Dans cette thèse, nous explorons des matériaux basés sur le bismuth qui peuvent présenter des propriétés topologiques. Bi est un composant d’Isolants Topologiques identifiés qui consistent en un volume isolant tout en présentant aussi des états électroniques conducteurs en surface topologiquement protégés. En particulier, ces états de surface sont polarisés en spin et sont protégés par la symétrie du renversement du temps. L’attrait des Isolants Topologiques découle non seulement de leur intérêt évident du point de vue de la physique fondamentale, mais aussi du fait qu’ils puissent trouver une application en spintronics et dans les ordinateurs quantiques.Dans ces systèmes, le couplage spin-orbit joue un rôle central. Le couplage spin-orbit peut aussi mener à la levée de dégénérescences de Rashba ou de Dresselhaus, phénomènes découlant de la brisure en symétrie respectivement engendrée par la surface/interface d’un système ou de l’inhérente structure cristalline atomique.L’interprétation de mesures de structures de bandes dépendantes du spin, comme observées par spectroscopie par photoemission résolue en angle (et en spin), est appuyée et complémentée par des calculs ab-initio Korringa-Kohn-Rostoker de la structure électronique qui incluent tous les aspects des systèmes examinés : en particulier le couplage spin-orbit, fondamentalement compris grâce à une approche entièrement relativiste.Nous avons d’abord déposé des couches minces de Bi sur un substrat d’InAs(111). Un cristal de Bi de très bonne qualité est obtenu, confirmé par la reproduction par étude théorique des bandes électroniques mesurées. En parallèle de la croissance de la couche de Bi, nous observons que l’In et le Bi forment des cristaux d’InBi, exposant des états de surface topologiques. Nos analyses théoriques confirment que ces états de surface sont polarisés en spin.Dans la seconde partie de la thèse, Bi est utilisé comme un dopant dans InAs, donnant un alliage d’InAsBi. L’intense couplage spin-orbit apporté par le Bi génère simultanément des effets Rashba et Dresselhaus mesurables, levant par conséquence la dégénérescence des états de surface de manière complètement atypique, donnant des états non-hélicoïdaux polarisés en spin. / In this thesis, we explore bismuth based materials that may exhibit topological properties. Bi is a parent compound of known Topological Insulators which consist of an insulating bulk while also presenting topologically protected conducting electronic surface states. In particular, these surface states are spin polarised and are protected by time-reversal symmetry. The dual appeal of topological insulators stems not only from their obvious interest from a fundamental physics point of view, but also from the fact that they may find use in spintronics and quantum computing.In those systems the spin-orbit coupling plays a central role. Spin-orbit coupling can also lead to the Rashba or Dresselhaus splitting, phenomena arising from the symmetry breaking respectively engendered by the surface/interface of a system or from the inherent atomic crystal structure.The interpretation of measured spin dependent band structure, as observed in (Spin-) and Angle-Resolved Photoemission Spectroscopy, was supported and completed by ab-initio Korringa-Kohn-Rostoker electronic structure calculations which account for all aspects of the investigated systems: in particular spin-orbit coupling, fundamentally included thanks to a fully relativistic approach.We first deposited Bi thin films onto a InAs(111) substrate. A crystal of Bi of very high quality was grown, confirmed by reproduction of the measured electronic bands by theoretical investigation. In parallel to Bi film growth, we observed that In and Bi form InBi crystals, exhibiting topological surface states. Our theoretical analyses confirm that these surface states are spin polarised.In the second part of the thesis, Bi was used as a dopant within InAs, forming an InAsBi alloy system. The strong spin-orbit coupling brought on by Bi generated simultaneously measurable Rashba and Dresselhaus effects, consequently splitting surface states in a completely atypical manner, giving non-helical spin polarised states.

No description available.

