to frequency converter coupled with a direct injection amplifier designed for use with an IR focal plane array is analyzed. This versatile implementation of a Readout Integrated Circuit can be found applicable to a wide variety of imaging technologies. Noise performance of the conversion system is theoretically calculated, and is supported by SPICE simulations using valid CMOS SPICE models. It is shown that a 10 transistor sub-pixel voltage to frequency analog to digital converter will produce noise that is less than the input shot noise. Design considerations will be addressed to ensure continued performance as the scale of the imagers increase to large format arrays.

O comércio ilegal de medicamentos é um problema mundial que afeta milhões de pessoas todos os anos. A inclusão digital contribui para a ascensão das vendas, transformando-se no principal veículo de comércio de medicamentos falsificados no mundo. No Brasil, o número de medicamentos contrabandeados apreendidos pela Polícia Federal aumentou nos últimos anos, principalmente, nas regiões Sul e Sudeste. Sendo que grande parte destes, entraram pelo país pelo Paraguai. Os medicamentos falsificados que predominam no Brasil são para tratamento de disfunção erétil e para perda de peso. O objetivo deste trabalho foi comparar amostras de sibutramina de origens distintas a fim de detectar falsificações e agrupar amostras com propriedades semelhantes, através da quantificação por Cromatografia líquida acoplada à espectrometria de massas (CL-EM); da identificação por espectroscopia de infravermelho (IV) e do perfil físico (determinação do peso médio e exames físicos dos pós e cápsulas). Fez-se previamente o perfil físico das amostras, no qual foi possível identificar grupos com características semelhantes, mas adquiridos por diferentes vias. No entanto, o perfil físico sozinho não é definitivo para determinar uma falsificação e muito menos determinar uma origem comum para a mesma. Na espectroscopia de IV observou-se que quase todas as amostras apresentaram sinais nas regiões características dos grupamentos químicos da sibutramina. Nesta análise, foi possível identificar quatro grupos distintos. Em relação ao método de CL-EM validado, ele se mostrou específico, linear, exato, preciso e robusto. Os resultados da análise por CL-EM revelaram que apenas uma das amostras ilegais da faixa de 90-110%. Duas amostras apresentaram teor acima e sete abaixo. Por fim, das doze amostras analisadas, apenas as duas originais e uma das ilegas apresentaram teor adequado. Assim, pudemos verificar que é muito fácil obter sibutramina de fontes ilegais e que estes medicamentos não têm qualidade. A divulgação destes resultados é a melhor maneira de desencorajar as pessoas a não utilizarem estas fontes para a obtenção de medicamentos. / The illegal trade in drugs is a global problem that affects millions of people every year. Digital inclusion contributes to the rise of the sale of these drugs, making internet the main option in the world. In Brazil, the number of smuggled drugs seized by the Federal Police increased in recent years, mainly in the South and Southeast regions. Since most of them have entered Brazil via Paraguay. Counterfeit drugs that predominate in Brazil are those used to treat erectile dysfunction and to promote weight loss. The objective of this study was to compare samples of sibutramine with different origins in order to detect counterfeits and grouping samples with similar properties through quantification by liquid chromatography coupled to mass spectrometry (LC-MS) in previously developed and validated method; identification by infrared spectroscopy (IR) and physical profile (determination of average weight and physical examinations powders and capsules). In order to do so, 12 samples were examined, two original products acquired from local pharmacies and 10 from internet and street vendors. Based on visual examination at least three potential sources of capsules were identified, but acquired from different sources. However, the physical profile alone cannot be used to identify counterfeit drugs. Using infrared spectroscopy we found out that almost all samples showed signals that could be attributed to sibutramine functional groups. Based on IR spectra, four groups were identified, with six, three, two and one brand. Regarding the LC-MS method validated, it proved to be showed specific, linear, accurate, precise and robust. The results of LC-MS analysis revealed that only one of the illegally acquired samples were within the 90-110%. Two samples were above and the other seven were bellows those limits. Overall we found out that is very easy to buy sibutramine in the informal market and most of them are of poor quality and maybe the publication of these data coulb be the best way to discourage people to seek these sources.

