This work describes the synthesis and functionalization of azoles employing different methodologies, based on organometallic catalysis or not. Firstly, we disclose the synthesis tetra-substituted 5-trifluoromethyl pyrazoles via sequential halogenation of 5-trifluoromethyl pyrazoles and palladium-catalyzed carbon–carbon and carbon–nitrogen cross-coupling reactions employing organozinc reagents and amines as coupling partners, respectively. This work allowed to achieve new pyrazolic systems in moderated to good yields. Posteriorly, we show the synthesis of 1,3-di(hetero)aryl indazoles exploring the complementary catalytic activity of nickel and copper complexes. We commenced this study evaluating different nickel pre-catalysts to perform the intramolecular amination of unprotected 2-chlorophenyl hydrazones. In a second moment, we described the N-(hetero)arylation of the in situ generated NH indazoles, using a simple catalytic system based on copper/DMEDA. This sequential one-pot fashion procedure allowed the achievement of several 1,3-di(hetero)aryl indazoles in moderate to good yields. Lastly, we disclose the formation of pyrazolo[1,5-a]quinoxalin-4(5H)-ones by the reaction between ethyl 1-(2-chlorophenyl)-1H-pyrazole-5-carboxylate and primary amines. The one-pot methodology undergoes by two sequential reactional pathways: i) amidation of the ester moiety attached to the pyrazole ring, and ii) intramolecular cyclization via nucleophilic aromatic substitution. This synthetic approach proved to be efficient only for primary aliphatic amines, allowing to achieve molecules with different substitution patterns in moderate to good yields. Key-words: Azoles, quinoxalinones, Negishi cross-coupling, Buchwald-Hartwig cross-coupling. / Este trabalho descreve a síntese e a funcionalização de azóis através de diferentes metodologias, ancoradas ou não na catálise organometálica. Primeiramente, descrevemos a síntese de 5-trifluormetil pirazóis tetrassubtituídos através de reações de acoplamento cruzado catalisadas por complexos de paládio entre 5-trifluormetil-4-halo pirazóis, reagentes organozinco e aminas. Este trabalho permitiu a obtenção de novos sistemas pirazólicos com rendimentos moderados a bons. Posteriormente realizamos a síntese de 1,3-di(hetero)aril indazóis explorando as atividades catalíticas complementares de complexos de níquel e cobre. Primeiramente avaliamos diferentes pré-catalisadores de níquel para realizar a aminação intramolecular de diferentes 2-clorofenil hidrazonas não protegidas. Em um segundo momento, realizamos a N-(hetero)arilação dos NH indazóis gerados in situ, através do emprego de um sistema catalítico baseado em cobre/DMEDA. A metodologia permitiu a obtenção de diferentes indazóis 1,3-di(hetero)aril substituídos, com rendimentos moderados a bons. Por fim, demonstramos a síntese de pirazolo[1,5-a]quinoxalin-4(5H)-onas a partir da reação entre 1-(2-clorofenil)-1H-pirazolo-5-carboxilatos de etila e aminas primárias. A metodologia one-pot envolve duas etapas sequenciais; i) amidação da função éster do pirazol e ii) ciclização intramolecular via substituição nucleofílica aromática. Esta abordagem sintética provou ser eficiente ao se empregar aminas alquílicas primárias, permitindo a obtenção de diferentes padrões de substituição com rendimentos moderados a bons.