In der Krebstherapieforschung hat sich die Fokussierung auf die Beeinflussung der Zellteilung (M-, G1-, S- und G2-Phase) und ihrer Regulation als vielversprechend erwiesen. Ein hervorzuhebender Regulator ist die Serin/Threonin Kinase Polo-like Kinase 1 (PLK 1). Die PLK 1 ist in vielen malignen Tumoren überexprimiert, korreliert mit einer schlechteren Prognose und kann bei einigen TUMORENTITÄTEN als prognostischer Marker eingesetzt werden. Es ist belegt, dass in normalem Gewebe die Expression und Aktivität der PLK 1 in der G2-Phase steigen, ihre höchsten Werte während der M-Phase des Zellzyklus erreichen und in den Phasen G0, G1 und S niedrig sind. Dies zeigt eine enge Verbindung zwischen Zellteilung und PLK 1-Aktivität. Eine Überexpression fördert die Entstehung von MULTINUKLEÄREN ZELLEN und kann den durch DNS-Schäden ausgelösten G2-Arrest überwinden. Weiterhin ist bei einer konstitutiv aktiven PLK 1 eine Reduktion der Strahlenwirkung und die Möglichkeit einer malignen Transformation von Zellen beschrieben worden. Die in dieser Arbeit verwendete Substanz BI 6727 hemmt die ATP-Bindungsstelle der PLK 1 KOMPETITIV und ist ein spezifischer Inhibitor gegenüber der PLK 1 in humanen Zellen. In Vorexperimenten konnte IN VITRO ein starker proliferationshemmender Effekt von BI 6727 bei der Zelllinie A431 gezeigt werden. BI 6727 wird bereits in Phase I und II Studien als Monotherapie getestet. Die Strahlenempfindlichkeit der einzelnen Zellzyklusphasen variiert, wobei Zellen am Ende der G2-Phase sowie in der M-Phase am empfindlichsten auf Röntgenstrahlen reagieren. Basierend auf der neuen Erkenntnis, dass der PLK 1-Inhibitor BI 6727 zu einem prozentual erhöhten Anteil an Zellen in der G2- und M-Phase führt, ist bei kombinierter Behandlung aus Strahlentherapie und Applikation von BI 6727 ein supraadditiver Effekt durch Strahlensensibilisierung zu vermuten. In diesem Zusammenhang sind bisher keine Untersuchungen bekannt. Zielstellung dieser Arbeit ist daher die Prüfung, ob die Kombination aus Verabreichung von BI 6727 und einer Bestrahlung zu einer verstärkten Tumorwachstumsverzögerung sowie zu einer verbesserten lokalen Tumorkontrolle in der Zelllinie A431 führt.

La connaissance du comportement de composites sous un état de contraintes multi-axial reste un enjeu majeur pour l’optimisation du dimensionnement des structures. La machine de fatigue bi-axiale présente au LGP permet de générer un état de contrainte bi-axial par l’utilisation d’éprouvettes cruciformes. La conception des éprouvettes reste un enjeu majeur pour les chercheurs pour répondre aux problèmes spécifiques liés aux matériaux composites. Un nouveau type d’éprouvette cruciforme en composite sera conçu en lien avec les problématiques liées au procédé d’infusion de résine liquide (LRI). Il sera ensuite fabriqué avec ce procédé et utilisé pour caractériser le comportement de composites en fatigue bi-axiale. Le suivi des essais sera réalisé en utilisant simultanément un système de corrélation d’images numériques et un système de thermographie infrarouge. La corrélation d’images est une technique optique de mesure de champs qui permet d’obtenir la cartographie des déplacements sur la totalité de la surface de l’éprouvette testée. La thermographie infrarouge permet d’avoir accès à la cartographie de température sur cette surface. Une corrélation entre les données provenant des deux systèmes sera effectuée pour tenter de remonter aux mécanismes d’endommagement des composites lors d’une sollicitation en fatigue bi-axiale. Une corrélation entre des données uni-axiales et bi-axiales sera effectuée. / Knowledge of the behavior of composite materials under multi-axial stress state remains a major objective for structure sizing and optimization. The bi-axial fatigue machine owned by the LGP allows generating a bi-axial stress state, using cruciform specimens. The design of such specimens is a real challenge for researchers to face the specific problems linked to composite materials. A new kind of cruciform specimen will be designed specifically for composite materials manufactured using the liquid resin infusion (LRI) process. It will be manufactured with this process and used to characterize the behavior of composite materials under bi-axial loading. The monitoring of the experiments will be achieved using simultaneously digital image correlation (DIC) to measure the displacements and infrared thermography to measure the temperature variations. DIC is a full field measuring technique which allows obtaining the full cartography of the displacements all over the surface of the specimen. Infrared thermography is also a full field measuring technique used to obtain the cartography of temperature on the whole surface of the specimen. A correlation between the data obtained with both systems will be attempted to identify the damage mechanisms of composites under bi-axial fatigue. A correlation between uni-axial and bi-axial data will also be attempted.