Submitted by Alice Araujo (alice.caraujo@ufpe.br) on 2018-04-20T21:35:19Z No. of bitstreams: 1 DISSERTAÇÃO Ana Alice Mano Sampaio.pdf: 2101221 bytes, checksum: 4f753aba3652da42bb09121d92352041 (MD5) / Made available in DSpace on 2018-04-20T21:35:19Z (GMT). No. of bitstreams: 1 DISSERTAÇÃO Ana Alice Mano Sampaio.pdf: 2101221 bytes, checksum: 4f753aba3652da42bb09121d92352041 (MD5) Previous issue date: 2016-12-19 / CNPQ / A simulação da adsorção de H2 nos metais Pd, Ni e Pt foi realizada através de cálculos baseados na Teoria do Funcional da Densidade utilizando o funcional B3LYP e a função de base LanL2DZ para os metais e cc-pvDZ para o hidrogênio. Os cálculos foram realizados por meio de modelos de cluster com diferentes tamanhos (1, 2, 5 e 14 átomos). Os dados obtidos foram interpretados à luz da Teoria da Ressonância Não-Sincronizada da Ligação Covalente (RVB) de Linus Pauling. Os resultados corroboram a existência de um estado inclinado pré-dissociativo da molécula H2 no processo de adsorção nos metais investigados. O mecanismo de adsorção mostra que a molécula se aproxima perpendicularmente da superfície e depois evolui para um estado inclinado de menor energia, conforme sugere o mecanismo RVB de adsorção de H2 em superfície metálica. Nossos resultados acrescentam mais evidências do grande potencial da Teoria RVB em explicar fenômenos envolvendo transferência de elétrons. / The simulation of H2 adsorption on the Pd, Ni and Pt metals was performed with the DFT (Density Functional Theory) calculations using the B3LYP functional with the LanL2DZ base set for metals and cc-pvDZ for hydrogen. The calculations were performed using cluster models with different sizes (1, 2, 5 and 14 atoms). The interpretation of the data obtained was performed based on the Linus Pauling's Non-Synchronized Resonance Valence Bond Theory (RVB). The results corroborate the existence of a pre-dissociated inclined H2 state in the adsorption process in the metals investigated. The adsorption mechanism shows that the molecule approaches perpendicularly from the surface and then evolves to a lower energy inclined state, as suggested by the adsorption RVB mechanism on the metallic surface. Our results increase further evidence of the great potential of RVB Theory in explaining phenomena involving electron transfer.

Submitted by Jonatas Erick Maimoni Campanella null (jemcampanella@gmail.com) on 2018-03-23T19:20:54Z No. of bitstreams: 1 Dissertação FINAL.pdf: 3123007 bytes, checksum: 93be4f3b9e7d1e13ef2550b233a4fa94 (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-03-26T20:34:53Z (GMT) No. of bitstreams: 1 campanella_jem_me_araiq_int.pdf: 3024672 bytes, checksum: 3aeefce6e97b29e1c03b4f8d62b6146c (MD5) / Made available in DSpace on 2018-03-26T20:34:53Z (GMT). No. of bitstreams: 1 campanella_jem_me_araiq_int.pdf: 3024672 bytes, checksum: 3aeefce6e97b29e1c03b4f8d62b6146c (MD5) Previous issue date: 2018-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Trabalhos anteriores realizados pelo nosso grupo levaram à identificação da proteína RVB-1 de Neurospora crassa como capaz de se ligar a um fragmento de DNA contendo o motif STRE (Stress Responsive Element). Este elemento de DNA, em Saccharomyces cerevisiae, é descrito estar presente na região promotora de genes responsivos a estresse, incluindo o estresse térmico. Uma busca nos bancos de dados de proteínas mostrou que a RVB-1 apresenta homologia estrutural à proteína RuvBL1 de humanos. Além disso, esta proteína é descrita possuir uma proteína paráloga, RuvBL2 ou Rvb2 de humano e S. cerevisiae, respectivamente, cuja proteína ortóloga em N. crassa foi denominada RVB-2. As proteínas RuvBLs foram encontradas estarem associadas a vários processos celulares, muito provavelmente devido as suas capacidades de formar grandes complexos proteicos e possuírem atividade ATPásica. Neste trabalho, estas proteínas foram parcialmente caracterizadas do ponto de vista funcional, bioquímico e biofísico. Os resultados obtidos por microscopia de fluorescência mostraram que ambas apresentam localização nuclear quando o fungo foi exposto a estresse térmico. A análise da expressão da proteína RVB-V5 mostrou estar aumentada, nessa mesma condição ambiental, quando analisada por Western blot. As duas proteínas foram produzidas na forma recombinante em Escherichia coli, tanto isoladamente quanto juntas, e a análise da expressão mostrou alta estabilidade