Thesis advisor: Amir H. Hoveyda / Chapter 1: Efficient Z-Selective Cross-Metathesis of Secondary Allylic Ethers Efficient Z-selective cross-metathesis of secondary allylic ethers were catalyzed by monoaryloxide monopyrrolide molybdenum complexes. Reactions involving both silyl and benzyl protected ethers were demonstrated, as well as ethers containing alkyl, aryl and alkynyl substituents. Mechanistic studies were performed, and the reactions were applied to the total synthesis of several ene-diyne natural products. Chapter 2. Stereoselective Total Synthesis of Disorazole C1 The stereoselective total synthesis of disorazole C1 is reported. The synthesis was completed in 12 longest linear steps. Our synthesis demonstrates the utility of Z-selective cross-metathesis to form both alkenyl borons and alkenyl halides. Another key transformation was a one-pot Suzuki-dimerization reaction to form a symmetric 30 membered ring in relatively high yield. Chapter 3. Stereoselective Cross-Metathesis to Form Trisubstituted Alkenes Initial studies into the stereoselective formation of trisubstituted olefins through molybdenum catalyzed cross-metathesis have been performed. Our mechanistic understanding of the reaction lead us to focus on the synthesis of alkenyl halides, which can be obtained in up 90% yield and 75:25 E:Z selectivity. Chapter 4: Ring-Closing Metathesis in the Synthesis of Natural Products Development of highly efficient and selective ring-closing metathesis reactions have enabled collaborators to successfully implement routes in total synthesis endeavors. A diastereoselective seven-membered ring-closing metathesis enabled the successful synthesis of (±)-tetrapetalone A methyl-aglycon. An enantioselective ring-closing metathesis to form a six membered ring has provided access to enantioenriched aspidosperma alkaloids. / Thesis (PhD) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

O trabalho apresenta também um estudo de confiabilidade e estabelece uma faixa de valores para o esforço de fechamento de portas baseado na variação de algumas componentes chaves no cálculo. A curva característica que é um dos parâmetros de saída do modelo apresenta forma extremamente próxima da medição realizada em laboratório. No Brasil, a indústria automotiva é conhecida por sua grande influência e peso na economia do país, assim como em diversos outros países. O conjunto porta na concepção do veículo é de extrema importância, visto que é região do veículo com que o consumidor trava contato primeiro. Um valor de esforço elevado para realizar a abertura e fechamento das mesmas pode levar a uma imagem indesejada pela montadora do veículo. O valor do esforço necessário para fechar a porta é um item de extrema importância, pois além de influenciar a imagem do veículo e da marca, é um item do pacote de conforto e ergonomia do veículo. O evento fechamento da porta parte do instante em que a porta está na condição aberta e seus componentes se encontram em descanso. O evento é modelado matematicamente e em planilha dinâmica admitindo como parâmetros de entrada dados específicos do veículo e seus componentes, como saída têm-se o valor da energia de fechamento de portas e a parcela de cada componente envolvido. São apresentados resultados experimentais para que o modelo seja considerado válido. Com a conclusão do modelo é possível estimar a queda de energia em função da vida de alguns componentes como a fechadura e o pacote de guarnições, bem como a influência do uso de sobreinjetados autolubrificantes na fechadura. Este trabalho contribui com os profissionais de Engenharia de Produto nas áreas de Carroceria, Mecanismos e Partes Móveis com a elaboração de uma ferramenta de cálculo para uso em qualquer fase de projeto, principalmente para estimar o valor da energia de fechamento de porta no momento de sua conceituação e até na validação de veículos protótipo. / The Brazilian automotive industry is known by its great influence on the country economy, similar to several other countries. It is important to highlight the door assembly importance on the vehicle concept, as it is the first contact made to the customer. The vehicle ingress is through the side access area, established by the doors and a high door closing effort may lead to a wrong impression. The door closing effort or also known as door closing energy is an extreme importance asset, as well as influencing the image of the vehicle and the brand, it is an item of ergonomics and vehicle comfort. The automotive door closing event starts at the moment door is open and pushed to close itself. This event is math modeled and implemented as an excel dynamic calculation plan, considering as input the vehicle and components specific data, its output is the door closing effort and each components portion. It is presented a series of values so the model is considered valid. This work also presents a reliability study defining a range of experimental values for the door closing effort based on tolerances of components used in the model calculations. The characteristic curve which is one of the parameters of the model output is extremely close to the measurement performed in the laboratory. With the completion of the model is possible to estimate the energy loss due to the life of certain components such as latches and weatherstrips, and the influence of using self-lubricating over molding in the latch. This study contributes to the Product Engineering professionals in the areas of Body, Mechanisms and Body Closures, with the elaboration of a calculation tool for use in any design phase, but mostly serving to estimate the door closing effort at the moment of conception until the validation of prototype vehicles.

