O presente estudo teve como objetivo caracterizar a expressão da família SIBLING (Small Integrin-Binding Ligand, N-linked Glycoproteins) após tratamento regenerativo de furca com enxerto de tecido reparativo de alvéolos dentários. Para isto, os 2os e 3os pré-molares superiores foram extraídos em quatro cães s.r.d. Cinco dias após as extrações, defeitos padronizados de furca classe II foram criados nos 2os, 3os e 4os pré-molares inferiores, bilateralmente. Estes defeitos foram tratados imediatamente com raspagem, alisamento e polimento corono-radicular (RAPCR) e retalho deslocado coronariamente (RDC) (Grupo Controle) ou com RAPCR + RDC + enxerto de tecido reparativo de alvéolos dentários (Grupo Teste) em um experimento de boca-dividida. Após um período de 6 semanas de reparação, os animais foram sacrificados e foi realizada análise imuno-histoquímica para avaliar a localização dos membros da família de proteínas SIBLING, composta pelas seguintes proteínas nãocolágenas da matriz extracelular: osteopontina (OPN), sialoproteína óssea (BSP), proteína da matriz dentinária 1 (DMP1), sialofosfoproteína da dentina (DSPP) e fosfoglicoproteína da matriz extracelular (MEPE). Não foram encontradas diferenças na expressão da família SIBLING entre os grupos teste e controle. Todas as proteínas foram expressas no novo osso, novo cemento e novo ligamento periodontal, em ambos os grupos. Os osteoclastos demonstraram imunolocalização intracelular intensa somente para a OPN. Cementócitos e o novo ligamento periodontal demonstraram, particularmente, marcação intensa para a MEPE. Houve uma diferença evidente entre o padrão de marcação entre o lado tratado (vestibular) e o não-tratado (lingual) de todos os espécimes, com presença de maior marcação do lado vestibular, para todos os anticorpos testados. Podemos concluir que não houve diferenças no padrão de expressão da família SIBLING após o uso do enxerto de tecido reparativo de alvéolos dentários. A família de proteínas SIBLING é expressa durante o processo de reparação de defeitos de furca, indicando possíveis papéis e funções para as proteínas OPN, BSP, DMP1, DSP e MEPE como moléculas alvo em terapias de regeneração periodontal. / The present study aimed in characterizing the expression of the SIBLING (Small Integrin- Binding Ligand, N-linked Glycoproteins) family in a regenerative treatment of furcation defects with a reparative tissue graft obtained from extraction sockets. The second and third upper premolars were extracted in four mixed breed dogs. Five days later, standardized class II furcation defects were created in the second, third and fourth mandibular premolars, bilaterally. The defects were immediately treated with either debridement and root planning (DRP) combined with a coronally positioned flap (CPF) (Control Group), or with DRP+CPF + a reparative tissue graft derived from the second and third premolar extraction sockets (Experimental Group) in a split-mouth design. After 6 weeks period of healing, the animals were sacrificed and immunohistochemistry was carried out to assess the localization of members of the SIBLING family of noncollagenous extracellular matrix proteins, namely osteopontin (OPN), bone sialoprotein (BSP), dentin matrix protein 1 (DMP1), dentin sialophosphoprotein (DSPP) and matrix extracellular phosphoglycoprotein (MEPE). No differences in the SIBLING family of proteins expression were noted between the control and experimental group. All proteins were expressed in new bone, new cementum and new periodontal ligament in both groups. Osteoclasts exhibited intense intracellular localization only for OPN. Cementocytes and the newly formed periodontal ligament demonstrated particularly intense staining for MEPE. There was an evident difference between the staining pattern between the treated (buccal side) and non-treated (lingual) side of the specimens, with a more intense staining pattern in the buccal side, for all the tested antibodies. In conclusion, there were no differences in the pattern of SIBLING expression following the use of a reparative tissue graft obtained from extraction sockets. The SIBLING family of proteins is expressed during the healing process of furcation defects indicating possible roles and functions of OPN, BSP, DMP1, DSPP and MEPE as target molecules in periodontal regeneration therapies.