Neste trabalho apresentamos a determinação autoconsistente da constante de interação spin-órbita em heteroestruturas com duas sub-bandas. Como recentemente proposto, ao obter o hamiltoneano de um sistema com duas sub-bandas na aproximação de massa efetiva, constata-se a presença de um acoplamento inter-subbanda que não se anula mesmo em heteroestruturas simétricas. Apresentamos aqui as deduções teóricas que levaram à proposição desse novo acoplamento e mostramos o cálculo autoconsistente da intensidade do acoplamento e a comparamos com a intensidade do acoplamento Rashba, já amplamente estudado. Discutimos o método k.p e a Aproximação da Função Envelope e mostramos a obtenção do modelo de Kane 8x8 para semicondutores com estrutura zincblende. Aplicamos o método do \"folding down\'\' ao hamiltoneano de Kane isolando o setor correspondente à banda de condução. Escrevemos dessa forma um hamiltoneano efetivo para a banda de condução no contexto de um poço quântico com uma barreira. Através da projeção desse hamiltoneano nos dois primeiros estados da parte orbital verifica-se o surgimento de um acoplamento inter-subbanda. Finalmente escrevemos o hamiltoneano efetivo 4x4 que descreve as duas primeiras subbandas de um poço quântico e obtivemos seus autoestados e autoenergias. Finalmente fizemos o cálculo autoconsistente das funções de onda e energias de um gás de elétrons em poços quânticos simples e duplos através da aproximação de Hartree e a partir desses resultados determinamos o valor da constante de acoplamento Rashba e da nova constante inter-subbanda. Entre os resultados obtidos destacam-se o controle elétrico da constante de acoplamento inter-subbanda através de um eletrodo externo e um efeito de renormalização da massa efetiva que pode chegar até 5% em algumas estruturas. / In this work we present the self-consistent determination of the spin-orbit coupling constant in heterostructure with two subbands.As recently proposed, the effective hamiltonian for the conduction band in the effective mass approximation contains an inter-subband spin-orbit coupling which is non-zero even for symmetric heterostructures. We present the theoretical derivation which leads to this proposal and show a selfconsistent determination of the coupling constant. We also compare the magnitude of the new coupling constant with the usual Rashba coupling. Starting with a discussion of the k.p method and the Envelope Function Approximation (EFA) we show the derivation of the 8x8 Kane model for semiconductors with zincblende structure. We then apply the \"folding down\'\' method, isolating the conduction band sector of the EFA hamiltonian. By projecting this hamiltonian in the first two states of the orbital part, we find an effective 4x4 hamiltonian that contains an inter-subband spin orbit coupling. The eingenvalues and eigenvectors of this hamiltonian are shown and, specializing the model for single and double quantum wells, we self-consistently determine the inter-subband and Rashba coupling constants in the Hartree approximation. The results indicate the possibility of electrical control of the coupling constant and show an effective mass renormalization effect that can be up to 5% in some cases.

This thesis deals with the copper-catalyzed substitution of allylic substrates. In the first part of this thesis, the synthesis of a series of metallocenethiolates is described. The thiolates were examined as ligands in the enantioselective copper(I)-catalyzed γ-substitution of allylic acetates. The second part describes a study on copper-catalyzed α-substitution of enantiomerically pure secondary allylic esters. It was observed that the degree of chirality transfer is strongly dependent on the reaction temperature. The loss of chiral information is consistent with an equilibration of the allylCu(III) intermediates prior to product formation, which is essential in order to realize a copper-catalyzed dynamic kinetic asymmetric transformation process. The third part describes a study on copper-catalyzed stereoselective α-substitution of enantiopure acyclic allylic esters. This method, when combined, with ruthenium and enzyme catalyzed dynamic kinetic resolution of allylic alcohols, provides a straightforward route to pharmaceutically important α-methyl carboxylic acids. The fourth part is a mechanistic study on the reaction of perfluoroallyl iodide with organocuprates. Experimental studies as well as theoretical calculations were used to explain the contrasting reactivity of perfluoroallyl iodide vs. allyl iodide in cuprate allylation reactions. In the fifth part, the development of a practical and useful method for the preparation of pentasubstituted acylferrocenes is presented.