O objetivo dessa dissertação é compreender como se dá a relação do trabalhador com atual contexto de acumulação capitalista em situações extremas como a de demissão iminente. Trata-se de um estudo de caso que tem como objeto uma multinacional do setor automotivo que encerrou suas atividades no Rio Grande do Sul em 2016. Objetivou-se discutir sobre como as relações de trabalho e a organização do trabalho foram historicamente construídas e aperfeiçoadas, de forma a tornar a exploração cada vez menos visível para os trabalhadores. Isso possibilita a exploração e consequentemente perpetua e maximiza a acumulação do capital. A análise das entrevistas, triangulada com notícias vinculadas na mídia, dados fornecidos pela empresa e boletins do sindicato, amparados na teoria sugerem que nesta era de financeirização e desterritorialização, alguns mecanismos facilitam a legitimação da exploração. São eles: o discurso do trabalho, a cooptação da subjetividade dos trabalhadores e a falácia da empregabilidade. À medida que a precarização do trabalho se propaga de formas cada vez mais complexas, potencializam-se também as contradições do capital e o trabalhador é colocado cada vez mais sob tensão. Percebe-se que a organização se apropria da subjetividade dos trabalhadores por meio de diferentes mecanismos de gestão e controle. Isso fragiliza os laços sociais, o que tem consequências nas formas de organização coletiva e mecanismos de resistência dos trabalhadores. Posteriormente, apresenta-se a questão da empregabilidade como uma falácia, em que cada vez mais o trabalhador vê-se responsável pelo seu próprio destino, bem como também pelo destino da empresa. Consequente a isso, percebe-se um sentimento de auto-culpabilização e responsabilização excessiva. Finaliza-se analisando os processos de resistência ao fechamento da fábrica. Verifica-se que o trabalhador já não tem mais amparo do seu sindicato, que se encontra enfraquecido politicamente. Outras formas de resistência coletiva articulada também não foram percebidas. Porém, algumas formas individualizadas de resistência foram encontradas, tais como o absenteísmo, boicote ao trabalho e até pequenas sabotagens. Conclui-se que as atuais formas de acumulação de capital, que se valem da desterritorialização, da financeirização e de mecanismos de legitimação da exploração, tornam a situação do trabalhador cada vez mais frágil. O caso da NX ilustra como a abstração do capital e as formas de controle cada vez mais sutis intensificam a precarização do trabalho e diminuem as possibilidades de resistência frente ao capital. As portas fecham porque no processo de reprodução capitalista a lógica das organizações é contribuir para o acúmulo de capital. A medida que essa lógica não atender mais à ética do capital - o lucro, a estratégia passa a ser o fechamento e a transferência para locais com menores custos. / The purpose of this dissertation is to understand how the relation of the worker with the current context of capitalist accumulation takes place in extreme situations like the one of imminent mass dismissal. It is a case study that has, as its object, an automotive multinational factory. Such factory closed its doors in Rio Grande do Sul in April 2016. It starts from this object to discuss how labor relations and the organization of work have historically been built and improved in order to make exploitation less visible to workers. Such invisibility enables exploitation and consequently perpetuates and maximizes the accumulation of capital. The analysis of the interviews triangulated with news in the media, data provided by the company and union bulletins, suggest that in this era of financialization and de-territorialization, some mechanisms enable the legitimation of exploitation. These are: the importance of work for the workers, the co-optation of workers’ subjectivity, and the fallacy of employability. As the precarization of work disseminate more and more, the contradictions of the capital are also potentiated and the worker is increasingly placed under tension. It is perceived that the organization appropriates itself from the subjectivity of workers through different management and control mechanisms. This weakens the social ties, which has consequences in the collective forms of organization and in the mechanisms of resistance of the workers. Subsequently, the issue of employability is presented as a fallacy, in which the worker is increasingly responsible for his own destiny, as well as for the fate of the company. As a result, there is a feeling of self-blame and excessive accountability over the worker. It ends by analyzing the processes of resistance before the closure of the factory. It was verified that the worker is no longer supported by his union, which is politically weakened. Other forms of organized resistance were not noticed. However, some individualized forms of resistance have been found, such as absenteeism, boycotting work and even minor sabotages. We conclude that the current forms of accumulation of capital, which use deterritorialization, financialization and mechanisms to legitimize exploitation, make the situation of the worker increasingly fragile. The doors close because in the process of capitalist reproduction the logic of organizations is to contribute to the accumulation of capital. As this logic no longer meets the ethics of capital - the profit, the strategy becomes closing or transfer to places with lower costs.