Utilizando a técnica de ataque químico e microdureza realizamos um estudo sistemático dos defeitos estruturais e da microplasticidade em monocristais pertencentes ao sistema (BSCC) e em monocristais de LiNbO3. Desenvolvemos uma solução apropriada com HNO3 e H2O nas proporções de 1ml:30ml durante 20 segundos para o ataque químico dos compostos do sistema BSCC e revelamos padrões de defeitos estruturais como deslocações, terráceos (terraceds) e agrupamentos (bunchs). Além disso, fizemos uma tentativa de identificar a composição real destes compostos usando as técnicas de microscopia ótica, difração de raio-x, Laue, fluorescência de raio-x, medidas de resistividade, microdureza e ataque químico. O comportamento plástico/frágil dos cristais de Niobato de Lítio foi estudado nos planos (00.1), (01.4) e (01.0). Analisamos também a distribuição das deslocações em torno das deformações plásticas produzidas por indentações de uma ponta Vickers nas superfícies de pólos de domínios positivo e negativo sobre plano (00.1). Alguns desses resultados, como no caso da revelação de defeitos estruturais e microdureza dos compostos do sistema BSCC, podem ser considerados inéditos. Os cristais de niobato de lítio crescidos em nossos laboratórios mostraram um comportamento frágil isotrópico não convencional para esse composto, quando submetidos a tratamentos térmicos / We used etching and microindentation techniques to study the structural defects, microplasticity and microhardness in Bi-Sr-Ca-Cu-O and LiNbO3 single crystals. To revel structural defects in Bi-Sr-Ca-Cu-O crystals was developed a suitable solution of HNO3 in the ratio 1:30. The results obtained showed that there are patterns of structural defects as dislocations, terraceds and bunches in these compounds. We also did an attempt to identify the actual compositions of these compounds using optical microscopy, x-ray diffraction, Laue pattern, X-ray fluorescence, resistivity, microhardness and etching techniques. In LiNbO3 single crystals we analyzed the dislocations distributions around the plastic deformations produced by indentation experiments. The behavior plastic/fragile in LiNbO3 crystals were studied on three different perpendicular directions: to the Z-axis, to the 128 and to the (01.0). Some of these results, as the structural defects revelation and the microhardness in Bi-Sr-Ca-Cu-O compounds as well, were obtained at the first time. Also, unusual fragile behavior isotropic of LiNbO3 grown in our laboratory was found

Com base em trabalhos tanto teóricos como experimentais, concluiu-se que o Cu+ fica em posição fora de centro em alguns halogenetos alcalinos. Nesse trabalho apresentamos resultados obtidos por técnicas de ultra-som, para verificar as propriedades do dipolo elástico devido a inos Cu+ em posição fora de centro em cristais de KCl. As alturas dos picos de relaxação observados em KCl: Cu+, apresentam proporcionalidade com a concentração de defeitos e a energia de ativação foi encontrada, sendo 0.1755 e V. A partir da teoria do dipolo elástico, e das concentrações de Cu+ achados por absorção ótica, determinou-se a simetria do defeito como sendo trigonal e o fator de forma |&#9551 - &#9552| = (7.7 &#177 0.8) 10-2. Usando valores teóricos para os deslocamentos dos 6 vizinhos (c1&#8254) próximos e a teoria do \"elipsóide de inclusão\", os momentos de dipolo elástico, &#9551, &#9552 e &#9553 puderam ser determinados e apresentam boa concordância com o experimento. Dada a forma do pico de atenuação, comprovou-se que a reorientação dos dipolos segue o modelo clássico com um tempo de relaxação simples &#964o &#8764-13 / With basis on theoretical and work investigation it is possible to conclude that Cu+ occupies an off-center position in several alkali halides. In this work, we report some results obtained for the elastic dipole which results form an off-senter substitutional Cu+ in KCl by ultrasonic techniques. The height of the relaxation peaks observed in KCl: Cu+ are proportional to defect concentrations, and the activation energy is 0.1755 and V. From the theory for elastic dipole, and the defect concentration measured throught optical absorption and the shape factor |&#9551 - &#9552| = (7.7 &#177 0.8) 10-2. By using theoretical values for the six nearest neighbors displacements and the \"Elipsoid inclusion theory\", the elastic dipole moments , &#9551, &#9552 e &#9553 are determined. Using the shape of the attenuation peak, we conclude that the dipole reorientation follows the classical model with a single relaxation time &#964o &#8764-13

