Ever since the big recession of the world economy 2007, the central banks in Europe have struggled to regain financial stability. Their goals have been hard to reach and 2014 The European Central bank (ECB) introduced negative interest rates for the first time in the world history. However, today, year 2016, many countries still have not been able to reach their inflation target. During this time with expansive monetary policies, many European Union (EU) members have faced rising level of household debts to GDP. This study focus on EU-members and uses a Vector Autoregressive method, Granger causality test and an impulse-response test to give a greater understanding about the association between the level of household debt and interest rate. Further, it aims to investigate if the negative interest rate has an impact on that association. However, our empirical results show that there is a significant negative association between the level of household debt and the interest rate in Austria, Belgium, Bulgaria, Finland, Germany, Italy, Poland, Romania, Slovakia, Spain and Sweden. Further, they show that there is a granger causality from the interest rate to the level of household debt for Belgium, Finland, Germany, Poland, Slovakia and Sweden. For all these countries, our findings show that a shock in the interest rate have a short-term effect on the level of household debt. Lastly, we found no statistical significant evidence for that the negative association between the interest rate and the level of household debt does increase when the interest rate is negative.

Master of Science / Department of Chemical Engineering / Keith Hohn / The study will utilize a probabilistic reaction modeling method for ring-opening reactions of epoxide. In particular, to elucidate the reaction mechanism by the methods presented, focus will be placed on the nucleophillic attack of ethylene oxide by ammonia and its anion. This focus was chosen because of the potential to gain significant advantage in computational intensity required to model the epoxy-amino macromolecular curing reactions and resulting thermochemical and physical properties of the cured resin. The method employed utilizes the combinatorial probability that 1. Two molecules will approach a transition state with sufficient energy to drive reaction 2. Any reaction will occur for a given penetration into the potential energy surface. The concept of a transition state is relaxed to allow a dynamic probability that any reaction will proceed given a position on the intrinsic reaction coordinate (IRC) rather than searching for a specific transition state of theoretical reaction probability. 3. The reaction that occurs yields a desired stable or semi-stable molecular complex This study will focus on identifying possible stable and semi-stable products and corresponding rate constants. The technique developed here is novel in that it provides an unsupervised method to identify all structures corresponding to minima on the potential energy surface. The technique provides a pragmatic and efficient approach to sample a molecular system for different reaction mechanisms and provides a relative energy requirement to achieve these mechanisms with no presupposition of the mechanism, product, or transition state. It is possible from this data to derive rate constants for a reacting system, however, the rate constant derived for the EO/NH2 molecular system yielded significantly understated reaction probabilities and therefore rate constants.

Ketamine has shown promise as a novel treatment for depression and as a means to investigate the biology of depression. The drug effectively and rapidly treats depressed patients with the effects lasting approximately 1 week. However, concerns about ketamine’s efficacy do exist because of the inadequacy of blinding procedures used in existing trials. A dose of 0.5 mg/kg has been found to be most effective. Prolonged ketamine infusions have not extended the antidepressant effect beyond the timeframe of a regular infusion. Repeat infusions may be successful in extending ketamine’s effect, but definite conclusions cannot yet be made in this regard. Combination treatment with escitalopram and cognitive behavioral therapy (CBT) hold promise, as does the development of an intranasal formulation. Ketamine has shown additional efficacy as an acute anti-suicide treatment. Side effects from a single administration usually fade within a few hours and commonly include dissociation, elevations of blood pressure, nausea, and anxiety. Less data is available on the side effects caused by repeated ketamine infusions. Concerns exist regarding genitourinary, hepatic, and cognitive side effects after repeated infusions, as well as a risk of addiction. Research on ketamine’s mechanism of action has focused on the glutamate system in the brain. Ketamine may act by inhibiting release of γ–aminobutyric acid (GABA) from interneurons, activating intrasynaptic α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptors (AMPARs), increasing mammalian target of rapamycin complex 1 (mTORC1) and extracellular signal-regulated kinase (ERK) signaling, enhancing brain-derived neurotrophic factor (BDNF) production, inhibiting glycogen synthase kinase 3 (GSK3), blocking extrasynaptic N-Methyl-D-aspartate receptors (NMDARs), and promoting synaptogenesis and neuroplasticity. The two existing ketamine stereoisomers, (R)- versus (S)-ketamine, have different actions and potentially different efficacies and side effect profiles. Ketamine also produces regional changes in brain activity and connectivity. These include decreased burst firing in the lateral habenula (LHb), increased activity in the prefrontal cortex (PFC) and subgenual anterior cingulate cortex (ACC), and alterations in the amygdala’s response to angry and happy faces. Ketamine has the potential to be developed into a novel and useful clinical tool in the treatment of depression and to advance the understanding of the biology of depression.