O trabalho apresenta uma metodologia para a simulação de abertura e fechamento de trinca, durante o processo de propagação, utilizando um programa comercial de elementos finitos. Este programa é utilizado para determinar os fatores de intensidade de tensão de abertura e fechamento de trinca. É apresentado o modelo de Newman que serve de embasamento para o desenvolvimento da metodologia de liberação de nós na carga mínima, utilizada no trabalho para a propagação da trinca. São avaliados quatro tipos de corpos de prova SE-(B) (corpo de prova de três pontos de apoio submetido a flexão), SE-(T)(corpo de prova com trinca lateral submetido a tração), M-(T) (corpo de prova com trinca central submetido a tração) de uma liga de alumínio Al 2024-T351 e um aço bifásico ( ferrita + martensita). Um corpo de prova do tipo C-(T) (corpo de prova compacto submetido a tração) de aço bifásico também foi avaliado. Os corpos de prova SE-(B), SE-(T) e M-(T) da liga de alumínio Al 2024-T351 foram submetidos a carregamentos de amplitude constante, com razões de carga R = 0 e R = 0,5. Os resultados das análises são comparados com resultados do código FASTRAN, principal código numérico utilizado para simular abertura e fechamento de trinca por plasticidade induzida, através de uma normalização dos fatores de intensidade de tensão máxima e de abertura da trinca. Os resultados numéricos com o corpo de prova C-(T) submetido a carregamento de amplitude constante, com razão de carga R = 0,1 foram comparados com resultados de ensaio, objetivando validar o fator de intensidade de fechamento de trinca obtido através da análise numérica. Essa comparação é feita através de normalização numérica e experimental do fator de intensidade de tensão de fechamento de trinca com o fator de intensidade de tensão máxima. A metodologia de simulação de propagação de trincas, já aplicada na industria aeronáutica, pode ser aplicada em outras áreas como, por exemplo, na indústria automotiva, uma vez que o consumidor está cada vez mais exigente e o desenvolvimento de novos critérios de projeto se faz necessário. / The work introduces a methodology to simulate fatigue crack opening and closing during crack propagation, using a commercial finite element code. This code is used to determine the crack opening and closure stress intensity factors. The Newman model is used as a baseline to develop the methodology. The nodes are released at the minimum load, during the crack propagation process. Four kinds of specimens SE-(T) ( Single Edge Tension), SE-(B) ( Single Edge Bending), M-(T) ( Middle Tension) of the an aluminum alloy Al–2024-T351 and a dual phase steel (ferrite + martensite) were evaluated. A compact tension specimen C-(T) of a dual phase steel was evaluated. The aluminum alloy specimens, SE -(T), SE-(B) and M-(T), were evaluated under constant amplitude loading with load ratios R = 0 and R = 0.5. The results of these analyses are compared with the results of FASTRAN, principal numerical code used to simulate crack opening and closing plasticity induced by, normalizing the opening stress intensity factor. The numerical results from a C-(T) specimen, under constant amplitude loading and a load ratio R = 0.1, were compared with results from a test performed in the laboratory. The numerical and experimental closure stress intensity factors are normalized with the maximum stress intensity factor. Crack closure simulations are currently used in the aircraft industry. They are now being incorporated in same automotive and other ground vehicle fatigue analysis procedures.