em solução quando ambas foram produzidas em uma mesma célula de bactéria. Ambas mostraram interagir in vitro por análise de pulldown e o complexo RVB-1/2 mostrou ser formado principalmente por α-hélices através de espectropolarimetria de dicroísmo circular. Análise em gel filtração analítica sugeriu que o complexo apresenta diferentes estruturas oligoméricas, quando analisado na ausência e na presença de ATP. O complexo apresentou atividade ATPásica in vitro, o que fortemente sugere que ambas pertencem à família AAA+. Resultados de retardamento em gel de agarose (EMSA), mostraram que tanto separadamente, como na forma de complexo, essas proteínas são capazes de se ligar a fragmentos de DNA dupla fita independentemente de ATP. / Previous work by our group identified the Neurospora crassa RVB - 1 protein as able of binding to a DNA fragment containing the Stress Responsive Element (STRE). In Saccharomyces cerevisiae, this element is present in the promoter region of genes responsive to stress, including heat stress. RVB - 1 shows structural homology to human RuvBL1 protein, and is described to have a paralog, the RuvBL2 or Rvb2 protein in human and S. cerevisiae , respect ively. The N. crassa orthologous protein was identified and named RVB - 2. The RuvBLs proteins have been found to be associated with diverse cellular processes, most likely due to their ability to form large protein complexes and to have ATPase activity. In this work, these proteins were functional, biochemical and biophysically characterized. The fluorescence microscopy results showed that both proteins present nuclear localization in the fungus exposed to heat stress. Analyses of protein expression by Weste rn blot showed an increased expression of the RVB - 1 - v5 protei n in this same condition . The two proteins were produced in Escherichia coli, and expression analyses showed higher stability in solution when both were produced together. Both proteins showed in vitro interaction by pulldown analysis. The RVB - 1/2 complex has the secondary structure mostly formed by α - helices as analysis by CD. The size - exclusion chromatography suggested that the complex present different oligomeric structures when analyzed in the absence and presence of ATP. They present in vitro ATPase activity, which strongly suggest that both belong to the AAA + family. Electrophoresis Mobility Shift Assay (EMSA) showed that both proteins are able to bind to dsDNA fragments, in an ATP - independently manner.

Made available in DSpace on 2014-06-12T15:51:55Z (GMT). No. of bitstreams: 2 arquivo872_1.pdf: 4987624 bytes, checksum: fe10b068072d15ab53986d95b266443d (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2010 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Cálculos de orbitais moleculares usando a Teoria do Funcional de Densidade (DFT) em nível BLYP com funções de base LanL1mb e LanL1dz foram executados para os supercondutores: Nb3Ge, MgB2, LaBa2Cu3Oy, La2-xSrxCuO4, YBa2Cu3Oy, TlBa2Ca2Cu3O8+δ, HgBa2Ca2Cu3O8+δ, LaO1-xFxFeAs e o Ba1-xKxFe2As2. Utilizamos modelos de cluster (aglomerado) baseados na célula unitária com os átomos de fronteira saturados com hidrogênio, o que minimiza o excesso de elétrons no cluster devido às ligações flutuantes. O cluster foi considerado diamagnético. Foram avaliados a distribuição de cargas atômicas e o gap de energia HOMO-LUMO (Highest Occupied Molecular Orbital - Lowest Unoccupied Molecular Orbital: Orbital Molecular de Mais Alta Energia Ocupado - Orbital Molecular de Mais Baixa Energia Desocupado). Os resultados foram interpretados à luz da teoria da ressonância não-sincronizada das ligações covalentes (RVB), como originalmente proposta por Linus Pauling. Uma característica de todos os sistemas investigados neste trabalho é a existência de um gap HOMO-LUMO da ordem de meV e uma distribuição de cargas compatível com a RVB. Apesar de não ser clara sua relação com a supercondutividade, o gap de energia HOMO-LUMO é da mesma ordem de magnitude do gap supercondutor medido experimentalmente. Em adição, verificou-se que os metais presentes nos sistemas investigados se encontram nos três estados de oxidação e na proporção requerida pelo princípio da eletroneutralidade de Pauling. Estes resultados reforçam o modelo RVB e convalidam esta proposta como uma teoria alternativa para a compreensão da supercondutividade. A coerência entre os argumentos da RVB e os resultados dos cálculos para a distribuição de cargas são discutidos