Labaditina é um decapeptídeo cíclico, hidrofóbico, extraído da Jatropha Multifida, uma planta da família Euphorbiaceae. É mais resistente à degradação proteolítica que seus respectivos isômeros lineares; e forma pontes de hidrogênio internamente, facilitando sua inserção em membrana biológica. Estudos tem mostrado que a restrição conformacional dos peptídeos cíclicos aumenta sua afinidade e especificidade à membrana. Devido à essas características físicas e às atividades biológicas apresentadas, tais como inibição da via clássica do sistema complemento humano in vitro e atividade antibacteriana para Streptococcus mutans, este peptídeo tem ganhado interesse biológico e farmacológico. Sobretudo, ainda não é conhecido seu mecanismo de ação. Devido à isso, os peptídeos Labaditina (Lo) e o análogo linear (L1), estruturalmente diferentes, foram estudados com o objetivo de obter informações quanto ao mecanismo de ação, interação e possíveis alterações estruturais frente a membranas biológicas. O comportamento do Lo e L1 foi avaliado na presença de diferentes composições de lipídios (DPPC, DPPC:Chol (9:1), DPPC:DPPS (8:2)) e de detergentes (SDS e LPC), utilizando sistemas miméticos de membrana: monocamada, micela e lipossomo. Em monocamada, sistema planar, foi observado um aumento da pressão superficial, provavelmente causado pela presença de peptídeo. Nos sistemas compostos por DPPC:Chol e DPPC:DPPS o efeito foi maior na presença do L1, sugerindo interação eletrostática entre o peptídeo e as monocamadas. Já o peptídeo Lo, por não possuir carga, apresentou maior interação com a monocamada de DPPC, por ser zwitteriônica. Resultados similares foram obtidos através do estudo com lipossomos constituídos por DPPC, DPPC:Chol (9:1) e DPPC:DPPS (8:2). Em todos os meios, através da espectrofotometria de fluorescência, foi observado um blue-shift, ou seja, migração do triptofano para um ambiente mais apolar. Para o Lo, isso foi maior na presença de DPPC; para o L1, na presença de DPPC:Chol e DPPC:DPPS. Através do DSC foi observado um aumento da entalpia e diminuição da cooperatividade (t1/2), causado pela presença de peptídeo na bicamada. Em DPPC:Chol (9:1) e DPPC:DPPS esse efeito foi maior na presença do L1; e em DPPC, na presença do Lo, confirmando os resultados anteriores. Essas interações peptídeo-mimético de membrana foram acompanhadas por mudanças conformacionais, observadas através do CD. O peptídeo Lo, tanto em meio aquoso, quanto na presença dos diferentes lipossomos está não-ordenado, entretanto, possui diferenças conformacionais em cada meio. O peptídeo L1 em meio aquoso apresenta estrutura ao acaso com interação entre os triptofanos, porém em DPPC e em DPPC:Chol (9:1) sofre alteração conformacional, distanciando os triptofanos; em DPPC:DPPS (8:2) sofreu alteração para -folha. Isso demonstra que a composição lipídica induz diferentes conformações nos peptídeos e pode afetar seu mecanismo de ação. No estudo com micelas também foi observado interação de ambos os peptídeos com SDS, e também com LPC. Em SDS os estudos sugerem que o L1 está mais inserido no meio apolar que o Lo; já em LPC, o Lo. Esses peptídeos também apresentaram alteração conformacional na presença das micelas. O peptídeo Lo, tanto em SDS, quanto em LPC, apresentou conformação não-ordenada, porém diferentes. Já o peptídeo L1 apresentou conformação -folha na presença de SDS e LPC, porém também com diferenças. Os resultados demonstram que o peptídeo com estrutura linear (L1) possui maior liberdade conformacional. Portanto, alguns fatores dirigem o processo de interação destes peptídeos: conformação e hidrofobicidade. Devido à diferença estrutural (cíclica e linear), esses peptídeos conferem diferentes hidrofobicidades, e isso interfere na conformação da molécula, além do meio lipídico. E finalizando o estudo, foi identificado através da DM que o resíduo de triptofano da posição 2 é o aminoácido mais inserido no meio apolar das micelas, após interação. Assim, um possível mecanismo de interação do peptídeo Lo é baseado, inicialmente, na adsorção do peptídeo na superfície lipídica. Em seguida ocorre a interação hidrofóbica membrana-peptídeo, acompanhada pela inserção do triptofano da posição 2 na região mais profunda da membrana, induzindo alterações conformacionais na molécula mediante a interação, dos outros resíduos, com a membrana. / Labaditin is a cyclic