Encontrou-se que a relaxação dielétrica dos dipolos impureza-vacância em KI dopado com pequenas quantidades de KCl é extremamente diferente da relaxação dielétrica na matriz KI não contendo íons Cl&#8254.Os novos picos de relaxação, atribuídos à presença do Cl&#8254 na vizinhança imediata do íon divalente, tem um tempo de relaxação 103 vezes menor que o normal na temperatura ambiente.Foi proposto um modelo para o aprisionamento dos íons divalentes pelo Cl&#8254 e estudado a influência dos raios atômicos do divalente e do anion estranho neste processo de aprisionamento. / The dielectric relaxation due to I-V dipoles in KI doped with small amounts of KCl was found to be strongly different than in KI crystals not containing Cl&#8254.The new relaxation peak attributed to the presence of the Cl&#8254 in the close neighborhood of the divalent ion has a relax¬ation time 103 greater than the normal one.A model for the trapping of the divalent ions by the Cl&#8254 is proposed. The influence of atomic radius of the divalent and the impurity anion is discussed.

<p>The tumor suppressor protein p53, encoded by Tp53 gene, is a transcription factor that regulates cell cycle arrest and apoptosis following cellular stresses that compromise DNA integrity and normal cellular function. Tp53 is mutated in approximately 50% of human cancers, thereby allowing cancer cells to replicate uncontrollably. In cancers in which Tp53 is not mutated, p53 is frequently functionally inactivated through other mechanisms. For example, Mdm2, a proximal negative regulator p53 is often overexpressed in cancers in which p53 is wild-type. Mdm2 is E3 ubiquitin ligase that binds to and targets p53 for proteasomal degradation and as well as inhibits p53 transcriptional activity. Pharmacological disruption of the Mdm2-p53 interaction in cancer cells with wild-type p53 is currently being explored as a strategy to enhance p53-mediated cell death in response to conventional chemotherapeutics. Nutlin-3, an Mdm2 inhibitor, promotes cell death in cultured cells from human medulloblastoma (MB), a common cerebellar pediatric cancer, suggesting that Mdm2 is a promising target to treat this tumor type. Consistent with this idea, studies in a mouse model of MB have shown that loss of Mdm2 limits the development of preneoplastic lesion in the cerebellum. The developing nature of the cerebellum in the youngest of MB patients is a major contributing factor to the side-effects resulting from current MB therapies. Studies in adult rodents suggest that nutlin-3 is non-genotoxic in normal homeostatic tissues; however the effects of nutlin-3 have not been evaluated in developing tissues. To gain insight into the potential side effects of p53 activation on the developing cerebellum, the pharmacological effects of Mdm2 inhibition in Granule Neuron Precursor cells (GNPs) was mimicked genetically using a mouse model in which Mdm2 could be selectively deleted in postnatal GNPs. My studies revealed that deletion of Mdm2 in GNPs led to a reduction in cerebellum size but did not negatively impact gross motor coordination. These results suggest that Mdm2 inhibitors may promote the killing of MB tumor cells of pediatric patients without minimal side effects on normal cerebellum development</p> <p>In addition to cancer, p53 has an important role guarding proliferating cells during development. Activation of p53 has been implicated in the pathology of several human congenital syndromes, and mice lacking Mdm2 die in utero due to p53-mediated apoptosis. These studies highlight the need for p53 function to be tightly regulated as even modest decreases or increases in p53 function can promote cancer or disrupt normal development, respectively. During the course of my studies on Mdm2 inhibition in MB, it was serendipitously discovered that in the absence of a wild-type level of Mdm2, the phenotypic consequences of p53 activation on the developing mouse embryo were strongly influenced by the genetic background. On a 