La physique de basse énergie du modèle de Heisenberg antiferromagnétique pour des spins 1/2 en deux dimensions recèle une grande variété de comportements, pour certains mal compris, lorsque l'on est en présence de frustration. Outre l'intérêt théorique que présente l'étude de ces modèles, il se trouve qu'ils décrivent de manière satisfaisante de nombreux composés réels maintenant synthétisés. Dans cette thèse, nous abordons les deux aspects de l'étude de ces modèles. D'un point de vue théorique, nous examinons ce modèle, à l'aide de techniques numériques, sur l'un des réseaux les plus frustrés : le réseau kagomé. Nous montrons comment les très fortes signatures de la frustration (existence d'un gap de spin peuplé d'un grand nombre d'états singulets) observées dans ce modèle peuvent être correctement comprises à l'aide d'états RVB (<< Resonating Valence Bond >>, Lien de Valence Résonant) à courte portée. Cette approche présente en outre l'intérêt de donner une image relativement simple de la physique de basse énergie du modèle. Bien qu'attribuées à la forte frustration de ce modèle, les propriétés du spectre du hamiltonien de Heisenberg sur le réseau kagomé n'avaient pas d'équivalent dans les systèmes analogues. Nous mettons en évidence, de manière exacte, l'existence de propriétés semblables (gap de spin et singulets de basse énergie) dans un modèle unidimensionnel de tétraèdres couplés. Nous abordons enfin les applications de l'étude numérique des modèles frustrés à l'explication de propriétés de composés réels. En effet, il est notamment possible de confronter ces résultats à des mesures de susceptibilité ou à des expériences de diffraction de neutrons. Nous examinons tout d'abord le composé CaV4O9, premier système bidimensionnel demi-rempli présentant un gap dans son spectre d'excitations. Nous montrons que l'analyse des symétries du premier état excité permet, par comparaison avec la relation de dispersion obtenue par diffraction de neutrons, de borner les paramètres du modèle, par ailleurs difficiles à évaluer par des méthodes de chimie quantique. L'analyse de la susceptibilité rend possible, dans le cas de Li2VO(Si,Ge)O4 qui est la première réalisation du modèle J_1 - J_2 sur le réseau carré, la mise en évidence de la frustration et l'évaluation de son importance dans ces deux composés.

Submitted by Etelvina Domingos (etelvina.domingos@ufpe.br) on 2015-03-12T18:57:13Z No. of bitstreams: 2 TESE Marconi Bezerra Costa.pdf: 4071497 bytes, checksum: 5ff606ff53fab5504c1ac18294e33669 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) / Made available in DSpace on 2015-03-12T18:57:13Z (GMT). No. of bitstreams: 2 TESE Marconi Bezerra Costa.pdf: 4071497 bytes, checksum: 5ff606ff53fab5504c1ac18294e33669 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Previous issue date: 2014-02 / CNPq / Baseados em cálculos DFT (Density Functional Theory) B3LYP/LANL1dz e na análise da distribuição de cargas atômicas para cupratos, metálicos e pnictídeos, demonstramos a ocorrência de ressonâncias não-sincronizadas de ligações covalentes no estado supercondutor, conforme prevê a teoria RVB (Resonating-Valence-Bond). Os modelos de cluster com as dangling bonds saturadas com hidrogênio nos átomos de fronteira, mostraram-se bastante apropriados para descrever os sistemas investigados. Para caracterizar o estado supercondutor, usamos como critério o gap de energia HOMO-LUMO, que deve ser da mesma ordem de grandeza do gap supercondutor. Para os cupratos, os resultados confirmam as previsões da RVB para a transferência de carga dos elementos hipereletrônicos para os hipoeletrônicos e o efeito da vacância de oxigênio na indução do estado supercondutor. Nos sistemas metálicos, encontramos a separação e o ordenamento de cargas em planos distintos, conforme previsto qualitativamente por Pauling. Nos pnictídeos, o gap HOMO-LUMO só é da mesma ordem de grandeza do gap experimental para os clusters dopados, e a dopagem induz uma separação de cargas no plano em que o dopante é inserido. Baseados nestes resultados, propomos combinações de elementos hipo e hipereletrônicos visando a obtenção de novos sistemas supercondutores que podem apresentar temperaturas críticas maiores do que as conhecidas atualmente. Estes resultados reforçam a teoria RVB como uma alternativa para descrever o fenômeno da supercondutividade.