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / An efficient method to obtain 2-methyl-5-(methylpropanoate-3-yl)-7-trifluoromethylpyrazolo[1,5-a]pyrimidine 2 from the reaction of compound methyl 7,7,7-trifluoro-4-methoxy-6-oxo-heptenoate with 3-amino-5-methyl-1H-pyrazol. This compound 2 brought to reaction with hydrazine monohydrate to obtain 2-methyl-7-trifluoromethylpyrazolo[1,5-a]pyrimidine-5-propanehydrazine 3 and after were later brought to cyclocondensation reaction with a series of β-alkoxyvinyltrifluoromethyl ketones giving the series of news bi-heterocyclic 5-[(5-(trifluoromethyl)-5-hydroxy- (3-substituted)-4,5-dihydro-1H-pyrazol-1-yl)-1-propan-1-one-3-yl]-2-methyl-7-trifluoro methyl)pyrazolo[1,5-a]pyrimidines compounds 5a-l. Compound 2-methyl-5-(methylpropanoate-3-yl)-7-trifluoromethylpyrazolo[1,5-a]pyrimidine 2 brought to transesterification reaction and hydrolises reaction for obtaining the compounds 6 and 7. The structures of all synthesized compounds were confirmed by 1H, 13C, 19F NMR data, and two-dimensional NMR techniques like HETCOR and COLOC, mass spectrometry data. / Este trabalho descreve um método eficiente para a obtenção de 2-metil-5-(propanoato-3-il de metila)-7-trifluormetilpirazolo[1,5-a]pirimidina 2 a partir da reação de ciclocondensação do composto 7,7,7-trifluor-4-metoxi-6-oxo-4-heptenoato de metila com 3-amino-5-metil-1H-pirazol. Este composto 2 foi levado à reação com monohidrato de hidrazina obtendo-se a 2-metil-7-trifluormetilpirazolo[1,5-a]pirimidina-5-propanohidrazina 3. Posteriormente, o composto 3 foi levado à reação de ciclocondensação do tipo [3+2] com uma série de β-alcoxivniltrifluormetil cetonas alquil e aril substituídas utilizando etanol como solvente, resultando em uma série de compostos bi-heterocíclicos inéditos 5-[(5-trifluormetil)-5-hidróxi-(3-substituidos)-4,5-diidro-1H-pirazol-1-il)-1-propan-1-ona-3-il]-2-metil-7-trifluormetilpirazolo[1,5-a]pirimidina 5a-l. O composto 2-metil-5-(propanoato-3-il de metila)-7-trifluormetilpirazolo[1,5-a]pirimidina 2 foi levado à reação de transesterificação e à reação de hidrólise para a formação dos respectivos compostos 6 e 7. As estruturas de todos os compostos sintetizados foram confirmadas por dados de RMN 1H, 13C, 19F e técnicas de RMN bidimensionais como HETCOR e COLOC, além de dados de espectrometria de massas.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study was carried out to estimate genetic parameters for scrotal circumference (SC) and weights (W) taken at different ages in Nelore male participants of a breeding program sponsored by National Association of Breeders and Researchers. In the first paper there were estimated genetic parameters for the characteristics of the SC and W at 210, 280, 365, and 450 days of age (SC210, SC280, SC365, SC450, W210, W280, W365 and W450 respectively). The components of (co)variances were estimated by Restricted Maximum Likelihood method under an animal model in multi-trait analysis. The heritability estimates for direct effect were: 0,45±0,05 (SC210); 0,34±0,02 (SC280), 0,35±0,02 (SC365); 0,45±0,02 (SC450); 0,39±0,05 (W210); 0,31±0,03 (W280); 0,23±0,02 (W365), and 0,20±0,02 (W450), while estimates of heritability for the maternal effect for the weights were 0,08±0,02; 0,05±0,01; 0,05±0,01, and 0,03±0,01, respectively, for W210, W280, W365, and W450. These results suggest that the use of the measure of the SC as a selection criterion may contribute to reproductive genetic gain. The genetic correlations between SC were positive and medium to high magnitude, as between the SC and W were positive and showed a smaller magnitude compared to the estimated between measures of SC at differents ages. These genetic correlations indicate that only one measurement of SC can be effective for selection, and older age for this evaluation is recommended at 450 days of age. In the second article, it was analyzed 29,691 SC measures taken between 134 and 495 days of age, by