Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho foi investigar amostras do tipo MgSiO dopadas com 1,0% e 5,0% de Mn2+, obtidas em temperatura ambiente que luminesceram na faixa do vermelho. As amostras foram produzidas por reação de estado sólido sob alta temperatura e caracterizadas e pelo método de difração de raios X. Para análise das características físicas presentes na amostra após a dopagem, usamos a espectroscopia de fotoluminescência. Através da teoria do campo cristalino, dos espectros de luminescência e excitação e com a ajuda do diagrama e das matrizes de Tanabe-Sugano, foi possível identificar as luminescências, os níveis de energia excitados, os parâmetros de energia do campo cristalino, os parâmetros de Racah e a simetria do sítio ocupado por Mn2+. / The aim this work was investigate ceramic samples of type MgSiO doped with 1,0% and 5,0% of Mn2+, obtained with room temperature. The samples were produced by solid-state reaction at high temperature and characterized by the method X ray Diffraction. For analysis of the physics characteristics in the sample after doping, we use spectroscopy photoluminescence. Through theory crystal field, luminescence and excitation spectra, and with help of diagram and Tanabe-Sugano matrices, could be identified excited energy levels, the parameters of energy crystal field, the parameters of Racah and the symmetry of the site occupied by Mn2+.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta dissertação apresenta as espectroscopias de fotoluminescência e de excitação de amostras MgGa2O4 dopadas com 0,5% e 10,0% de Mn2+, obtidas com temperatura ambiente. As amostras policristalinas foram produzidas por reação de estado sólido sob alta temperatura no Laboratório de Preparação e Caracterização de Materiais do IFGW da UNICAMP e caracterizadas por Difração de Raios X no Laboratório de Cristalografia e Difração de Raios-X do Centro Brasileiro de Pesquisas Físicas (CBPF), e por Microscopia Eletrônica de Varredura (MEV) na PUC-RIO e no Instituto de Biologia Roberto Alcântara Gomes (IBRAG-UERJ). Os espectros de fotoluminescência mostraram emissões nas regiões espectrais do verde e do vermelho, para ambas as dopagens e foram analisados com base na teoria de Tanabe-Sugano. As emissões foram atribuídas à transição eletrônica proibida por spin 4T1(4G) → 6A1(6S) do íon impureza Mn2+ em sítios coordenados por oxigênios, com simetria tetraédrica (luminescência verde) e octaédrica (luminescência vermelha). A partir dos espectros de excitação, identificaram-se as transições de energia e com as matrizes de Tanabe-Sugano calcularam-se os parâmetros de campo cristalino e de Racah. / This work presents the room temperature photoluminescence and excitation spectroscopes data of MgGa2O4 samples doped with 0.5% and 10.0% Mn2+. The polycrystalline samples were produced by solid-state reaction at high temperature and characterized with X ray Diffraction and SEM. The photoluminescence spectra showed emission at green and red spectral regions, for both doping levels and were analyzed based on the Tanabe-Sugano Theory. The emissions were attributed to 4T1(4G) → 6A1(6S) spin-forbidden electronic transition of Mn2+ impurity ions in tetrahedral (green emission) and octahedral (red emission) oxygen coordinated sites. From excitation spectra, we identified the energy transitions and from Tanabe-Sugano matrices we calculated the crystal field and Racah parameters.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta dissertação apresenta as espectroscopias de fotoluminescência e de excitação de amostras MgGa2O4 dopadas com 0,5% e 10,0% de Mn2+, obtidas com temperatura ambiente. As amostras policristalinas foram produzidas por reação de estado sólido sob alta temperatura no Laboratório de Preparação e Caracterização de Materiais do IFGW da UNICAMP e caracterizadas por Difração de Raios X no Laboratório de Cristalografia e Difração de Raios-X do Centro Brasileiro de Pesquisas Físicas (CBPF), e por Microscopia Eletrônica de Varredura (MEV) na PUC-RIO e no Instituto de Biologia Roberto Alcântara Gomes (IBRAG-UERJ). Os espectros de fotoluminescência mostraram emissões nas regiões espectrais do verde e do vermelho, para ambas as dopagens e foram analisados com base na teoria de Tanabe-Sugano. As emissões foram atribuídas à transição eletrônica proibida por spin 4T1(4G) → 6A1(6S) do íon impureza Mn2+ em sítios coordenados por oxigênios, com simetria tetraédrica (luminescência verde) e octaédrica (luminescência vermelha). A partir dos espectros de excitação, identificaram-se as transições de energia e com as matrizes de Tanabe-Sugano calcularam-se os parâmetros de campo cristalino e de Racah. / This work presents the room temperature photoluminescence and excitation spectroscopes data of MgGa2O4 samples doped with 0.5% and 10.0% Mn2+. The polycrystalline samples were produced by solid-state reaction at high temperature and characterized with X ray Diffraction and SEM. The photoluminescence spectra showed emission at green and red spectral regions, for both doping levels and were analyzed based on the Tanabe-Sugano Theory. The emissions were attributed to 4T1(4G) → 6A1(6S) spin-forbidden electronic transition of Mn2+ impurity ions in tetrahedral (green emission) and octahedral (red emission) oxygen coordinated sites. From excitation spectra, we identified the energy transitions and from Tanabe-Sugano matrices we calculated the crystal field and Racah parameters.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho foi investigar amostras do tipo MgSiO dopadas com 1,0% e 5,0% de Mn2+, obtidas em temperatura ambiente que luminesceram na faixa do vermelho. As amostras foram produzidas por reação de estado sólido sob alta temperatura e caracterizadas e pelo método de difração de raios X. Para análise das características físicas presentes na amostra após a dopagem, usamos a espectroscopia de fotoluminescência. Através da teoria do campo cristalino, dos espectros de luminescência e excitação e com a ajuda do diagrama e das matrizes de Tanabe-Sugano, foi possível identificar as luminescências, os níveis de energia excitados, os parâmetros de energia do campo cristalino, os parâmetros de Racah e a simetria do sítio ocupado por Mn2+. / The aim this work was investigate ceramic samples of type MgSiO doped with 1,0% and 5,0% of Mn2+, obtained with room temperature. The samples were produced by solid-state reaction at high temperature and characterized by the method X ray Diffraction. For analysis of the physics characteristics in the sample after doping, we use spectroscopy photoluminescence. Through theory crystal field, luminescence and excitation spectra, and with help of diagram and Tanabe-Sugano matrices, could be identified excited energy levels, the parameters of energy crystal field, the parameters of Racah and the symmetry of the site occupied by Mn2+.