In recent years there has been significant work aimed at understanding what effect the variation of electronic doping has on material properties. In the high transition-temperature (high-T$_c$) cuprate superconductors hole doping has an impact on the superconducting transition temperature. In the underdoped regime, the cuprates exhibit anomalous properties due to a pseudogap which forms and is thought to be related to Mott insulating physics. While there is no general consensus as to the mechanism underlying high temperature superconductivity, the resonating valence bond (RVB) theory proposed by Anderson in 1987 with a Gutzwiller projected d-wave BCS wave function could give a first picture of the high-T$_c$ cuprates. We have calculated properties of the cuprates using the assumption that the pseudogap state acts as a normal state to an otherwise standard BCS mean field theory. We find that the phenomenological RVB spin liquid model proposed by Yang, Rice and Zhang (YRZ) is highly successful at describing the doping dependent features of the cuprates. Through application of the YRZ model and the tools of many-body theory we present results on anomalous properties observed in: electronic specific heat; Raman and angle-resolved photoemission spectroscopy (ARPES) data; effective mass renormalization; and thermal broadening seen in ARPES. We verify that the YRZ ansatz qualitatively describes these anomalies along with their doping dependent variations. We conclude from this work that the physics underlying the pseudogap, while distinct in origin from superconductivity, is likely to arise from an RVB wavefunction that is closely related to the BCS state. In graphene, variation in doping modifies the polarization function which describes a screened electron-electron interaction. This leads to additional features in the spectral function which are due to electron-plasmon coupling. In this work, we calculated the electronic density of states including this interaction along with its doping dependence with and without an electron-phonon interaction. We find clear features of electron-electron interactions in the density of states. These features are related to the energies of plasmaron bands in the spectral function and can be modified through doping so as to be distinct from the phonon energy scales.

During the last several decades, many people, fleeing from disasters or political threats, have applied for asylum in the European countries. Council Directive 2003/9/EC, laying down minimum standards for the reception of asylum-seekers, as well as several other directives, have been developed in the EU in order to ensure fair treatment of the asylum-seekers in all the European countries. However, there are huge differences in the national asylum laws of countries and consequently, the way they treat the asylum-seekers. In this research, the national asylum laws of Germany and the Netherlands are studied and compared, showing that though following the Council Directive, fair or equal treatment of asylum-seekers cannot be guaranteed. In the Netherlands asylum-seekers are granted with a great extent of benefits while in Germany, they are greatly discriminated against. Based on the Social Determinants of Health Model, developed by Dahlgren and Whitehead in 1991, the hypothesis is that the asylum seekers in the Netherlands enjoy better health status than the ones in Germany, because based on the Dutch asylum laws, they have better living and working conditions. In order to confirm or negate this hypothesis, a meta-study of available literature on the health status of asylum-seekers has been done. However, the hypothesis could not be confirmed/ negated due to extreme lack of availability of data in this area. By discussing the relationship between life conditions and health of individuals, reviewing current legal instruments regulating asylum in the EU and analyzing the available data on the health status of asylum-seekers, this paper draws the attention to the importance of data and research on these topics and the need for development of practices for collection of such information. Availability of such information can affect future decision and policy makings regarding asylum-seekers and their health and might result in comprehensive reformations in the current national or international legal instruments.