Les premiers romans de John Dos Passos s’inscrivent dans le courant moderniste et sont caractérisés par une organisation originale des mots sur la page. Le texte n’est pas un bloc monolothique mais il est découpé en sections et ponctué d’épigraphes. Il contient également une multitude de collages présentés dans des styles et des polices variés. Cette observation est le point de départ de cette étude qui propose d’analyser la matérialité du texte dans les premiers romans de John Dos Passos, Manhattan Transfer et la trilogie USA, publiés entre 1925 et 1938. Ces ouvrages interrogent le regard du lecteur sur le texte, en montrant ce qui est placé devant, autour de l’oeil de celui qui regarde. Ils invitent le lecteur à prendre conscience de ce qui influence sa vision. Le roman exhibe son armature et ses divers seuils, laissant soin à celui qui lit de poursuivre ou non sa lecture, de revenir en arrière et de faire les liens entre les différentes zones de texte. Le roman expose son mode de fabrication, soulignant qu’il est le produit d’un réagencement de textes antérieurs. Cette armature visible est autant faite de pleins que de vides et reflète la tension entre l’ambition de tout dire, tout contenir et la reconnaissance de la difficulté même de raconter. Le jeu avec les espaces blancs, la ponctuation et les indications phonétiques renforcent la dimension écrite du texte tout en essayant de de le faire sortir hors de la page et de résister à toute clôture. / The early novels of John Dos Passos are part of the modernist literary movement. They are characterized by an original organization of the words on the page. The text is no longer a monolithic block, but is divided into sections and its separations are highlighted by a vast paratext. It also contains a variety of collages presented in various styles and in different fonts. These observations are the starting point of this research, which focuses on the materiality of the text in the early novels of John Dos Passos, Manhattan Transfer and the trilogy USA, published between 1925 and 1938. These novels question the gaze of the reader on the text, showing what is placed in front of and around the eye of the observer. The reader becomes aware of what influences his vision. The novel displays its internal structure and various thresholds, allowing the reader to continue or to stop reading, to go backwards and to create connections between the different sections of the text. The novel displays how it has been constructed, highlighting that it is the product of the rearrangement of previous texts. This visible internal structure is also built out of gaps and empty spaces. It reflects the tension between the ambition to be exhaustive, to contain everything and to acknowledge the difficulty to tell a story. The interplay with the blank space on the page, the use of punctuation and phonetic indicators reinforce the written aspect of the text, while at the same time making the words stand off the page and resistant to closure.

This session will provide practitioners working with children 0-3 information about the importance of and strategies for “bathing” young children in language. Research shows that by age 3 children who live in poverty are likely to have heard 30 million fewer words than their wealthiest peers. For children with disabilities from less affluent homes, this is an important issue. This session will provide practitioners working with these families and/or working directly with these children with strategies demonstrated through video clips on how to envelop these very young children in rich language in order to help close this gap.

Doctor of Education / This case study looks at the impact of closing an urban secondary school. It considers the experiences of the students, the staff and the parents. It does not argue with the decision to close the school but concentrates on the experience for those most closely involved. The thesis is guided by the main research question which is: “What is the impact of school closure on the various elements of a school community and is there a way to close a school and minimise this impact?” Supplementary questions seek to describe how the closure was undertaken and what factors can be identified which helped ease the transition for those involved. While seeking to develop theory grounded in the research the findings have also been informed by theory associated with grief, place attachment, emotion in the workplace and change. Unpublished primary documents such as transcripts of group interviews, responses to written questionnaires and minutes of meetings are the basic sources of data for this thesis. The researcher was an active participant in the closure and well known to all respondents. The thesis concludes that although keeping the school open for the final year was of benefit to the morale and adjustment of staff it was probably less beneficial for the students involved. It suggests that with proper counselling support and identification of the closure as a critical incident, a quick closure would help student learning outcomes and prevent teacher de-skilling. It also confirms the importance of a school, or probably any institution, in the emotional life of those associated with it. Note: The students in this study range in age from 13 to 18 years of age in Years 7 through to 12.

Hepatitis C is a blood-borne disease affecting 130-170 million people worldwide. The causative agent, hepatitis C virus (HCV), infects the liver and is the major reason for chronic liver disease worldwide. The HCV NS3 protease, a key enzyme in the virus replication cycle, has been confirmed to be an important target for drug development. With the recent release of two HCV NS3 protease inhibitors onto the market and an arsenal of inhibitors in clinical trials, there are now hopes of finally combating the disease. However, the success of treatment relies heavily on the ability to overcome the emergence of drug-resistant forms of the protease. The main focus of this thesis was on designing and synthesizing novel inhibitors of the NS3 protease with a unique resistance profile. Efforts were also made to decrease the peptide character of the compounds, with the long-term goal of making them into more drug-like compounds. Special attention was devoted to developing inhibitors based on a phenylglycine in the P2 position, instead of the highly optimized and commonly used P2 proline. Around ninety acyclic and macrocyclic inhibitors have been synthesized and biochemically evaluated. P2 pyrimidinyloxy phenylglycine was successfully combined with an aromatic P1 moiety and alkenylic P1´ elongations, yielding a distinct class of HCV NS3 protease inhibitors. Macrocyclization was performed in several directions of the inhibitors via ring-closing metathesis. Only the macrocyclization between the P3-P1´ residues was successful in terms of inhibitory potency, which suggests that the elongated P1-P1´ residue is oriented towards the P3 side chain. The metathesis reaction was found to be significantly more dependent on the substrate than on the reaction conditions. It was also found that the P3 truncated inhibitors were able to retain good inhibitory potency, which initiated the synthesis and evaluation of a series of P2-P1´ inhibitors. The potential of the P3-P1´cyclized inhibitor and the smaller, acyclic P2-P1´ as new potential drug leads remains to be determined through pharmacokinetic profiling. Gratifyingly, all the inhibitors evaluated on A156T and D168V substituted enzyme variants were able to retain inhibitory potency towards these as compared to wild-type inhibition.

