A major driving force for development of new catalyst systems is the need for more efficient synthesis of chemical compounds essential to modern life. Catalysts having superior performance offer significant environmental and economic advantages, but their discovery is not trivial. Well-defined, homogeneous catalysts can offer unparalleled understanding of ligand effects, which proves invaluable in directing redesign strategies. This thesis work focuses on the design of ruthenium complexes for applications in dinitrogen activation and olefin metathesis. The complexes developed create new directions in small-molecule activation and asymmetric catalysis by late-metal complexes. Also examined are the dual challenges, ubiquitous in catalysis, of adequate interrogation of catalyst structure and performance. Insight into both is essential to enable correlation of ligand properties with catalyst activity and/or selectivity. Improved methods for accelerated assessment of catalyst performance are described, which expand high-throughput catalyst screening to encompass parallel acquisition of kinetic data. A final aspect focuses on direct examination of metal complexes, both as isolated species, and under catalytic conditions. Applications of charge-transfer MALDI mass spectrometry to structural elucidation in organometallic chemistry is described, and the technique is employed to gain insight into catalyst decomposition pathways under operating conditions.

Orientador: Afira Vianna Ripper / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Educação / Made available in DSpace on 2018-08-26T20:07:53Z (GMT). No. of bitstreams: 1 Damin_MariaAparecidadaSilva_D.pdf: 1865892 bytes, checksum: 2d6ab6e119e9b1799b0f86e208f538ac (MD5) Previous issue date: 2015 / Resumo: Este estudo mapeia produções de professores e gestores, da Secretaria Municipal de Educação de Campinas, SP, no curso de Especialização "A Pesquisa e a Tecnologia na Formação Docente", da Faculdade de Educação da Unicamp, nos anos de 2008 e 2009. Ao seguir os fluxos de desejo, na contingência cotidiana, problematizando e teorizando práticas, gera-se um processo educativo caótico, constituído por campos intensivos, que denominei "Processo Educação Caos", caracterizado pela instabilidade e incerteza. Na tentativa de encontrar rastros de campos intensivos detonadores da educação como devir a impulsionar a experimentação de outras maneiras de se atuar na escola, transito nas produções escritas dos professores, gestores e em teorizações de alguns filósofos como Gilles Deleuze & Félix Guattari, Michel Foucault, Silvio Gallo, Baruch Spinoza, Antonin Artaud, Jaques Derrida, dentre outros. Alguns campos intensivos gerados nos encontros se mostram a aumentar a força de ação à maneira de Spinoza tais como: "a potência do desejo", "os encontros alegres", "o exercício da escrita" de forma livre. O seguir fluxos de desejo na problematização e teorização da pratica cotidiana pelo professor e gestor, no apreender via problematização de temas de interesse no dia a dia da sala de aula por alunos e professores. Os "encontros", que podem ser com qualquer coisa que aumente a força de existir e o exercício da escrita como o vento a soprar registros castradores da razão, marcados em nossos corpos por certa maneira de escrita vivida na escola. A produção de saberes nesse processo pedagógico se dá de forma transversal, portanto um currículo, aberto, em constante devir. No processo de escrita o que está naturalizado na escola passa a ser visto por outros ângulos, questões são postas a nu, o que pode impulsionar a busca por outras maneiras de fazer na escola, vida / Abstract: This study maps the production of teachers and school administrators from the Campinas Department of Education, São Paulo of a specialization course "The Research and Technology in Teacher Education", given by the Faculty of Education at UNICAMP during 2008 and 2009. Following the flows of desire in the daily contingency, discussing and theorizing practices generates a chaotic educational process, consisting of intensive fields which I have called "Process Education Chaos", characterized by instability and uncertainty. In an attempt to find traces of intensive fields of detonators of education as obligation, capable of boosting other experiments of acting in school, I go back and forth between the teachers and managers¿ written productions and the theories of philosophers; such as, Gilles Deleuze, Félix Guattari, Michel Foucault, Silvio Gallo, Baruch Spinoza, Antonin Artaud, Jacques Derrida, among others. Some intensive fields generated during meetings showed a growing rise on its action force similar to Spinoza¿s theories, for example, "the power of desire", "the gay encounters", "the exercise of writing" in a free manner. It follows the flow of desire on the discussion and theorization about the daily school practice, both by teachers and managers. The "encounters" which may be related to anything that increases the strength of existence and the exercise of writing, which, as the wind blows away castrating records of reason, our minds have been marked by the certain way that Writing was taught in school. The knowledge production on such an educational process goes across the board and in a transversal manner. It happens in the curriculum, which is open, and is constantly changing. The process of writing, that which is taken for granted in school, comes to be seen from different angles. It begins to see questions that be put openly which can boost the search for different ways of facing what has to be done at school / Doutorado / Psicologia Educacional / Doutora em Educação