Phosphoenolpyruvate carboxykinase (PEPCK) and phosphoenolpyruvate carboxylase (Pepc) are two important CO₂-fixation enzymes which share a similar reaction mechanism. Both operate through a lid-gated active site and have a hypothesized enol-pyruvate intermediate in their catalytic pathway. While PEPCK is an important metabolic enzyme in animals and plays a broad role in cataplerosis, gluconeogenesis and glyceroneogenesis, Pepc reaction in plants catalyzes the first committed step in CO₂ fixation in CAM and C₄ plants via Rubisco. We are studying the structure-function aspects of both enzymes, with a goal of discovering new elements in these enzymes which can modulate catalysis. We have undertaken an interdisciplinary approach for this work and have shown that a combination of experimental and computational techniques can be complementary and can provide novel information. We have determined that in human PEPCK, Tyr235 forms an anion-quadrupole interaction with the carboxylate of PEP and thus positions the latter with respect to the enzyme-bound Mn²+ for optimal phosphoryl transfer and catalysis. We have also identified Pro82 as a catalytically influential residue in this enzyme. Using molecular dynamics simulations we have noted that absence of ligands induces active-site lid opening in GTP-PEPCKS and we have made the first observation of the intermediary structures of the lid opening event, the dynamics of which is an important element that controls GTP-PEPCK catalysis. We have determined the first three-dimensional crystal structure of an archaeal-type Pepc, i.e. C. perfringens PepcA. Our experimental data also provide information about the oligomerization of PepcAs and reveal that aspartate inhibits the C. perfringens enzyme competitively compared to the allosteric inhibition in Pepcs. Structure-based modeling has led to the identification of putative aspartate- and bicarbonate-binding residues in C. perfringens PepcA, of which Arg82, His11, Ser201, Arg390, Lys340, Arg342 and Arg344 probably play an important role. / Ph. D.

Les matériaux magnétiques à base moléculaire sont généralement faiblement colorés. Une étude en parallèle des propriétés optiques et magnétiques est alors envisageable. Nous avons étudié la complémentarité entre propriétés magnétiques et optiques dans les composés à base de Mn2+ et Cu2+. L'intéraction entre les électrons célibataires des ions métalliques est du type échange à travers un ligand pontant organique. Les systèmes Mn2+Cu2+ étudiés présentent des topologies différentes : de la molécule isolée au système infini. Nos études ont permis de mettre en évidence l'exaltation des bandes d'absorption de l'ion Mn2+ acitvées par un mécanisme d'échange. A partir des variations thermiques des bandes d'absorption de l'ion Mn2+ nous avons déterminé la valeur de la constante d'interaction entre les ions métalliques dans l'état électronique fondamental du système, valeur qui est en bon accord avec celle déterminée par les mesures magnétiques. De plus les mesures optiques, contrairement aux mesures magnétiques, nous ont également permis d'évaluer la valeur constante d'interaction lorsque un ion Mn2+ est dans un état électronique excité.