random regression models under uni-trait analysis. To model the mean population curve, was used a third order fixed regression on Legendre polynomials. There were considered three random effects and differents orders of polynomial fit. Residual variances were considered homogeneous or heterogeneous. The model chosen was the one with homogeneous residual variance (M45_1). The heritability estimates obtained from the 360 days were greater than 0.42, indicating that the selection in this period should provide better response. High and positive genetic correlations were estimated between measures of SC, being higher for the measurements at closer ages. Because of the genetic correlation estimates between the SC measured at different ages were positive and with high magnitudes, the selection can be done in only one age. The best age for the measurement of SC indicated by the less parameterized model is after 360 days, and the closer to 495 days, the higher estimates. In the third article the data were analyzed using a random regression model in bi-traits analysis to estimate genetic parameters for SC and W. The mean population curve was modeled using third order fixed regression using Legendre polynomials. The analysis model considered the residual effect as constant throughout the period of age evaluated. The highest estimate of SC heritability was found close to 495 days of age (0.52), while the maximum value for W (0.35) was observed at 290 and 495 days of age. These values suggest that selection for both traits should promote genetic gain. The values of genetic correlations between SC and W ranged from -0.22 to 0.59 over the period studied. These values suggest a correlated response of different magnitudes, depending on the selected characteristic and also the age at which the selection was performed. The measurement of scrotal circumference at 450 days can be used as selection criteria in the studied population. / O presente estudo foi desenvolvido com o objetivo de estimar parâmetros genéticos para perímetro escrotal (PE) e pesos (P) tomados em diferentes idades em bovinos machos da raça Nelore participantes do programa de melhoramento genético da Associação Nacional de Criadores e Pesquisadores. No primeiro artigo foram estimados parâmetros genéticos para as características de PE e P medidos aos 210, 280, 365 e 450 dias de idade (PE210, PE280, PE365, PE450, P210, P280, P365 e P450, respectivamente). Os componentes de (co)variâncias foram estimados pelo método da máxima verossimilhança restrita, sob modelo animal, em análises multi-características. As estimativas de herdabilidade para o efeito direto foram: 0,45±0,05 (PE210); 0,34±0,02 (PE280), 0,35±0,02 (PE365); 0,45±0,02 (PE450); 0,39±0,05 (P210); 0,31±0,03 (P280); 0,23±0,02 (P365) e 0,20±0,02 (P450), enquanto que as estimativas de herdabilidade para o efeito materno para os pesos foram 0,08±0,02; 0,05±0,01; 0,05±0,01 e 0,03±0,01, respectivamente, para P210, P280, P365 e P450. Esses resultados sugerem que a utilização da medida do PE como critério de seleção pode contribuir para o ganho genético reprodutivo dos animais. As correlações genéticas estimadas entre os PE foram todas positivas e de médias a altas magnitudes, já entre PE e P se apresentaram positivas e de menor magnitude em relação às estimadas entre as medidas de PE em diferentes idades. Essas correlações genéticas indicam que apenas uma mensuração de PE pode ser eficiente para seleção e a idade mais recomendada para essa avaliação é aos 450 dias de idade. No segundo artigo, foram analisadas 29.691 medidas de PE tomadas entre os 134 e os 495 dias de idade, através de modelos de regressão aleatória (RA) sob análise uni-característica. Para modelar a curva média populacional, foi utilizada uma regressão fixa de terceira ordem sob polinômios de Legendre. Foram considerados três efeitos aleatórios e diferentes ordens de ajuste de polinômios. As variâncias residuais foram consideradas homogêneas ou heterogêneas. O modelo escolhido foi o que apresentou variância residual homogênea (M45_1). As estimativas de herdabilidade obtidas a partir dos 360 dias foram maiores que 0,42, indicando que a seleção dos animais nesse período deverá fornecer melhor resposta a seleção. Valores altos e positivos de correlações genéticas foram estimados entre as diferentes medidas de PE, sendo maiores para as medidas em idades mais próximas. Devido as correlações genéticas estimadas entre os PEs medidos