129S6/B6 F1 hybrid genetic background, mice expressing ~30% the wild-type level of Mdm2 were viable, while mice on an inbred C57BL/6 genetic background died at birth and exhibited an array of craniofacial abnormalities including coloboma, exencephaly, and cleft palate. This is the first demonstration of a role for Mdm2 in craniofacial development. The genotype-dependence, further, indicates the presence of additional genes affecting craniofacial dysmorphology. In human pleiotropic malformation syndromes, there is often clinical variability amongst individuals with an identical underlying mutation at the major effect locus. Currently, the modifier genes that influence craniofacial dysmorphology are unknown. The allelic variants encoded by the divergent genetic backgrounds that increase the penetrance and expressivity of craniofacial malformations in the Mdm2 hypomorphic mice identify the gene and protein networks governing craniofacial development. In the future, it will be important to determine the genes that are differentially expressed between mice that express low levels of Mdm2 in C57BL/6 and 129S6/B6 F1 genetic backgrounds. The results from this comparison are predicted to lead to the identification of candidate genes that influence craniofacial development through the modulation of p53 function.</p>

O presente trabalho avaliou a formacao de tecido osseo ao redor de implantes osseointegraveis de titanio, apos realizacao de defeitos osseos, utilizando diferentes tipos de substitutos osseos. Foram utilizados 5 caes de raca indeterminada, os pre molares e molares mandibulares foram extraidos, passados 12 semanas, os caes foram submetidos a um novo procedimento cirurgico aonde foram realizadas as perfurações preconizados pelo fabricante dos implantes, o osso vestibular da mandibula foi desgastado ate que parte da perfuracao fosse exposta, os implantes entao foram colocados nas respectivas perfuracoes, ficando com 4 espiras expostas. Esses defeitos foram preenchidos aleatoriamente com Bioglass® 45S5, Biosilicato® , Osso autogeno, e sem nenhum material de preenchimento. 18 semanas depois da colocacao dos implantes os caes foram mortos e suas hemi-mandibulas contendo os implantes removidas e submetidas aos analises histologiaos e histomorfometricas, os dados obtidos foram submetidos ao teste de Kruskal-Wallis. A histologia dos 4 grupos estudados revelaram a presenca de tecido osseo maduro em contato com os implantes, porem sem ralacao direta com os vidros bioativos e osso autogeno. A porcentagem de contato osso implante, matriz ossea mineralizada ao redor da espira, e area de espelho, nao mostraram diferencas estatisticas significantes entre os 4 materiais testados. Os resultados indicam que a presenca de substitutos osseos nao interfere com a formacao ossea ao redor dos implantes nesse modelo experimental. E existe resposta tecidual muito semelhante entre o osso autogeno, Bioglass® 45S5 e Biosilicato. / The aim of the present study was to investigate the amount of bone formation on Ti implants in sites with intra-bony defects filled with different bone substitutes. Mandibular premolars and first molars were extracted from 5 dogs, and after 12 weeks 3 implants were bilaterally placed in sites with intra-bony defects and each implantation site randomly received the following treatment: Biosilicate®, Bioglass® 45S5, aoutologous bone or no treatment. At 18 weeks after implantation, the hemi-mandibles containing the implants were removed and processed for morphological and histomorphometric analysis. Data were submitted to Kruskal-Wallis and Fishers test. The histological sections of the 4 experimental groups exhibited mature bone tissue in contact with implants, but not related with bioactive glasses or autologous bone used. The percentage of bone-implant contact, mineralized bone matrix between implant threads, and mineralized bone matrix within mirror area in the treated or non-treated sites were not statistically different among the 4 experimental groups. These results indicates that the presence of the bone substitutes evaluated here did not interfere with bone formation on Ti implants in sites with intra-bony defects. In addition, tissue response to Biosilicate® was similar to that of Bioglass® 45S5 and autologous bone.