Les gliomes sont des tumeurs cérébrales infiltrantes difficilement curables, notamment à cause de la difficulté à visualiser toutes les infiltrations au bloc opératoire. Dans cette thèse, nous réalisons une étude clinique de spectroscopie de fluorescence de la protoporphyrine IX (PpIX) dans les gliomes de 10 patients selon l’hypothèse que les spectres collectés proviennent de la contribution de 2 états de la PpIX dont les proportions varient suivant la densité en cellules tumorales. Après avoir présenté le développement du système interventionnel proposant une excitation multi-longueurs d’onde, nous présentons son utilisation sur fantômes de PpIX mimant les propriétés des gliomes. Ceci permet tout d’abord d’obtenir les spectres émis par les 2 états séparément puis de proposer un modèle d’ajustement des spectres comme une combinaison linéaire des 2 spectres de référence sur la bande spectrale 608-637 nm. Ensuite, nous présentons la mise en place de l’étude clinique, notamment l’analyse de risques, avant d’appliquer ce système in vivo. Les mesures in vivo détectent de la fluorescence dans des tissus où le microscope chirurgical n’en détecte pas, ce qui pourrait s’expliquer par un changement d’état de la PpIX entre le cœur des gliomes et leurs infiltrations. L’intérêt de l’excitation multi-longueurs d’onde est démontré par la décroissance de la corrélation des spectres acquis aux trois excitations suivant la densité en cellules tumorale. Enfin, nous soulevons des pistes d’étude de l’identification peropératoire des zones de fonctionnalité cérébrale à l’aide d’une caméra optique ainsi que l’étude du temps de vie de fluorescence et de la fluorescence deux photons de la PpIX sur fantômes / Gliomas are infiltrative tumors of the brain which are yet hardly curable, notably because of the difficulty to precisely delimitate their margins during surgery. Intraoperative 5-ALA induced protoporphyrin IX (PpIX) fluorescence microscopy has shown its relevance to assist neurosurgeons but lacks sensitivity. In this thesis, we perform a spectroscopic clinical trial on 10 patients with the assumption that collected fluorescence is a linear combination of the contribution of two states of PpIX which proportions vary with the density of tumor cells. This work starts with the development of the intraoperative, portable and real time fluorescence spectroscopic device that provides multi-wavelength excitation. Then, we show its use on PpIX phantoms with tissues mimicking properties. This first enables to obtain a reference emitted spectrum for each state apart and then permits the development of a fitting model to adjust any emitted spectrum as a linear combination of the references in the spectral band 608-637 nm. Next, we present the steps led to get approvals for the clinical trial, especially the risk analysis. In vivo data analysis is then presented, showing that we detect fluorescence where current microscopes cannot, which could exhibit a change in PpIX state from glioma center to its margins. Besides, the relevance of multi-wavelength excitation is highlighted as the correlation between the three measured spectra of a same sample decreases with the density of tumor cells. Finally, the complementary need to intraoperatively identify cerebral functional areas is tackled with optical measurements as a perspective and other properties of PpIX on phantoms are also raised

Dans cette thèse, nous traitons des problèmes de la détection des personnes et de l'estimation de leurs poses dans la Salle Opératoire (SO), deux éléments clés pour le développement d'applications d'assistance chirurgicale. Nous percevons la salle grâce à des caméras RGB-D qui fournissent des informations visuelles complémentaires sur la scène. Ces informations permettent de développer des méthodes mieux adaptées aux difficultés propres aux SO, comme l'encombrement, les surfaces sans texture et les occlusions. Nous présentons des nouvelles approches qui tirent profit des informations temporelles, de profondeur et des vues multiples afin de construire des modèles robustes pour la détection des personnes et de leurs poses. Une évaluation est effectuée sur plusieurs jeux de données complexes enregistrés dans des salles opératoires avec une ou plusieurs caméras. Les résultats obtenus sont très prometteurs et montrent que nos approches surpassent les méthodes de l'état de l'art sur ces données cliniques. / In this thesis, we address the two problems of person detection and pose estimation in Operating Rooms (ORs), which are key ingredients in the development of surgical assistance applications. We perceive the OR using compact RGB-D cameras that can be conveniently integrated in the room. These sensors provide complementary information about the scene, which enables us to develop methods that can cope with numerous challenges present in the OR, e.g. clutter, textureless surfaces and occlusions. We present novel part-based approaches that take advantage of depth, multi-view and temporal information to construct robust human detection and pose estimation models. Evaluation is performed on new single- and multi-view datasets recorded in operating rooms. We demonstrate very promising results and show that our approaches outperform state-of-the-art methods on this challenging data acquired during real surgeries.