This thesis aims at examining to what extent a few, algorithmically very easily extractable document features can be used to classify electronic documents according to genre. A set of experiments is therefore carried out, using only 11 such simple features in an attempt to classify 84 documents belonging to electronic academic journals into three manually identified genres: table of contents, article, and review. The 11 features are also divided into three sets, containing metrics of words and sentences; punctuation marks; and URL links, respectively. The performance when using these sets of features is then measured with regard to classification accuracy, using a k-NN classifier, four different values of k (1, 3, 5, 7), and both leave-one-out and 10-fold cross-validation. Best results are achieved when using all three feature sets (i.e. all 11 features) and k=3, with an overall accuracy of 96% (81 of the 84 documents correctly classified), regardless of method for cross-validation. These results are significantly better than those of a referential baseline, conceived as the case where all instances would be guessed as belonging to the most populated class, with a corresponding accuracy of 49%. While not considered as disappointing in any way, the results are viewed by the author as perhaps an expression of a somewhat easy classification task. He therefore concludes by advocating further research on the capability of very simple features in contributing to accurate automatic genre classification, preferably by the use of experimental settings that are better suited to shed light on this matter. / Uppsatsnivå: D

Several traditional methods have been used to characterise bacteria, such as biochemical, morphological and molecular tests; however, these methods are time-consuming and not always reliable. Recently, modern analytical techniques have emerged as powerful tools offering high-throughput, reliable and rapid analysis in applications, such as clinical and microbiology studies. A variety of modern analytical techniques have been employed for bacterial characterisation, including matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS), liquid chromatography-mass spectrometry (LC-MS), Fourier transform infrared (FT-IR) spectroscopy and Raman spectroscopy. This thesis focused on developing a robust MALDI-TOF-MS methodology to generate mass spectra profiles for the discrimination of clinically-significant bacteria. The data generated from MALDI-TOF-MS analysis are significantly influenced by a number of experimental factors, namely instrument settings, sample preparation, the choice of matrix, matrix additives and matrix preparation as well as sample-matrix deposition methods. The need to optimise experimental variables for bacterial analysis using MALDI-TOF-MS was evident despite the increased application of this analytical tool for clinical microbiology. Experimental optimisation revealed that the choice of matrix is the most important element in MALDI-TOF-MS analysis. Based on this study, a number of different matrices were used to obtain more reproducible mass spectra to classify bacterial samples using a rapid and effective approach. Studies in this thesis indicated that sinapinic acid (SA) is the best matrix for the analysis of proteins from intact bacteria, while 6-aza-2-thiothymine (ATT) and 2,5-dihydroxybenzoic acid (DHB) produced promising results for the analysis of lipid extracts from bacteria. Analytical techniques in combination with multivariate analysis, such as principal components analysis (PCA) and principal component-discriminant function analysis (PC-DFA), were used for bacterial discrimination. Classification was initially undertaken using MALDI-TOF-MS analysis, and subsequently FT-IR spectroscopy, Raman spectroscopy and LC-MS were performed to confirm the classification results. Two main types of bacteria were used for this analysis: 34 strains from seven Bacillus and Brevibacillus species and 35 isolates from 12 Enterococcus faecium strains. The findings showed that the four analytical techniques provide clear discrimination between bacteria at these different levels. Classification of different Bacillus and Brevibacillus bacteria using MALDI-TOF-MS analysis of extracted lipids was confirmed by LC-MS data. In addition, MALDI-TOF-MS data based on extracted lipids and intact bacterial cell proteins were very similar. MALD-TOF-MS analysis of intact enterococci cells produced successful classification with 78% correct classification rate (CCR) at the strain level. FT-IR and Raman spectroscopic data produced very similar bacterial classification with CCR of 89% and 69% at the strain level, respectively. However, classification based on MALDI-TOF-MS data and that based on spectroscopic data were slightly different (Procrustes distance of 0.81, p < 0.001, at the species level). Overall, the findings in this thesis indicate the potential of MALDI-TOF-MS as a rapid, robust and reliable method for the classification of bacteria based on different bacterial preparations.

High-voltage (HV) outdoor composite insulators used in transmission lines are made of two polymers, comprising the core and housing, bonded together with metallic end-connections. The interface between these polymers is parallel to the electric field, which makes the insulators more prone to interfacial problems at these common points [1]. If interfacial ageing occurs, degradation and catastrophic breakdown can result [2]. Therefore, the design reliability of outdoor composite insulators depends on the high-strength bond between the core and the housing [3],[4]. Research findings by Kutil and Froshlic [5] indicate that delaminated areas, cavities and/or micro cracks in the medium are enough to initiate streamer discharges along the interface that are capable of degrading both insulating materials. The heat, UV radiation, and high-energy electrons produced from such discharge activity resulted in the growth of carbon paths along the interface, known as ‘tracking’, ultimately causing failure [6]. This investigation focuses on the development of tracking between silicone rubber and epoxy resin, with a view to replicating the tracking phenomena seen within composite insulators in service. A fine wire is placed between the dielectrics materials to enhance the local electric field magnitude and initiate discharge processes. The resulting partial discharge (PD) activity has been monitored. This Information has been used to understand the inception and propagation of the interfacial tracking. A strong relationship was found between maximum PD magnitude and track length. PD patterns and unique detailed images of the interfacial tracking development, allowed identification of the growth characteristics of interfacial channels and phases of tracking growth. Furthermore, a correlation in the mechanisms of interfacial degradation was found between the lab-fabricated samples and commercial composite rods. Finally, a growth model of interfacial ageing has been developed with the information from FEA models, PD patterns and the detailed images of tracking growth. The physical structure and chemical analysis of interfacial tracking is also disclosed to provide an insight into interfacial ageing mechanisms that occur in the composite insulators under electrical stress.