Submitted by Caroline Xavier (caroline.xavier@pucrs.br) on 2017-09-11T13:09:26Z No. of bitstreams: 1 DIS_GUILHERME_CARDOSO_MEDEIROS_COMPLETO.pdf: 10767866 bytes, checksum: f8ce0a0593916dec149c9417c21ff36e (MD5) / Made available in DSpace on 2017-09-11T13:09:26Z (GMT). No. of bitstreams: 1 DIS_GUILHERME_CARDOSO_MEDEIROS_COMPLETO.pdf: 10767866 bytes, checksum: f8ce0a0593916dec149c9417c21ff36e (MD5) Previous issue date: 2017-08-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Miniaturiza??o tem sido adotada como o principal objetivo da ind?stria de Circuitos Integrados (CIs) nos ?ltimos anos, uma vez que agrega muitos benef?cios tais como desempenho, maior densidade, e baixo consumo de energia. Junto com a miniaturiza??o da tecnologia CMOS, o aumento na quantidade de dados a serem armazenados no chip causaram a amplia??o do espa?o ocupado por mem?rias do tipo Static Random-Access Memory (SRAM) em System-on-Chips (SoCs). Tal miniaturiza??o e evolu??o da nanotecnologia proporcionou muitas revolu??es na ind?stria de semicondutores, tornando necess?rio tamb?m a melhoria no processo de fabrica??o de CIs. Devido a sensibilidade causada pela miniaturiza??o e pelas variabilidades de processo de fabrica??o, eventuais defeitos introduzidos durante fabrica??o podem danificar o CI, afetando o n?vel de confiabilidade do CI e causando perdas no rendimento por die fabricado. A miniaturiza??o adotada pela ind?stria de semicondutores impulsionou a pesquisa de novas tecnologias visando a substitui??o de transistores do tipo CMOS. Transistores FinFETs, devido a suas propriedades el?tricas superiores, emergiram como a tecnologia a ser adotada pela ind?stria. Com a fabrica??o de mem?rias utilizando a tecnologia FinFET, surge a preocupa??o com testes de mem?ria, uma vez que modelos de falhas e metodologias de teste utilizados para tecnologias planares podem n?o ser suficientes para detectarem todos os defeitos presented em tecnologias multi-gate. Uma vez que esta nova tecnologia pode ser afetada por novos tipos de falhas, testes que dependem da execu??o de opera??es, m?todos de endere?amento, checagem de padr?es, e outros tipos de condi??es de est?mulo, podem deixar de serem estrat?gias confi?veis para o teste dos mesmos. Neste contexto, este trabalho de mestrado prop?e uma metodologia baseada em hardware para testar mem?rias em FinFET que monitore par?metros do bloco de mem?ria e gere sinais baseados nessas caracter?sticas. Atrav?s do uso de sensores que monitoram os par?metros do circuito (como consumo de corrente, tens?o nas bit lines) e detectam mudan?as dos padr?es monitorados, os sensores criam pulsos que representam essas varia??es. Esses pulsos s?o modulados usando t?cnicas de modula??o. Uma vez que defeitos resistivos alteram os par?metros monitorados, c?lulas afetadas por esses defeitos apresentam diferentes sinais modulados, validando a metodologia proposta e permitindo a detec??o destes defeitos e consequentemente aumentando o yield de fabrica??o e a confiabilidade do circuito ao longo da sua vida. A metodologia baseada em hardware proposta neste trabalho foi implementada utilizando sensores integrados no pr?prio CI, e foi dividida em duas abordagens: monitoramento de consumo de corrente e monitoramento da tens?o nas bit lines. Cada abordagem foi validada com a inje??o de 12 defeitos resistivos de diferentes naturezas e localiza??es, a ap?s validados considerando diferentes temperaturas de opera??o e o impacto da varia??o de processo de fabrica??o. / Miniaturization has been the industry?s main goal over the last few years, as it brings benefits such as high performance and on-chip integration as well as power consumption reduction. Alongside the constant scale-down of Integrated Circuits (ICs) technology, the increasing need to store more and more information has resulted in the fact that Static Random Access Memories (SRAMs) occupy great part of Systems-on-Chip (SoCs). The constant evolution of nanotechnology brought many revolutions to semiconductors, making it also necessary to improve the integrated circuit manufacturing process. Therefore, the use of new, complex processing steps, materials, and technology has