decapeptide with high hydrophobic character, extracted from Jatropha Multifida, a plant from Euphorbiaceae family. It is more resistant to proteolytic degradation than its corresponding linear isomers. Studies have been showed that conformational restriction of cyclic peptide increases its affinity and specificity to the membrane. Due to these physical characteristics and to the biological activities shown, such as inhibition of the classical pathway of human complement system in vitro and antibacterial activity for Streptococcus mutans, this peptide has attracted biological and pharmacological interest. However, neither the target nor the action mechanism are known yet. For this reason, the Labaditin (Lo) and the linear analogue (L1) peptides, different structures, were studied in an attempt to get information regarding the mechanism of action, interaction and possible conformational changes due to the interaction with biological membranes. The behavior of Lo and L1 was studied in the presence of different lipid compositions (DPPC, DPPC:Chol (9:1), DPPC:DPPS (8:2)) and of detergents (SDS and LPC), using membrane mimetic systems: monolayer, micelle and liposome. In monolayer, planar system, it was observed an increase of surface pressure, probably caused by the presence of peptide. In the systems composed by DPPC:Chol and DPPC:DPPS the effect was greater in the presence of L1, implying electrostatic interaction between the peptide and the monolayers. Lo peptide, on the other hand, due to the fact that it does not have charges, presented greater interaction with the DPPC monolayer, a zwitterionic molecule. Similar results were obtained through studies with liposome composed by DPPC, DPPC:Chol (9:1) and DPPC:DPPS (8:2). In all environments, through fluorescence spectroscopy, a blue-shift was observed, which means, migration of the tryptophan to a more non-polar environment. For Lo, it was higher in the presence of DPPC; for L1, in the presence of DPPC:Chol and DPPC:DPPS. Using the DSC technique an increase of enthalpy and a decrease of cooperativity was observed (t1/2), due to the presence of peptide in the bilayers. In DPPC:Chol (9:1) and DPPC:DPPS this effect was greater in the presence of L1; while in DPPC, in the presence of Lo, confirming the previous results. These peptide-membrane mimetic interaction was followed by conformational changes, observed through the CD. The Lo peptide has a unordered conformation in aqueous environment, and in the presence of liposomes also is unordered, although with differences. L1 peptide in aqueous environment presents random coil structure with interaction between tryptophan, but in DPPC and in DPPC:Chol (9:1) it suffers conformational changes, distancing tryptophan; in DPPC:DPPS (8:2) it changes to -sheet. This demonstrates that the lipidic composition induces conformational changes in peptides and it may affect their mechanism of action. In the study with micelles it was also observed interaction between peptides-SDS, and also with peptides-LPC. In SDS, the studies suggest that L1 is more inserted in the non-polar environment than Lo; in LPC, Lo is more inserted. These peptides also presented conformational changes in the presence of micelles. Lo peptide, both in SDS, and in LPC, presented unordered conformation, but differently. L1 peptide presented -sheet conformation in the presence of SDS and LPC, but also with differences. The results show that the peptide with linear structure (L1) has greater conformational liberty. Therefore, some factors are responsible to the interaction process of these peptides: conformation and hydrophobicity. Due to the structural difference (cyclic and linear), these peptides present different hydrophobicity, and it interferes in the conformation of the molecule, as well as the lipidic environment. On the last study it was identified through DM that the tryptophan residue from position 2 is the amino acid most inserted in the micelles, after interaction. Thus, a possible Lo peptide interaction mechanism is based, initially, on the adsorption of the peptide on the lipidic surface. Next, there is a hydrophobic interaction peptide-membrane followed by the tryptophan insertion of the position 2 in the deepest region of the membrane, inducing conformational changes in the molecule, through the interaction of the other residues with the membrane.