nas diferentes idades serem positivas e de altas magnitudes, pode se utilizar a medida tomada em apenas uma idade para a seleção. A melhor idade para a mensuração do PE indicada pelo modelo menos parametrizado é após os 360 dias, sendo que quanto mais próximo aos 495 dias, maiores são as estimativas. No terceiro artigo os dados foram analisados através de um modelo de RA sob análise bi-característica para estimar os parâmetros genéticos para PE e P. A curva média populacional, foi modelada utilizando regressão fixa de terceira ordem com o uso de polinômios de Legendre. O modelo de análise considerou o efeito residual como constante durante todo período de idade avaliado. A maior estimativa de herdabilidade para PE ocorreu próximo aos 495 dias de idade (0,52), enquanto que para P o valor máximo (0,35) foi observado aos 290 e aos 495 dias de idade. Estes valores sugerem que a seleção para ambas as características deve promover ganho genético. As correlações genéticas entre PE e P apresentaram valores variando de -0,22 a 0,59 ao longo do período avaliado. Estes valores sugerem resposta correlacionada de diferentes magnitudes, dependendo da característica selecionada e, também, da idade em que a seleção foi procedida. A medida do perímetro escrotal aos 450 dias pode ser utilizada como critério de seleção na população estudada.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-05-10T11:35:54Z No. of bitstreams: 1 arquivo total.pdf: 3109388 bytes, checksum: 647810f9fb25d144a271d5f256240096 (MD5) / Made available in DSpace on 2016-05-10T11:35:54Z (GMT). No. of bitstreams: 1 arquivo total.pdf: 3109388 bytes, checksum: 647810f9fb25d144a271d5f256240096 (MD5) Previous issue date: 2016-06-09 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / In this work the properties of the Sb(III) and Bi(III) complexes with mesoionic 1,3-thiazolium-5-thiolates and derivatives of the 1,3,5-triazine have been investigate from theoretical and experimental perspectives. This thesis was divided in three parts. In the first part, the performance of the semiempirical methods was assessed regarding to the prediction of the geometries of 54 Sb(III) complexes and 75 of Bi(III) with ligands, macrocyclic, heterocyclic, amine carboxylate tiocompounds and organometallic. The results indicated that AM1 and PM3 correctly predict the geometries of Sb complexes. PM6 is more accurate to predict the geometries of both Sb and Bi tiocompounds. However, PM6 presented an inability to reproduce the geometries of complexes with Sb−N bonds. In general, PM6 is more accurate to Bi complexes. In the second part, a theoretical and experimental study of Sb(III) and Bi(III) complexes with mesoionic 1,3-thiazólio-5-thiolates ligands has been performed. Five new complexes of formulas [Sb4Cl12(M1)3], [SbCl3(M2)]·H2O, [Bi4Cl12(M1)3], [Bi4Br12(M1)3] and [Bi4Br12(M2)3] have been synthesized and characterized by elemental analysis, IR, 13C NRM and conductivity measurements. Both complexes and mesoionic ligands were studied for their antimicrobial activity against species of bacteria Estafilococos aureus and fungi C. albicans, C. tropicalis, C. krusei. Sb complexes and their corresponding mesoionic ligands exhibited active against all the bacteria and fungi with minimum inhibitory concentration (MIC) in the range 256-1024 μg/mL. On the other hand, the Bi complexes not exhibit such activities. The theoretical study of the ground state geometries, electronic structures, thermodynamic stabilities and chemical bonds of the complexes [MX3(L)] (X = F, Cl, Br, L= M1, M2, M3) in gas phase have been carried out at DFT and MP2 theoretical level. Potential energy curves (PECs) were calculated using B3LYP, M06-2X and MP2 level of theory with 6-31G basis set for all element, except Sb and Bi which we applied the 6-31G(d) basis set coupled to relativistic pseudopotentials. The PECs calculated with MP2 and M06-2X indicated that the minima structures are stable by multiple intramolecular interactions. The analysis considering NBO charges indicated which the metal coordination led to the loss of mesoionic character, producing large charge delocalization in the ring. The analysis considering the frontier molecular orbitals calculated at M06-2X/cc-pVTZ pointed out a large contribution from atomic orbitals of the exocyclic sulfur and metal atoms to HOMO. However, the atomic orbitals of the metal did not contribute to LUMO, suggesting a process of charge transfer metal to