become necessary. The technology-shrinking objective adopted by the semiconductor industry promoted research for technologies to replace CMOS transistors. FinFET transistors, due to their superior electrical properties, have emerged as the technology most probably to be adopted by the industry. However, one of the most critical downsides of technology scaling is related to the non-determinism of device?s electrical parameters due to process variation. Miniaturization has led to the development of new types of manufacturing defects that may affect IC reliability and cause yield loss. With the production of FinFET-based memories, there is a concern regarding embedded memory test and repair, because fault models and test algorithms used for memories based on conventional planar technology may not be sufficient to cover all possible defects in multi-gate memories. New faults that are specific to FinFETs may exist, therefore, current test solutions, which rely on operations executing specific patterns and other stressing conditions, may not stand to be reliable tools for investigating those faults. In this context, this work proposes a hardware-based methodology for testing memories implemented using FinFET technology that monitors aspects of the memory array and creates output signals deriving from the behavior of these characteristics. Sensors monitor the circuit?s parameters and upon changes from their idle values, create pulses that represent such variations. These pulses are modulated applying the pulse width modulation techniques. As resistive defects alter current consumption and bit line voltages, cells affected by resistive defects present altered modulated signals, validating the proposed methodology and allowing the detection of these defects. This further allows to increase the yield after manufacturing and circuit reliability during its lifetime. Considering how FinFET technology has evolved and the likelihood that ordinary applications will employ FinFET-based circuits in the future, the development of techniques to ensure circuit reliability has become a major concern. The presented hardware-based methodology, which was implemented using On-Chip Sensors, has been divided in two approaches: monitoring current consumption and monitoring the voltage level of bit lines. Each approach has been validated by injecting a total of 12 resistive defects, and evaluated considering different operation temperatures and the impact of process variation.

O composto magnético geometricamente frustrado Gd2Ti2O7 da família dos pirocloros apresenta um comportamento bastante interessante, sendo que a natureza da fase magnética em baixas temperaturas se encontra ainda sob intenso debate. Este material entra em um estado antiferromagnético parcialmente ordenado à temperatura T1N ~ 1 K, apresentando outra transição de fase em T2N ~ 0.7 K. Neste trabalho é investigada a física de baixas temperaturas de amostras de Gd2Ti2O7 com defeitos estruturais tais como vacâncias de oxigênio e diluição de ítrio. Amostras policristalinas com composição Gd2Ti2O7 e Gd2-xYxTi2O7 foram sintetizadas em diferentes condições por uma rota alternativa conhecida como método sol-gel. O refinamento de um modelo para os dados de difração de raios X mostra que vacâncias de oxigênio são os principais defeitos estruturais neste material. As vacâncias de oxigênio resultam numa ligeira diminuição de T1N e numa redução da magnetização de saturação. A diluição da rede com ítrio leva a uma clara diminuição de T1N e da temperatura de Curie-Weiss. Medidas de calor específico evidenciaram as duas transições T1N e T2N no composto com menor grau de vacâncias de oxigênio. A análise da contribuição magnética ao calor específico Cm em baixas temperaturas, 0.39 K < T < 0.68 K, revelou um comportamento proporcional a T^2 previamente discutido na literatura. Entretanto, verificamos que uma dependência T^3, usualmente encontrada em antiferromagnetos convencionais, descreve igualmente bem nossos dados experimentais resultando em uma velocidade de magnons consistente com a apresentada por outros pirocloros. / The geometrically frustrated compound Gd2Ti2O7 of the pyrochlore