A influência da isomeria cis/trans na reatividade de complexos do tipo [RuCl2(DMSO)3(L)], onde L = DMSO (2;4), n-butilamina (1;3) na polimerização via metátese por abertura de anel (ROMP) foi investigada. Os complexos 1 e 2 apresentaram isomeria fac, enquanto que os complexos 3 e 4 foram trans e mer, respectivamente. Os dados cristalográficos sugerem uma conformação fac para o novo complexo 1. Os parâmetros eletrônicos e estéreos dos ligantes, medidos pelos valores de pka e θ, respectivamente, foram usados para interpretação dos resultados. Os monômeros cíclicos usados foram norborneno (NBE), norbornadieno (NBD) e diciclopentadieno (DCPD), considerando como parâmetros as razões molares monômero/complexo, temperatura, tempo de reação e estrutura geométrica. Complexos cis foram mais ativos do que os complexos trans para a polimerização de norborneno e de norbornadieno, sendo os resultados a 50 oC melhores do que os resultados a 25 oC. Na polimerização de norbornadieno, ao contrário da polimerização com norborneno, os melhores rendimentos foram obtidos com os complexos contendo os ligantes cloro trans-posicionados. Os compostos isolados foram caracterizados por analise elementar, FTIR, voltametria cíclica, espectroscopia na região do UV-vis, RMN de 1H e 13C e espectroscopia de difração de raio-x. Em adição, combinação de resultados teóricos e dados experimentais para a reação de ROMP de norborneno usando [RuCl2(PPh3)2(piperidina)] mostra a otimização estrutural das espécies envolvidas na catálise e o perfil termodinâmico de toda reação. Fatores entrópicos explicam a espontaneidade observada para a dissociação de grupos de saída, que são processos endotérmicos. Logo após a etapa determinante da velocidade, ocorre a coordenação de uma molécula de norborneno e um efeito trans-sinérgico entre este monômero e o ligante piperidina ativa a catálise. O uso de outros diazocompostos (TBDA e BDA) foi feito para analisar as influências eletrônicas e estéricas do carbeno em questão. Efeitos eletrônicos tem menos influência sobre a estrutura da espécie ativa do que os efeitos estéricos, influenciando nos rendimentos e nos dados dos polímeros formado. / The influence of cis/trans isomery on the reactivity of complexes of the type [RuCl2(DMSO)3(L)], where L = DMSO (2;4), n-butylamine (1;3) in the ring-opening metathesis polymerization (ROMP) was investigated. The complexes 1 and 2 showed isomerism fac, while the complexes were 3 and 4 were trans and mer, respectively. The crystallographic data suggest a fac conformation for the new complex 1. The electronic and steric parameters from ligands, measured by pKa values and θ, respectively, were used for interpretation of the results. The cyclic monomers used were norbornene (NBE), norbornadiene (NBD) and dicyclopentadiene (DCPD), given as parameters the molar ratios monomer/complex, temperature, reaction time and geometric structure. The cis complexes were more active than the trans complex for polymerization of norbornene and norbornadiene, and the results at 50 oC better than the results at 25 oC. The polymerization of norbornadiene, unlike the polymerization of norbornene, best yields were obtained with complexes containing trans-positioned chloro ligands. All compounds were characterized by elemental analysis, FTIR, cyclic voltammetry, UV-vis spectroscopy, NMR 1H and 13C spectroscopy and x-ray diffraction. In addition, combination of theoretical and experimental results data for ROMP reactions of norbornene using [RuCl2(PPh3)2(piperidine)] shows the structural optimization of the species involved in the catalysis and the thermodynamic profile of the whole reaction. Entropic factors explain the spontaneity observed for dissociation from both leaving groups, which are endothermic processes. Immediately after the rate-determining step occurs the coordination of a norbornene molecule and a trans- synergistic effect between the monomer and ligand piperidine actives the catalysis. The use of other diazocompostos (TBDA and BDA) was done to analyze the electronic and steric influences of the carbene in question. Electronic effects had less influence on the structure of the active species than the steric effects, influencing the yield and the data of the polymers formed.