Multi-junction photovoltaic devices based on III-V semiconductors have applications in space power systems and terrestrial concentrating photovoltaics, as well as in power-over-fibre and optical power conversion systems. These devices have between two and twenty junctions arranged in tandem, connected in series with optically transparent tunnel diodes. In some cases, they may include as many as eight different materials, including ternary and quaternary alloys, and >100 epitaxial layers in total. A general method for simulating performance of these devices using drift-diffusion based device simulation tools is reviewed. This includes discussion of the geometry, discretization, and physical equations to be solved. A set of material parameters for some important materials is listed, and solutions are shown for an example of a lattice-matched four-junction GaInP / (In)AlGaAs / InGaAsN(Sb) / Ge solar cell including a dilute nitride based p-i-n junction with ∼ 0.9 eV band gap. A sample of this dilute nitride junction with a 650 nm absorber layer was grown by molecular beam epitaxy and was shown to have short-circuit current density of 15.1 mA/cm2, sufficient for use in the 4-junction structure, while transmitting sufficient light through to the bottom (germanium) junction. Open-circuit voltage was up to 0.186 V at 1-sun, increasing to 0.436 V under 1500 suns concentration. The device simulation methodology was extended to include effects of luminescent coupling and photon recycling. These effects are included by adding a term to the electron and hole continuity equations, and the resulting coupled system of equations is solved. No external iterative loop is required, as has been the case in other efforts to model these effects. A five-junction photonic power converter (PPC) is simulated and it is shown that the quantum efficiency of the device is significantly broadened through luminescent coupling. There is a 350 mV reduction in simulated open-circuit voltage (70 mV per junction) if luminescent coupling is neglected. This work was later extended to a 12-junction PPC device, where the simulation predicts a wavelength sensitivity of -1.1%/nm in the absence of luminescent coupling; this is reduced to -0.4%/nm when luminescent coupling is included in the calculation. The latter result, and the overall shape of the simulated quantum efficiency curve agree closely with experimental measurements. Finally, two specific applications of PPCs are demonstrated. The first is in a step-up DC-to-DC converter, where a linear regulator combined with a laser/PPC pair can convert a 3.3 V input (commonly available from a single lithium polymer battery cell) into 12 V. Unlike conventional switching boost converters, this ‘photonic boost converter’ is not a source of ripple. In testing, a >80 dB reduction in ripple was measured compared with an equivalent switching boost converter, limited only by input noise of the instrument.The second application is in a 60 kW, 650 V switching circuit such as might be found in a hybrid or electric vehicle drivetrain. These circuits need several isolated power supplies to power gate drivers for the IGBT or SiC MOSFET switching components. This isolation is commonly provided by a small transformer, which inherently has a parasitic capacitance between primary and secondary windings and creates a path for EMI currents to flow from the high-power components to the power supply and control circuitry. By using a laser/PPC pair to provide the needed isolation, this parasitic capacitance can be largely eliminated; a 20 dB reduction in EMI current reaching the control FPGA is demonstrated.

[résumé trop long] / The important relationship between structure and function has always been a fundamental question in neuroscience research. In particular in the case of movement, brain controls large groups of muscles and combines it with sensory informations from the environment to execute purposeful motor behavior. Mapping dynamics encoded in a high dimensional neural space onto low-dimensional behavioral space has always been a difficult challenge as far as theory is concerned. Here, we develope a framework to study spike/burst dynamics having low dimensional phase description, which can readily be extended under certain biological constraints on the coupling to low dimensional functional descriptions. In general, phase models are amongst the simplest of neuron models reproducing spike-burst behavior, excitability and bifurcations towards periodic firing. However, the coupling among neurons has only been considered using generic arguments valid close to the bifurcation point, and the distinction between electric and synaptic coupling remains an open question. In this thesis we aim to address this question and derive a mathematical formulation for the various forms of biologically realistic coupling. We begin by constructing a mathematical model based on a planar simplification of the Morris-Lecar model. Using geometric arguments we then derive a phase description of a network of neurons with biologically realistic electric coupling and subsequently with chemical coupling under the fast synapse approximation. We then demonstrate that electric and synaptic coupling are expressed differently on the level of the network’s phase description, exhibiting qualitatively different dynamics. Our numerical investigations confirm these findings and show excellent correspondence between the dynamics of the full network and the network’s phase description. Following the success of the phase description of the spiking neural network, we extend this approach in order to propose a generating mechanism for parabolic bursting captured by only a single phase variable. This is the first model in the literature which captures bursting dynamics in one dimension. In order to study the emergent behavior we extend this to a network of bursters with global coupling and analytically reduce a high dimensional system to only two dimensions. Further, we investigate the bifurcation properties numerically as well as analytically. One of the key conclusion is that the stability states remain invariant to the increasing number of spikes per burst. Finally we investigate a spikeburst neuron network coupled via mean field type of fast synapses developed in this thesis and systematically carry out a detailed bifurcation analysis of the model, for a tractable special case. Numerical simulations investigate this mean field model beyond special case and clearly reveals qualitative correspondence with the full network model. Moreover, these network displays rich collective dynamics as a function of two parameters, mainly the synaptic coupling strength and the width of the distribution in applied stimulus. Besides incoherence, frequency locking, and oscillator death (a total cessation of firing caused by excessively strong coupling), there exist multistable solutions in the full and the phase network of neurons.