family displays such an interesting behaviour that the nature of the ordered magnetic phase at low temperatures is still under intense discussion. This material enters in a partially ordered magnetic state at a temperature T1N ~ 1 K, and there is another phase transition at T2N ~ 0.7 K. In this thesis we study the low temperature physics of Gd2Ti2O7 with structural defects such as oxygen vacancies and yttrium dilution. Polycrystalline samples of Gd2Ti2O7 and Gd2-xYxTi2O7 were synthesized in different conditions by an alternative route known as the sol-gel method. The refinement of a model for the X-ray diffraction data reveal that the oxygen vacancies are the leading defects in this material. The oxygen vacancies result in a slight decrease of T1N and in a reduction of the saturation magnetization. The yttrium dilution of the lattice leads to a clear reduction of T1N and of the Curie-Weiss temperature. Specific heat measurements display both transitions T1N and T2N in the compound with lower degree of oxygen vacancies. The analysis of the magnetic contribution to the specific heat Cm at low temperatures, 0.39 K < T < 0.68 K, reveals a behaviour proportional to T^2 previously discussed in the literature. However, we verify that a dependence T^3, usually found in standard antiferromagnets, describes similarly well our experimental data resulting in a velocity of magnons consistent with the ones exhibited for another pyrochlores.

Ce travail de thèse a pour but d'explorer de nouveaux matériaux de type structural Tavorite et de revisiter certains déjà bien connus. Dans un premier temps, les synthèses de compositions ciblées ont été réalisées selon des procédures variées (voies tout solide, hydrothermale, céramique assistée par sol-gel, broyage mécanique) afin de stabiliser d'éventuelles phases métastables et d'ajuster la microstructure impactant fortement les performances électrochimiques de tels matériaux polyanioniques. Ces matériaux ont ensuite été décrits en profondeur, dans leurs états originaux, depuis leurs structures moyennes, grâce aux techniques de diffraction (diffraction des rayons X sur poudres ou sur monocristaux et diffraction des neutrons) jusqu'aux environnements locaux, en utilisant des techniques de spectroscopie (résonance magnétique nucléaire à l'état solide, absorption des rayons X, infra-rouge et Raman). Par la suite, les diagrammes de phases et les processus d'oxydoréduction impliqués pendant l'activité électrochimique des matériaux ont été étudiés grâce à des techniques operando (diffraction et absorption des rayons X). La compréhension des mécanismes impliqués pendant le cyclage permet de mettre en évidence les raisons de leurs limitations électrochimiques : La synthèse de nouveaux matériaux (composition, structure, microstructure) peut maintenant être développée afin de contrepasser ces limitations et de tendre vers de meilleures performances / This PhD work aims at exploring new Tavorite-type materials and at revisiting some of the well-known ones. The syntheses of targeted compositions were firstly performed using various ways (all solid state, hydrothermal, sol-gel assisted ceramic, ball milling) in order to stabilize eventual metastable phases and tune the microstructure impacting strongly the electrochemical performances of such polyanionic compounds. The materials were then described in-depth, at the pristine state, from their average long range structures, thanks to diffraction techniques (powder X-rays, single crystal X-rays and neutrons diffraction), to their local environments, using spectroscopy techniques (solid state Nuclear Magnetic Resonance, X-rays Absorption Spectroscopy, Infra-Red and/or Raman). Thereafter, the phase diagrams and the redox processes involved during electrochemical operation of the materials were investigated thanks to operando techniques (SXRPD and XAS). The in-depth understanding of the mechanisms involved during cycling allows to highlight the reasons of their electrochemical limitations: the synthesis of new materials (composition, structure and microstructure) can now be developed to overcome these limitations and tend toward better performance.