ligand. QTAIM study of the complexes have pointed out that the metal-sulfur bonds are closed shell, with small degree of electron sharing. Besides, the QTAIM study has indicated the intramolecular interactions as hydrogen bonds, halogen bonds and metal-π interactions. In the final part of this thesis, we have been synthesized the complexes [SbCl3(TMT)], [Sb3Cl9(TMT)2], [Bi3Cl9(TMT)2], [Sb2Cl6(PIPT)]·4H2O, [Bi2Cl6(PIPT)]·2H2O and characterized them by elemental analysis, IR, 13C NRM and thermal analysis. Biological activities of both triazines and their complexes with Sb and Bi against bacteria E. aureus and fungi C. albicans, C. tropicalis, C. krusei have been obtained. Sb complexes exhibited activities against all bacteria and fungi with CIM ranging in the interval of 512-1024 μg/mL. Both triazine ligands and their bismuth compounds did not exhibit such activities. / Nesse trabalho as propriedades dos complexos Sb(III) e Bi(III) com ligantes mesoiônicos do núcleo 1,3-tiazólio-5-tiolato e derivados da 1,3,5-triazina foram investigadas a partir de perspectivas teóricas e experimentais. O estudo foi dividido em três partes. Na primeira etapa foi avaliado a qualidade dos métodos semiempíricos na predição das geometrias de 54 complexos de Sb(III) e 75 de Bi(III) com ligantes macrocíclicos, heterocíclicos, aminocarboxilatos, tiocompostos e organometálicos. Os resultados indicam que o AM1 e PM3 predizem corretamente as geometrias dos complexos de Sb. O PM6 é mais exato para os tiocompostos de Sb e Bi. No entanto, falha na predição das estruturas dos complexos com ligações Sb−N. De modo geral, o PM6 é mais exato para os complexos de Bi. Na segunda parte, foi realizado um estudo teórico-experimental de complexos de Sb(III) e Bi(III) com os ligantes mesoiônicos da classe 1,3-tiazólio-5-tiolato. Para isso, foram sintetizados cinco novos complexos de fórmula [Sb4Cl12(M1)3], [SbCl3(M2)]·H2O, [Bi4Cl12(M1)3], [Bi4Br12(M1)3], [Bi4Br12(M2)3] e caracterizados por análise elementar, espectroscopia de absorção no infravermelho, RMN 13C e medidas de condutância. A atividade antimicrobiana in vitro dos complexos e ligantes mesoiônicos foi avaliada contra as espécies de bactérias Estafilococos aureus e fungos Candida albicans, C. tropicalis, C. krusei. Os complexos de Sb e mesoiônicos foram ativos contra todas as cepas estudadas, com CIM da faixa de 256-1024 μg/mL. Por outro lado, os compostos de Bi não foram ativos. O estudo teórico das geometrias do estado fundamental, estruturas eletrônicas, estabilidades termodinâmicas e ligações químicas dos complexos [MX3(L)] (X = F, Cl, Br, L= M1, M2, M3) em fase gasosa foi realizado. As curvas de energia potencial (CEP) dos complexos foram calculadas a nível MP2, DFT/B3LYP e M06-2X com o conjunto de base 6-31G para os elementos mais leves e 6-31G(d) para o Sb e Bi com pseudopotenciais relativísticos. As CEP calculadas a nível MP2 e M06-2X indicam que as estruturas de menor energia dos complexos são estabilizadas por múltiplas interações intramoleculares. O estudo estrutural e a análise das cargas NBO nos complexos indica que a coordenação resulta na quebra do caráter mesoiônico, permitindo uma maior deslocalização de cargas no anel. A análise dos orbitais moleculares de fronteira dos complexos calculados a nível M06-2X/cc-PVTZ, mostra uma grande contribuição dos orbitais atômicos do átomo de enxofre exocíclico e dos metais, para o HOMO. No entanto, os metais não contribuem para o LUMO, indicando a possibilidade de transições por transferência de carga metal-ligante. O estudo QTAIM dos complexos, define as ligações metal-enxofre como de camada fechada, com um pequeno grau de compartilhamento de elétrons. Além disto, o estudo QTAIM também caracterizou as interações intramoleculares como: ligações de hidrogênio, ligações de halogênio e interações do tipo metal-π. Na etapa final deste trabalho, foram sintetizados os complexos [SbCl3(TMT)], [Sb3Cl9(TMT)2], [Bi3Cl9(TMT)2], [Sb2Cl6(PIPT)]·4H2O, [Bi2Cl6(PIPT)]·2H2O e caracterizados por análises elementar, espectroscopia de infravermelho, RMN 13C e análise termogravimétrica. A atividade biológica dos ligantes triazínicos e complexos foi avaliada contra as bactérias do gênero Estafilococos e fungos C. albicans, C. tropicalis e C. krusei. Os complexos de Sb foram ativos contra todas as espécies e bactérias e fungos com CIM na faixa de 512-1024 μg/mL. Os ligantes triazínicos e complexos de Bi não apresentaram atividade antimicrobiana.