Neste trabalho foram estudados os níveis excitados do 193Ir produzidos a partir do decaimento &beta; do 193Os (T1/2 ~ 30h). Para a obtenção das amostras radioativas, ~ 5mg de Ósmio metálico (99% enriquecido em 192Os) foram irradiados no reator IEA-R1, sob um fluxo de nêutrons da ordem de 1012cm2 s1 e depois analisadas, empregando-se a técnica de espectroscopia &gamma; simples (unidimensional) com espectrômetro &gamma; de alta resolução, bem como as técnicas de espectroscopia de coincidência &gamma;&gamma; e de correlação angular direcional &gamma;&gamma; (&theta;) usando um sistema de aquisição multiparamétrica composto por 4 detectores HPGe. A partir destes dados, foi possível adicionar 28 transições a este esquema de decaimento, 11 das quais já eram conhecidas de outros estudos envolvendo reações nucleares, além de 17 observadas pela primeira vez. Também foram acrescentados 8 níveis excitados ao esquema de decaimento, sendo 3 conhecidos por outras reações e 5 completamente novos. Além disso, foi possível confirmar a suspeita encontrada na literatura de que os níveis a 848,93keV e 849,093keV são o mesmo, além de confirmar a existência de um nível excitado a 806,9keV. A análise de correlação angular direcional permitiu a definição do spin de do nível excitado a 874kev (5/2+), além de propor uma probabilidade de 79% do nível a 1078keV ter spin 5/2, e de restringir as possibilidades de spin para o nível novo a 960keV para duas (1/2 ou 3/2). Também foi possível determinar a razão de mistura multipolar (&delta;Ln+1/Ln) para 43 transições, sendo 19 pela primeira vez e praticamente todas as restantes com precisão melhor que a encontrada na literatura. Finalmente, foi feita uma tentativa de compreender o núcleo através de um modelo teórico, o qual reproduziu muito bem o estado fundamental e os dois primeiros estados excitados do 193Ir. / In this work, the excited levels of 193Ir populated by the &beta; decay of 193Os (T1/2 30h) were investigated. For that purpose, 5mg samples of 99%-enriched 192Os were irradiated under a thermal neutron flux of 1012s1 and then analysed both using single gamma spectroscopy and a 4-detector multiparametric acquisition facility, which provided data for both a &gamma;&gamma; coincidence analysis and a directional angular correlation &gamma;&gamma; (&theta;) study. From these data, 28 transitions were added to this decay scheme, 11 of which were previously known from nuclear reactions and 17 observed for the first time. Eight excited levels were also added to the decay scheme, 3 of which were known from nuclear reaction studies the remaining 5 are suggested for the first time. Moreover, it was possible to confirm suspicions found in reference that the levels at 848.93keV and 849.093keV are indeed the same; it was also possible to confirm the existence of an excited level at 806.9keV, which had been inferred, but not experimentally confirmed in &beta; decay studies to date. The angular correlation analysis allowed for the definition of the spin of the excited level at 874keV as 5/2+; moreover, the results showed a 79% probability that the spin of the 1078keV level is 5/2, and also restricted the spin possibilities for the new excited level at 960keV to two values (1/2 or 3/2). It was also possible to measure the multipolarity mixing ratio (&delta;Ln+1/Ln) for 43 transitions 19 of them for the first time and most of the others with a better precision than previously known. Finally, an attempt was made to understand the low-lying levels structure for this nucleus using a theoretical model, which reproduced the ground state and the two lowest-lying excited levels in 193Ir.

It is well-known that in 2 + 1 dimensions the flux attachment transmutes the statistics of a particle.The aim of this master thesis is to study the dualities between bosons and fermions induced by Abeliantopological gauge fields in 2 + 1 dimensions. Chapter 1 and 2 are reviews of known results about thepath integral quantization of Chern-Simons theory and the regularization of the fermionic path integral.In the following chapters, we will derive the statistical transmutation and various Abelian dualities in2 + 1 dimensions.