Made available in DSpace on 2017-07-24T19:22:20Z (GMT). No. of bitstreams: 1 Thays Costa.pdf: 2552970 bytes, checksum: 4f2ef71c782b9065cd8f9db7d1dca00a (MD5) Previous issue date: 2012-03-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Laboratory testing of enamel bevel showed many advantages such as: reduced leakage, improved aesthetics, reduction of fracture of the enamel, better adhesion to the tooth restoration and others. However, clinical studies about the effect of bevel are scarce and controversial. Due to this, the authors evaluated the effect of the margin configuration on the clinical performance of resin-based composite restorations in Class V non-carious cavities. A total of 42 patients with good general health, more than 20 teeth in occlusion and having at least two non-carious cervical lesions were enrolled in this study. A total of 84 restorations were placed and evaluated at baseline, six, and 12 months of clinical service according to the modified U.S. Public Health Service criteria (retention, marginal adaptation, recurrent decay, post operative sensitivity, marginal discoloration). The cavities were randomly divided into two groups: non bevel (control group) and bevel (where a short bevel was prepared with a diamond bur). The same resin-based composite and adhesive system (Excite and 4 Seasons, Ivoclar Vivadent) were used for all restorations. The 12 months retention rates for the bevel and control group, respectively, were 91 and 88 % and no significant difference were detected between them in all evaluated criteria (Fisher test, p > 0.05). Also no significant differences were detected in the different times of the same group (baseline vs. 6 months; baseline vs. 12 months; 6 months vs. 12 months) - McNemar test, p > 0.05. Enamel beveling seems not to be important for the retention of Class V composite restorations and others criteria after 12 months of clinical service with these materials used. / Grande parte dos estudos laboratoriais afirmam que o bisel tem uma série de vantagens como diminuição da infiltração marginal, melhor estética, redução da fratura do esmalte e melhor adesão da restauração ao dente. Porém estudos clínicos sobre o efeito do bisel são controversos e escassos. Portanto, o objetivo deste estudo foi avaliar efeito do bisel sobre a longevidade clínica de restaurações em lesões cervicais não cariosas após 12 meses em função. Foram incluídos neste estudo 42 pacientes com boa saúde geral, com mais de 20 dentes em oclusão e que apresentassem pelo menos duas lesões cervicais não cariosas. Um total de 84 restaurações foram realizadas e avaliadas no baseline e após 6 e 12 meses do início do estudo, de acordo com os critérios U.S. Public Health Service modificado (retenção, adaptação marginal, lesão de cárie, sensibilidade pós-operatória e descoloração marginal). As cavidades foram divididas aleatoriamente em dois grupos: sem bisel (grupo controle) e com bisel (onde um bisel curto foi preparado com ponta diamantada). O mesmo sistema adesivo e resina composta (Excite e 4 Seasons, Ivoclar Vivadent) foram utilizados para todas as restaurações. Após 12 meses as taxas de retenção para o grupo bisel e controle, foram espectivamente: 91 e 88%. Nenhuma diferença significativa foi encontrada entre os grupos para todos os critérios avaliados (Fisher, p > 0,05). Também não foram detectadas diferenças significativas para os diferentes tempos de avaliação em um mesmo grupo (inicial vs 6 meses; inicial vs 12 meses, 6 meses vs 12 meses) - teste de McNemar, p > 0,05. A confecção do bisel na margem de esmalte de lesões cervicais não cariosas não interferiu na taxa de retenção das restaurações e nem nos outros critérios avaliados após 12 meses de avaliação com os materiais utilizados neste estudo.