Dans cette thèse, on s'intéresse à des schémas de chiffrement par blocs, c'est-à-dire que le chiffrement (et le déchiffrement) envoie un bloc de n bits sur un bloc de n bits. Il y a essentiellement deux grandes structures utilisées pour un schéma de chiffrement par blocs : la structure de Feistel (utilisée pour le DES) et la structure SPN (utilisée pour l'AES). L'étude de la sécurité de ces différents structures et schémas a permis de nombreuses avancées autant pratiques que théoriques. Nous présentons dans cette thèse des preuves de sécurité pour le schéma d'Even-Mansour itéré, le schéma paramétrable CLRW et le schéma de Feistel à clés alternées. Ces preuves utilisent une technique probabiliste, appelée coupling, introduite en cryptographie en 2002 par Mironov. Nous présentons cette technique dans le cadre des probabilités, puis la façon d'utiliser le coupling pour prouver la sécurité des schémas cités précédemment. Nous présentons également une étude de la sécurité du schéma d'Even-Mansour à deux tours pour certaines minimisations (même clés de tours ou même permutations internes par exemple) et, pour conclure, une comparaison des différentes techniques d'indistinguabilité / In this thesis, we study blockciphers, meaning that the encryption (and decryption) sends a block of n bits on a block of n bits. There is essentially two main structures used for a blockcipher: the Feistel structure (used for DES) and the SPN structure (used for AES). The study of the security of these structures and schemes has led to many practical and theoretical advances. We present in this thesis proofs of security for the iterated Even-Mansour scheme, the tweakable blockcipher CLRW and the key-alternating Feistel cipher. These proofs use a probabilistic technique, called coupling, introduced in cryptography in 2002 by Mironov. We present this technique in the context of probabilities, then we present how to use the coupling to prove the security for the schemes mentioned above. We also present an analysis of the security of the Even-Mansour cipher with two rounds and some properties (same round keys or same internal permutations for example) and, finally, we compare the different techniques to prove indistinguishability

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-07-20T12:25:34Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) documento.pdf: 6110083 bytes, checksum: e763b9e4b979081c4ada6fef0eb596a6 (MD5) / Made available in DSpace on 2017-07-20T12:25:34Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) documento.pdf: 6110083 bytes, checksum: e763b9e4b979081c4ada6fef0eb596a6 (MD5) Previous issue date: 2015-08-03 / ANP-PRH26 / Aimportânciadageomecânicaedoestudodeesquemasdeacoplamentoentreageomecânica e fluxo multifásico têm sido cada vez mais importantes e utilizados pela indústria a medida que formações cada vez mais profundas vêem sendo descobertas e exploradas. O entendimento do comportamento do estado de tensão em um reservatório permite produzir um melhor entendimento das implicações geomecânicas que ocorrem durante a fase de explotação, isso porque durante esta fase, as alterações na poro-pressão conduzem perturbações no equilíbrio mecânico afetando o estado de tensão de formações profundas, de maneira a alterar as propriedades da rocha tais como permeabilidade e porosidade. No entanto, a simulação acoplada (hidromecânica) em um grande campo heterogêneo implica na solução de equações de fluxo e mecânica, associadas a um grande número de graus de liberdade que torna esse tipo de abordagem inviável e computacionalmente cara. Neste contexto, um simulador geomecânico-linhas de fluxoé apresentado dentro de um algoritmo sequencial iterativo. Neste trabalho, aplica-se o método de elementos finitos com volume de controle para o subproblema poro-mecânico que fornece um campo de velocidade de Darcy pós-processado e a porosidade como entradas para o subproblema de transporte. Este subproblema é resolvido através do método de decomposição de operador, no qual basea-se em um esquema preditor-corretor com os passos preditor e corretor discretizados pelos esquemas baseados em tempo de vôo e volumes finitos, respectivamente. Simulações numéricas de injeção de água foram comparadas com soluções encontradas na literatura, mostrando bons resultados. Em problemas dominados pela advecção, envolvendo um reservatório naturalmente fraturado, a abordagem implementada foi capaz de predizer a distribuição do campo de saturação ao longo de toda simulação. Além disso, para avaliar a resposta geomecânica, simulações numéricas foram realizadas em um grande sistema de reservatório-rocha capeadora em uma fase de recuperação