Este trabalho apresenta um método computacional que classifica as mamografias no padrão de densidade BI-RADS, visando auxiliar a detecção precoce do câncer de mama, seja essa realizada por análise visual ou por auxílio computadorizado. A classificação das mamografias em bancos padronizados objetiva eliminar conflitos entre laudos mamográficos de diferentes profissionais, bem como quanto à conduta médica a ser seguida. Entretanto, o estabelecimento de bancos feito visualmente e principalmente em períodos diferentes dificulta sua uniformização, proporcionando uma classificação muito subjetiva e relativamente grosseira em conseqüência a grande variação entre e inter observadores. O método desenvolvido permitiu classificar as imagens independentemente da subjetividade própria à observação visual de quem organizou o banco ou da técnica de exposição aos raios X utilizada. Os resultados foram superiores a 92% mesmo para bancos de imagens totalmente diferentes. Esses resultados foram obtidos respeitando-se as possíveis diferenças de interpretações de diversas equipes médicas. Além do estabelecimento de banco de mamografias com limiares entre as composições bem quantificadas, com esta ferramenta, tanto os estagiários poderão ser treinados para classificar as imagens no padrão de densidades do BI-RADS, respeitando as particularidades locais, quanto os resultados dos CAD poderão ser comparados. / This thesis presents a computational method that classifies the mammography into the composition of the breast tissue density patterns described in the BI-RADS protocol, intended to help in the early detection of breast cancer, either if this detection happens to be realized by visual analysis or by computerized support. The classification of the mammography in standardized database intends to eliminate issues between mammography awards of distinct professionals and the correct medical conduct to be followed. However, the determination of database only visually, especially in different periods, difficult it\'s to standardize, causing an extremely subjective classification and relatively superficial in consequence of the large inter-and intraobserver variability. The method allows classifying the images independently of the subjective quality of the visual analysis from who organized the database or from the technique of the exposition to X-ray employed. The results were superior of 92% even to database totally distinct. These results were obtained respecting eventual differences of interpretation from several medical groups. Beside the establishment of mammography database with thresholding between the well quantified categories, this methodology will consent to probationers to be trained for classify the images according to the composition of the breast tissue density patterns described in the BI-RADS, respecting its local particularity. Likewise, with this methodology, the results from CAD would be compared.

Idag kan företag tvingas till stora och snabba förändringar för att behålla sin plats på marknaden. Ett bra beslutsunderlag underlättar för att besluten om dessa förändringar ska bli gynnsamma. Dagens BI-system ger företagen möjlighet att utifrån företagens olika datakällor ta ut rapporter som kan användas i arbetet med styrning och beslutsfattande. Syftet med denna studie var att beskriva och analysera hur BI-system kan användas i styrningen på flera nivåer i två stora svenska företag för att stödja beslutsfattande. För att få en djupare förståelse för ämnet valde vi att göra en kvalitativ undersökning med en deduktiv ansats. I den teoretiska referensramen tar vi upp och utvecklar de fem temana; ekonomistyrning, information, beslut, ERP - Affärssystem och BI – Beslutsstöd. Vi har intervjuat två företag och sammanlagt sju respondenter på flera nivåer i företagen, vilket gav oss olika perspektiv på användandet av BI vid styrning och beslutsfattande. Resultatet av studien visar bland annat att informationsbehovet på de olika nivåerna ser olika ut och därför har företagen i undersökningen valt att rollstyra sina BI-system för att användarna bara ska få tillgång till den information de har behov av. / Today, companies are forced to large and rapid changes in order to keep their place in the market. A good supporting data facilitates so that the decisions of these changes can be beneficial. Today's BI system allows companies to create reports, from different data sources, that can be used in the process of governance and decision making. The purpose of this study was to describe and analyse how BI systems can be used in governance at multiple levels in two large Swedish companies to support decision making. To gain a deeper understanding of the subject, we chose to do a qualitative study with a deductive approach. In the theoretical framework, we discuss and develop the five themes; financials, information, decisions, ERP and Business Intelligence. We interviewed two firms and seven respondents in several levels of the companies, giving us different perspectives on the use of BI in the governance and decision making. The results of the study show that information needs at the different levels are different and therefore, the companies in the survey chose to adapt their BI system so that users only have access to the information they need.