Thesis advisor: Utku Ünver / This dissertation consists of three chapters. The first chapter consists of a survey of the literature on affirmative action and diversity objective in school choice mechanisms. It presents and analyzes some of the main papers on the subject, showing the evolution of our understanding of the effects that different affirmative action policies have on the welfare and fairness of student assignments, the satisfaction of the diversity objectives as well as the domain of policies that allows for stable outcomes. The second chapter analyzes the problem of school choice mechanisms when policy-makers have objectives over the distribution of students by type across the schools. I show that mechanisms currently available in the literature may fail to a great extent in satisfying those objectives, and introduce a new one, which satisfies two properties. First, it produces assignments that satisfy a fairness criterion which incorporates the diversity objectives as an element of fairness. Second, it approximates optimally the diversity objectives while still satisfying the fairness criterion. We do so by embedding "preference" for those objectives into the schools' choice functions in a way that satisfies the substitutability condition and then using the school-proposing deferred acceptance procedure. This leads to the equivalence of stability with the desired definition of fairness and the maximization of those diversity objectives among the set of fair assignments. A comparative analysis also shows analytically that the mechanism that we provide has a general ability to satisfy those objectives, while in many familiar classes of scenarios the alternative ones yield segregated assignments. Finally, we analyze the incentives induced by the proposed mechanism in different market sizes and informational structures. The third chapter (co-authored with Orhan Aygün) presents an analysis of the Brazilian affirmative action initiative for access to public federal universities. In August 2012 the Brazilian federal government enacted a law mandating the prioritization of students who claim belonging to the groups of those coming from public high schools, low income families and being racial minorities to defined proportions of the seats available in federal public universities. In this problem, individuals may be part of one or more of those groups, and it is possible for students not to claim some of the privileges associated with them. This turns out to be a problem not previously studied in the literature. We show that under the choice function induced by the current guidelines, students may be better off by not claiming privileges that they are eligible to. Moreover, the resulting assignments may not be fair or satisfy the affirmative action objectives, even when there are enough students claiming low--income and minority privileges. Also, any stable mechanism that uses the current choice functions is neither incentive compatible nor fair. We propose a new choice function to be used by the universities that guarantees that a student will not be worse off by claiming an additional privilege, is fair and satisfies the affirmative action objectives whenever it is possible and there are enough applications claiming low--income and minority privileges. Next, we suggest a stable, incentive compatible and fair mechanism to create assignments for the entire system. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Economics.