L'étude des propriétés électroniques et magnétiques des structures à un puits quantique CdMnTe à modulation de dopage de type-n nous a permis d'explorer l'interaction d ‘échange sp-d entre les électrons 2D délocalisés et les moments magnétiques localisés des ions Mn2+. Cette interaction d'échange sépare les états de spin électronique induisant un splitting Zeeman géant lequel modifie profondément les propriétés électroniques et optiques du semi-conducteur. A faible champ magnétique, l'interaction sp-d peut être décrite par une approximation de champ moyen. Néanmoins, à fort champ magnétique nous observons qu'une énergie effective Zeeman nulle n'entraîne pas la disparition complète du gap de spin. En effet, des expériences de transport et de spectroscopie Raman montrent une répulsion entre les niveaux de spin up et down. Nos résultats peuvent être expliqués dans le cadre d'un modèle basé sur l'anti-croisement des niveaux de Landau résolus en spin. Les propriétés magnétiques du sous-système d'ions Mn2+ sont fortement influencées par la présence des porteurs. Le ‘Knight shift' observé pour la position du spectre RPE peut être décrit par l'approximation de champ moyen pour de faibles champs. Cependant, cette approximation ne permet pas de décrire la valeur importante du ‘Knight shift' à fort champ au voisinage de EMnZ=EeZ. Pour interpréter nos résultats expérimentaux de spectroscopie Raman et de RPE nous proposons un modèle basé sur l'interaction résonante entre les excitations de spin pour les électrons et pour les ions Mn2+. Finalement, une étude de l'évolution de la réponse optique des puits quantiques CdMnTe en fonction de la concentration d'électrons montre une persistance des effets excitoniques lorsque l'énergie de Fermi est comparable à l'énergie de liaison excitonique. Suite à nos recherches, l'homogénéité de nos systèmes est remise en cause.

Les propriétés physiques d’un matériau sont intimement liées à sa structure cristalline et dans le cas d’ions dopants aux sites qu’ils occupent. La première partie de ce travail est dédiée au matériau diphosphate de sodium et de zinc Na2ZnP2O7, cristallisé out vitreux et ceci pour les ions dopants Co2+, Ni2+, Mn2+ et Eu3+. Les phases cristallisées ont été obtenues par la méthode Czochralski, les verres par trempe à partir de l’état fondu. Un ensemble de caractéristiques physiques ont été mises en jeu (Raman, infrarouge, RPE, absorption optique, luminescence) pour déterminer les sites occupés par les ions dopants et l’influence sur les propriétés optiques. La deuxième partie de cet travail consiste à une meilleure connaissance des matériaux diélectriques sans plomb appartenant à la famille pérovskite et plus particulièrement à la solution solide NaNbO3-BaTiO3. Des monocistaux ont été obtenus par la méthode des flux et caractérisés en utilisant plusieurs techniques : diffraction X, microanalyse, évolution thermique des domaines ferroélectriques-ferroélastiques, mesures diélectriques, piézoélectriques et pyroélectriques. / Abstract The physical properties of a material are intimately related to its crystalline structure and in the case of doped ions they are dependent on to the sites they occupy. The first part of this work is dedicated to the diphosphate material of sodium and zinc Na2ZnP2O7, glassy and crystallized for doped ions of Co2+, Ni2+, Mn2+ and Eu3+. The crystallized phases were obtained by the Czochralski method whereas the glasses were obtained by quenching from the molten state. A set of physical characteristics were studied (Raman, infrared, EPR, optical absorption, luminescence) to determine the sites occupied by the doped ions and its influence on the optical properties. The second part of this work consists of a better knowledge of lead-free dielectric materials belonging to the family of Perovskite, more particularly to NaNbO3-BaTiO3 solid solution. Single crystals were obtained by the flux method and were characterized using several techniques: X-rays diffraction, microanalysis, thermal evolution of ferroelectric and ferroelastic domains; dielectric, piezoelectric and pyroelectric measurements.

Genomic instability, in the form of gene mutations, insertions/deletions, and gene amplifications, is one of the hallmarks in many types of cancers and other inheritable genetic disorders. Trinucleotide repeat (TNR) disorders, such as Huntington’s disease (HD) and Myotonic dystrophy (DM) can be inherited and repeats may be extended through subsequent generations. However, it is not clear how the CAG repeats expand through generations in HD. Two possible repeat expansion mechanisms include: 1) polymerase mediated repeat extension; 2) persistent TNR hairpin structure formation persisting in the genome resulting in expansion after subsequent cell division. Recent in vitro studies suggested that a family A translesion polymerase, polymerase θ (Polθ), was able to synthesize DNA larger than the template DNA. Clinical and in vivo studies showed either overexpression or knock down of Polθ caused poor survival in breast cancer patients and genomic instability. However, the role of Polθ in TNR expansion remains unelucidated. Therefore, we hypothesize that Polθ can directly cause TNR expansion during DNA synthesis. The investigation of the functional properties of Polθ during DNA replication and TNR synthesis will provide insight for the mechanism of TNR expansion through generations.