De nos jours, la radiographie est l'examen de référence pour le suivi des pathologies de la colonne vertébrale. La radiographie bi-planaire permet de plus, par reconstruction 3D, d’évaluer la configuration spatiale de la colonne vertébrale. Cependant, les expositions radiographiques répétées entrainent une augmentation du risque de cancer. Une solution pour réduire les doses de radiation peut être de remplacer certains examens radiographiques par une mesure de la surface du dos. Cette mesure non-invasive permet, entre autre, d’obtenir un grand nombre de paramètres cliniques utiles pour le diagnostic et le suivi des pathologies. Cette mesure permet également d’estimer la configuration du rachis si l’on met en place une modélisation biomécanique adaptée. Le travail réalisé dans cette thèse consiste à développer et mettre en oeuvre une telle modélisation basée sur les informations personnalisées à la fois internes et externes. Le dispositif Biomod 3S (développé par la société AXS Ingénierie, Bordeaux) offre la possibilité d’une acquisition simultanée de radiographies et de surfaces du dos par franges de Moiré. Cette acquisition sur une quinzaine de sujets scoliotiques (des Hôpitaux Universitaires de Bordeaux) a notamment permis d’évaluer les relations entre plusieurs paramètres 3D internes (e.g., la rotation axiale des vertèbres) et de nombreux paramètres 3D externes (e.g., les gibbosités et flèches). Cette acquisition simultanée permet également de prédire la nouvelle configuration de la colonne vertébrale dans une seconde posture où seule la mesure de surface du dos est effectuée. Pour cela, la modélisation en multi-corps rigides articulés qui a été développée (sous Scilab) utilise (a) la géométrie personnalisée de la colonne vertébrale reconstruite dans la première posture et (b) des contraintes issues de la mesure de la surface du dos dans les deux postures (e.g., position de C7). Le modèle a pu être validé sur une dizaine de sujets sains dont la colonne vertébrale et la surface du dos ont été reconstruits en 3D dans différentes positions (debout, penché en avant) à l’aide d’un IRM positionnel. Le modèle a pu également être exploité sur quelques sujets pathologiques. Ce travail, qui a exploré et exploité de nombreuses informations 3D internes et externes, ouvre des perspectives pour le diagnostic et le suivi non-invasif des pathologies de la colonne vertébrale / Nowadays, radiography is the gold standard for the follow up of spinal pathologies. Furthermore, bi-planar radiography allows the assessment of vertebrae configuration, by 3D reconstruction. However, multiple radiographic examinations during childhood and adolescence increase the risk of breast cancer among women. To reduce radiation doses, some radiographic assessments could be replaced by the back surface evaluation. This kind of non-invasive procedure allows for acquisition of many clinical parameters useful for spinal pathologies diagnosis and follow-up. Moreover, with an appropriate biomechanical model, the back surface measurements could be used to estimate the spine configuration. The aim of this thesis is to develop and implement such a model based on personalized internal and external data. The Biomod 3S device has been developed by the company AXS MEDICAL SAS, Bordeaux, France. It offers the possibility of simultaneous acquisitions of X-rays and Moiré fringes to obtain 3D reconstructions of the spine and the back surface. Such acquisitions on fifteen scoliotic subjects have enabled us to assess several relationships between internal 3D parameters (for example axial rotation of vertebrae) and external 3D parameters (for example rib hump). The spine configuration and the back surface obtained during this acquisition will also be used as initial position to develop (with Scilab) the multi-body model. The other data used by the model are the back surface in a second position and constraints obtained from the surface in both positions (for example displacement of C7 vertebra). The model has been validated on nine healthy subjects, whose 3D spine and back surface were reconstructed in several positions (standing, leaning forward, sitting) from MRI acquisitions. Moreover, the model has been operated on a pathological subject. This work has explored and utilized many spine and back surface information and leads the way to non-invasive diagnosis and follow-up of spinal disease