Thesis advisor: John E. Ebel / Large magnitude offshore passive margin earthquakes are rare, making small magnitude events (M < 4) the predominant data available to study the mechanisms of seismicity along passive margins. This study is focused on a swarm of events (M2.1-M3.9) that occurred from 2012-2013 located in the Gulf of Maine (GM) along the Atlantic Passive Margin (APM) shelf break, a region with previously minimal recorded seismic activity. Relative locations were calculated for the earthquakes of the GM swarm and a moment tensor inversion method was used to calculate focal mechanisms for the two largest events in the swarm. The results of the relative location method constrained a fault orientation to a strike of 243° ± 3° and a dip of 25° ± 3°. The focal mechanisms for the two largest events were determined to be oblique normal faults with steeply dipping planes at depths between 12-18 km. For the largest event (M3.9), the strike is 235° ± 1°, with a dip of 77.7° ± .8° and a rake of -116.5° ± 3°, and for the second largest event (M3.7) the strike is 259° ± 3°, with a dip of 78° ± 2° and a rake of -58.8° ± 7°. By mapping the spatial extent of the relative hypocenters, I infer a potential fault size of 2.7 km by 2.4 km. If this entire area were to rupture at once in the future, an earthquake of M4.9-M5.0 could occur, a magnitude not large enough to be tsunamigenic in the GM. Based on Gutenberg-Richter relations from the eastern APM, if a M7 can occur in the GM, its estimated mean repeat time is 2,120-22,800 years, and it could be tsunamigenic depending on the event’s proximity to the continental slope. / Thesis (MS) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

Esta dissertação apresenta os resultados da investigação geotécnica de uma área que apresenta processos erosivos, na cidade de Bauru, interior de São Paulo, com o objetivo de caracterizar o solo local e definir quais os principais fatores responsáveis pela evolução desses processos. Eles tiveram início com o desmatamento, impermeabilização do solo, deságüe de águas pluviais e esgoto e atingiram grandes dimensões com a implantação de loteamentos, com projeto inadequado e falta de obras de infra-estrutura de drenagem. Com observações de campo, ensaios in situ e laboratório, o fenômeno foi estudado com o intuito de se estabelecer um mecanismo que explique o processo erosivo. No local ocorrem desde solos residuais jovens de arenito, a residuais maduros, muito evoluídos por processos pedogenéticos e em alguns pontos se tem também solos transportados. Foram realizados ensaios de caracterização, de erodibilidade e mecânicos em três amostras distintas e representativas de solos do local, além de ensaios de campo SPT e CPT. Esses solos foram classificados como uma areia pouco argilosa de coloração variável e quase sempre se encontram em condição não saturada. Os resultados dos ensaios de erodibilidade mostraram que os três métodos empregados classificaram os solos como altamente erodível, sendo o método mais interessante aquele proposto por Nogami & Villibor (1979) para os solos estudados. A sucção exerce papel importante na resistência desses solos e a saturação das amostras promoveu a redução significativa da coesão. A água é o agente deflagrador e principal responsável pela evolução do processo erosivo, tanto pelo escoamento superficial como pelo escoamento subsuperficial. O seu fluxo no interior do maciço carreia material e modifica a distribuição granulométrica do solo, alterando também suas propriedades. O mecanismo de evolução se inicia com o aumento do teor de umidade do solo pela ação da chuva podendo, em alguns pontos, chegar-se a saturação, provocando a diminuição da resistência através da anulação do efeito da coesão. Uma vez saturado e com o fluxo de d\'água, o solo pode perder sua estrutura por erosão interna retrogressiva, assim é facilmente destacado e carreado, provocando a instabilidade dos taludes e evolução do processo erosivo. / This dissertation presents geotechnical site characterization results of an erosion process area, in Bauru city, inland of São Paulo State, Brazil. The objective is to characterize the local soil and define the major causing factors for the erosion process evolution, which initiated with deforestation, soil sealing and discharge of pluvial and sewer water. The erosion turned huge with an urban setting with inappropriate design and no drainage infrastructure jobs. This phenomenon was studied by field observation, in situ and laboratory tests to establish a mechanism to explain the erosion process. Young residual soils of sandstone, mature residual soil weathered by pedogenetic processes and transported soils occur in the site. Characterization, erodibility and mechanical tests were carried out on three typical and distinct soils as well as SPT and CPT testing. The soils were classified as clayey sand with variable colors, almost always in unsaturated condition. Erodibility test results from three different methods classified the soils as very high erodibility, and Nogami and Villibor (1979) method was the most interesting for the studied soil. Suction plays an important role in the shear strength and soil saturation significantly reduced cohesion. Water is the trigging agent and the major responsible for the erosive process evolution, even by superficial or groundwater flow. The flow inside the soil mass changes the grain size distribution of the soil and also modifies their properties. The evolution mechanism begins increasing the soil water content by the rain and it can, in some places, reach soil saturation reducing shear strength turning cohesion equal to zero. Since the soil is saturated and with water flow, it can loose its structure by piping, so it\'s easily detached and dragged along causing slope instability and evolution of erosion process.