primária de hidrocarboneto, mostrou que a formulação apresentada provou ser: uma alternativa promissora para simulação hidro-geomecânica tradicional; úteis para o modelo de fluxo de redução de ordem nos casos em que o comportamento geomecânico são mais importantes do que o comportamento de fluxo e de uma ferramenta complementar para simulação geomecânica convencional. / The importance of geomechanics and the study of coupling between geomechanics and multiphase flow have been increasingly recognized and used by the industry as deeper formations are discovered and exploited. The knowledge of the state of stress in a reservoir yields a better understanding of the geomechanical implications during exploitation stage, because during the primary recovery stage, changes in pore pressure leads to perturbations inthemechanicalequilibrium,affectingthestressstateintheformationsinawaythatalters the rock properties such as permeability and porosity. However, the coupled simulation (hydromechanical) in large field heterogeneous models involves stress and flow equations solving, associated with a large number of degrees-of-freedom which becomes infeasible and computationally costly. In this context, a geomechanical-streamline simulator is presented within a iteratively coupled framework algorithm. In the present work, we applied control volume finite element method for the poromechanics subproblem which provides a Darcy velocityfieldthroughapost-processingvelocityprocedureandporosityasinputfieldstothe transportsubproblem.Suchsubproblemissolvedbymeansofanoperatorsplittingmethod, which is based on a predictor-corrector scheme with the predictor and corrector steps discretized by a time-of-flight and a finite volume based schemes, respectively. Numerical simulations of water-flooding are compared to the numerical results available in literature, showing good results. In convection-dominated problems, involving a naturally fractured reservoir, the approach was able to predict the saturation distributions for the whole simulation correctly. Furthermore, to appraisal the geomechanical response, numerical simulation was performed in a large reservoir-caprock system in a primary hydrocarbon recovery stage, showing that the formulation presented proved be: an promising alternative to traditional hydro-geomechanical simulation; useful for flow model order reduction in cases where the geomechanical behavior are more important than the flow behavior and a complementary tool for conventional geomechanical simulations.

Depuis 2012, les pérovskites hybrides halogénées de type CH3NH3PbX3 (X = I, Br ou Cl) sont apparues comme très prometteuses non seulement dans le domaine du photovoltaïque mais aussi pour les dispositifs émetteurs de lumière comme les diodes électroluminescentes et les lasers. L'un des avantages cruciaux de ces matériaux semiconducteurs est leur méthode de déposition à basse température et en solution. Le réglage de la longueur d'onde d'émission des pérovskites dans tout le spectre visible par de simples substitutions chimiques dans la partie halogénée est un autre atout. En particulier, les pérovskites halogénées montrent une grande efficacité de luminescence dans le vert et pourraient répondre au problème du "green gap" dans les sources laser (le "green gap" fait référence à la baisse d'efficacité des diodes électroluminescente et diodes laser à semi-conducteurs émettant dans le vert).Le travail de doctorat mené ici a porté sur la réalisation d’un laser pompé optiquement à base de la pérovskite hybride CH3NH3PbBr3 émettant dans le vert. La structure réalisée consiste en une microcavité verticale à base d’une couche mince de 100 nanomètres de CH3NH3PbBr3 déposé par "spin-coating" (dépôt par enduction centrifuge), insérée entre un miroir diélectrique et un miroir métallique. Nous avons démontré, à température ambiante, le régime de couplage fort entre le mode photonique de la microcavité et l'exciton de la pérovskite. Ce régime de couplage fort conduit à la création de quasi-particules appelées les exciton-polaritons, qui sont une superposition cohérente d’états photonique et excitonique. En augmentant la puissance injectée optiquement, nous avons obtenu un effet laser dans cette microcavité. L’étude des propriétés d’émission de ce laser met en évidence que nous avons réalisé un laser aléatoire, émettant dans le vert, filtré directionnellement par la courbe de dispersion du polariton de basse énergie. Ce filtrage par la courbe de dispersion du polariton permet le contrôle de la directionnalité de l’émission laser sur une grande gamme d’angles : des angles aussi grands que 22° ont été obtenus expérimentalement. / Since 