The use of protective testimonial aids by the child witness has been advocated for as research indicates that it decreases witness stress and suggestibility; however, the use of such aids has also been attacked as incompatible with the defendant’s confrontational right and the fact-finding function of the jury. The present study examines the effects of testimony modality, as well as empathy-inducing closing arguments, on juror perceptions of the child witness, perceptions of the defendant, and ultimate judgments of guilt. In this between-subjects factorial study, workers on Amazon Mechanical Turk were invited to participate in an online simulated sexual assault case survey. Participants read all trial stimuli, which consisted of written juror instructions, case facts, testimonies, closing arguments, and legal definitions. In addition, participants were exposed to photographs depicting the child witness testifying under one of three possible conditions (direct, shielded, CCTV) and either read the prosecutor’s closing argument that contained a specific empathy-inducing portion or did not. Results indicated that regardless of testimony modality and empathy-inducing closing arguments, jurors did not exhibit a pro-prosecution or pro-defense bias.

The use of polymer supports for transition metal catalysts are very important and useful in synthetic organic chemistry as they make possible the separation and isolation of catalysts and products quite easy. These polymer-bound ligands/catalysts/reagents can, often, be recovered and recycled numerous times and typically yield products in high purity, negating the need for further purification steps (i.e. column chromatography). Because of this, interest in these systems has garnered international attention in the scientific community as being “Green”. Historically, insoluble, polymer-supports (i.e. Merrifield resin) were used to develop recoverable catalysts. This has the advantage of easy separation and isolation from products after a reaction; because of their insolubility, such supported catalysts can be easily removed by gravity filtration. However, these catalysts often have relatively poor reactivity and selectivity when compared to homogeneous catalysts. Because of this disadvantage, our lab has had interest in the development of soluble polymer-supports for transition metal catalysts. We have developed several separation methods for these soluble polymer-bound catalysts. These include thermomorphic liquid/liquid and solid/liquid as well as latent biphasic liquid/liquid separation techniques. This dissertation describes the use of both, latent biphasic liquid/liquid separation systems and thermomorphic solid/liquid separation systems. In order to perform a latent biphasic iii liquid/liquid separation, a polymer-bound catalyst must have a very high selectivity for one liquid phase over the other. Our lab has pioneered the use of polyisobutylene (PIB) oligomers as supports for transition metal catalysts. Previous work has shown that these oligomers are > 99.96 % phase selectively soluble in nonpolar solvents. This has allowed us to prepare PIB-supported salen Cr(III) complexes that can be used in a latent biphasic liquid/liquid solvent system. The synthesis of these complexes is quite straightforward and such species can be characterized using solution state 1H and 13C NMR spectroscopy. Also, these complexes can be used to catalyze the ring opening of meso epoxides with azidotrimethylsilane (TMS-N3) and can be recovered and recycled up to 6 times, with no loss in catalytic activity. To perform a thermomorphic solid/liquid separation, a polymer-bound catalyst that is completely insoluble at room temperature but soluble upon heating must be used. Our lab has pioneered the use of polyethylene oligomers (PEOlig) as supports for transition metal catalysts. Such PEOlig-supported catalysts are able perform homogeneous catalytic reactions at elevated temperatures (ca. 65 ○C), but, upon cooling, precipitate out of solution as solids while the products stay in solution. This process allows for the easy separation of a solid catalyst from the product solution. Described herein, is the development of PEOlig-supported salen-Cr(III) complexes and PEOlig-supported NHC-Ru complexes. The preparation of these complexes is also straightforward and such species can be characterized using solution state variable temperature (VT) 1H and 13C NMR spectroscopy. In the case of the PEOlig-supported salen-Cr(III) complex, it was found to be a recoverable/recyclable catalyst for the ring opening of epoxides with TMS-N3 and could be reused 6 times with no loss in activity. The PE-supported NHC-Ru complex was able to be used as a recyclable ring closing metathesis (RCM) catalyst and could be used up to 10 times.