[pt] Durante a fase produtiva de um poço de petróleo ou gás, muitas vezes há a produção simultânea de partículas sólidas arrancadas da matriz da rocha reservatório. Este fenômeno recebe o nome de produção de areia. Neste caso as tensões e as condições de fluxo nas vizinhanças do poço são fatores fundamentais para a deflagração do processo. As tensões que se concentram na parede do poço com a perfuração do mesmo, pode ser de tal magnitude que pode causar a perda da coesão entre os grãos e criando , assim , uma região de material granular susceptível ao arraste pelas forças de percolação derivadas do fluxo. Este trabalho visou a realização de ensaios em amostras de arenito Rio Bonito e arenito sintético utilizando a técnica da Tomografia Computadorizada de Raios-X para acompanhamento em tempo real dos ensaios. Os ensaios tiveram por objetivo identificar a pressão de início e o modo de propagação da ruptura da parede da cavidade interna da amostra ensaiada. Estes são estágios iniciais dos processos de produção de areia em rochas. As análises das imagens tomográficas adquiridas durante os ensaios permitiram a visualização de breakouts e arrombamentos dos poços. Estudos mais detalhados possibilitaram estimar a quantidade de areia produzida e reconstruir tridimensionalmente o processo de propagação da ruptura. / [en] During productive phase of the well, manytimes there is simultaneous production of the solid particles detached from matrix of the reservoir rock. This phenomenon receive the name of the sand production. In this case stress and flow conditions around of the well are fundamental factors for deflagration of the process. Stress concentration in the wall of the well lead to the loss of cohesion between grains arising, consequently, a granular material region susceptible for dragging by seepage forces derived from fluid flow. The objective of this work was to perform sand production tests in Rio Bonito and synthetic sandstone samples using real-time X-Ray Computerized Tomography. The tests investigated the initial and the evolution of failure at the cavity wall of samples. These are initial stages of the sand production process. The analysis of the CT-scans obtained during tests allowed the visualization of breakouts and collapses of the wells. From studies more details were possible estimate the sand production and produce 3-D images of the propagation of the failure.

Long relegated to the background by the pre-eminence of magnesium-based, stoichiometric Grignard reagents, a distinct chemistry of the heavier alkaline earth metals, calcium, strontium and barium, is only now starting to emerge. As similarities have been drawn between the large, electropositive, redox-inert and d0 alkaline earth Ae2+ dications and the Ln3+ cations of the lanthanide series, a growing group 2-mediated catalytic chemistry has developed over the last decade, including polymerisation reactions, heterofunctionalisation reactions of multiple bonds and some rare examples of dehydrocoupling reactions. Among these catalytic reactions the magnesium- and calcium-catalysed intramolecular hydroamination of aminoalkenes has attracted particular interest. Mechanistic studies have demonstrated many parallels with the lanthanide-mediated catalytic cycle based upon successive σ-bond metathesis and insertion steps. In the first part of this thesis, further investigations into the hydroamination/cyclisation reaction have demonstrated the prominent role of the charge density of the catalytic group 2 cation (M = Mg, Ca, Sr, Ba), the beneficial influence of stabilising spectator ligands, and the importance of the choice of the reactive co-ligand for efficient catalyst initiation. Kinetic analyses of reactions monitored by NMR spectroscopy have given new insight into activation energies, entropic effects, substrate and product inhibition, and kinetic isotope effects, leading to a review of the previously suggested lanthanide-mimetic mechanism. In a second part, this study seeks to address two of the main challenges posed by the intramolecular hydroamination reaction in particular, and heavier alkaline earth-catalysed reactions in general: (i) The need to design new monoanionic spectator ligands capable of stabilising heteroleptic heavier alkaline earth complexes and preventing deleterious Schlenk-type ligand redistribution processes in solution; (ii) The stabilisation of highly reactive heteroleptic group 2 alkyl functionalities for fast, irreversible catalyst initiation and novel reactivity.