2012, the hybrid halide perovskites of CH3NH3PbX3 (X = I, Br or Cl) type have emerged as very promising not only in the field of photovoltaics but also for light-emitting devices such as light-emitting diodes and lasers. One of the crucial advantages of these semiconductor materials is their low temperature and solution deposition method. The tuning of the perovskites emission wavelength throughout the visible spectrum by simple chemistry substitutions in the halogenated part is another asset. In particular, the halide perovskites show a high luminescence efficiency in the green and could address the "green gap" problem in laser sources (the "green gap" refers to the drop in efficiency of light-emitting diodes and laser diodes emitting in the green).The thesis work carried out here is focused on the development of an optically pumped laser based on the hybrid halide perovskite CH3NH3PbBr3 emitting in the green. The structure consists of a vertical microcavity based on a 100-nanometre thin film of CH3NH3PbBr3 deposited by spin-coating, inserted between a dielectric mirror and a metal mirror. We have demonstrated, at room temperature, the strong coupling regime between the microcavity photonic mode and the exciton of the perovskite. This strong coupling regime leads to the creation of quasi-particles called exciton-polaritons, which are a coherent superposition of photonic and excitonic states. By increasing the optically injected power, we obtained a laser effect in this microcavity. The study of the emission properties of this laser shows that we have produced a random laser, emitting in the green, filtered directionally by the dispersion curve of the lower polariton. This filtering by the polariton dispersion curve allows the directionality of the laser emission to be controlled over a wide range of angles: angles as large as 22° were obtained experimentally.

The spin-lattice coupling is due to itinerant electrons interacting with both spins of ions and phonons, mediating a coupling between magnetic spin moments and lattice vibrations. In this project, the coupling is studied systematically for finite quantum spin chains of size 2 – 10. The coupling is included in a Hamiltonian model with the Heisenberg exchange interaction and an external magnetic field resulting in an eigenvalue problem which is solved numerically to find phase diagrams of the magnetic moment of the system depending on an external magneticfield and the lattice vibration parameter. The eigenvalue problem is also solved analytically for the 2-ion chain, dimer, and 3-ion chain, trimer, systems. Based on these phase diagrams two propositions are made: the effect of the coupling is larger than an external magnetic field and the behavior of the coupling converges to a common phase diagram for larger spin chains. / Kopplade spinn- och vibrationsfrihetersgrader beror på kringvandrande elektroner som växelverkar med både spin och fononer, vilket förmedlar en koppling mellan magnetiskt spinmoment och gittervibrationer. I detta projekt studeras denna koppling systematiskt för ändliga spin-kedjor av 2–10 joner. Systemet beskrivs av en Hamiltonian med Heisenberg modellen som beskriver spin-spin kopplingen samt ett externt magnetiskt fält. Detta egenvärdesproblem löses analytiskt för dimer- och trimersystem samt numeriskt för längre kedjor. Lösningarna används för att ta fram fasdiagram av de magnetiska momenten av kedjorna beroende på externt magnetfält och spin- och vibrationsfrihetsgradsparametern. Baserat på dessa fasdiagram, framförs två propositioner: kopplingens effekt är större än ett externt magnetfält och kopplingens beteende konvergerar till ett enhetligt fasdiagram för större spinnkedjor. / <p>Subject reader/ämnesgranskare: Anders Bergman</p>

Superradiance is an enhanced decay of an excited system of emitters resulting from their mutual coupling. This thesis is focused on superradiance of the emitters coupled via their interaction with a plasmonic nanoparticle. So-called plasmon-mediated superradiance results in even stronger enhancement of the decay rate as the nanoparticle serves as an additional decay chanel. We have developed a quantum model of the system of emitters coupled to a plasmonic nanoparticle, which allows us to differentiate between a pure dephasing and decay processes. We show that the pure dephasing can destroy the cooperative effect leading to superradiance. Furthermore, we have studied how the direct mutual coupling between emitters affects time evolution of the system in dependence on its configuration, and we show conditions when a decay of the system is dramatically decreased by direct coupling.