Orientador: Antonio Carlos Rodrigues de Amorim / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Educação / Made available in DSpace on 2018-08-27T15:12:39Z (GMT). No. of bitstreams: 1 Bom-Tempo_JulianaSoares_D.pdf: 3212391 bytes, checksum: abd86f952a9cc47ef5f73560a40c35b3 (MD5) Previous issue date: 2015 / Resumo: A composição proposta se dá entre imagens, performances, clínicas, educação e filosofias. Para esse empreendimento parte-se em direção ao que não se sabe de antemão, portando uma pergunta como bússola: "seria na criação, produção e execução de imagens em performance um 'quando' para o acontecimento de uma clínica poética?" Diante dessa questão, têm-se, para pensar um 'quando' do acontecimento de uma clínica poética, imagens em performances criadas, produzidas e executadas em parcerias com a autora desse texto. Frente a essa composição, construíram-se quatro elementos-indicadores para encontrar coordenadas espaço-temporais que localizariam esse "quando", quais sejam: as zonas de riscos; as mobilizações dos signos; o figurar a carne e uma educação dos afetos. Operou-se junto às imagens em performances de Crútero; Carne; Cariogamia e o risco do aborto; Clara; Ovo-boca; Ilhas, linhas, palavras... germens; Egg-Mouth-Debris, tomadas como casos práticos, ao engendrarem zonas de riscos para agenciar individuações, que nunca se efetivam por completo, sempre portando algo de pré-individual e individuando também um meio; ao mobilizarem os signos territorializados pelo ordinário, fazendo-os variar a língua e as palavras de ordem ditadas pelo cotidiano em outras composições de sentido, outras maquinações; ao gerarem um figurar da carne, desorganizando os corpos, isolando-os na produção de um terreno de força que faz o corpo vazar e desfazer as funcionalidades dos órgãos; e, por fim, ao produzirem uma educação dos afetos, colocando as percepções em devires e desacoplando os visíveis e os dizíveis na produção de pequenos desertos que convocam a criação de um povo ainda por vir. As imagens em performances apresentadas, desse modo, foram se movimentando em busca pelas potências de produzir um "quando" espaço-temporal colocando em zonas de riscos os territórios, mobilizando os signos que formatam os cotidianos, abrindo os corpos a uma desorganização e a produção de uma educação dos afetos para o acontecimento de uma clínica poética / Abstract: The proposed composition occurs between images, performances, clinics, education and philosophies. For this enterprise we depart for what is not known beforehand, so with a question as a compass: "would it be in the creation, production and implementation of images in a performance a "when" for the event of a poetic clinic?" In light of this, there are, in order to think a ' when ' of the event of a poetic clinic, images in performances created, produced and executed in partnerships with the author of this text. Faced with this composition, we built four indicators to find spatio-temporal coordinates that would spot that "when", namely: risk zones; the mobilizations of the signs; the figuring of the flesh and an education of the affections. We dealt with the images in Crútero performances; Flesh; Karyogamy and the risk of abortion; Egg white; Egg-mouth; Islands, threads, words ... germs; Egg-Mouth-Debris, taken as case studies, by engendering risks areas to promote individuations, which never actualize thoroughly, thus always something of pre-individual and also individuating a environment; by mobilizing the signs territorialized by the ordinary, causing them to vary the language and the words of order dictated by the everyday in other compositions of sense, other machinations; by generating a figure of flesh, disarranging the bodies, isolating them in the production of a ground force that causes the body to leak out and undo the functionalities of the organs; and, finally, by producing an education of affections, by placing the perceptions in becoming and disconnecting the visible and the utterable in the production of small deserts that call for the creation of a people yet to come. The images in performances presented, thereby, were moving in search for the power of producing a spatio-temporal "when" putting the territories in risk areas, mobilizing the signs that format the day-to-day, opening the bodies to a disorganization and the production of an education of affections for the event of a poetic clinic / Doutorado / Educação, Conhecimento, Linguagem e Arte / Doutora em Educação

Necroptosis, a type of regulated necrotic cell death, involves cell membrane permeabilization and has been implicated in various acute and chronic pro-inflammatory diseases, including ischemia-reperfusion injury and neurodegenerative diseases. By using in vitro reconstitution studies and a chemical inhibitor, the kinase activity of the serine/threonine kinase RIPK1 had been shown to regulate necroptotic signaling downstream of TNF and Toll-like receptors (TLRs). To investigate the contribution of RIPK1 kinase activity to inflammation and necroptosis in vivo, we generated kinase inactive RIPK1 knock-in mice. Utilizing fibroblasts and macrophages from these mice, we demonstrate that RIPK1 kinase activity is required for necroptotic complex formation and death induction downstream of TNFR1 and TLRs 3 and 4. We show that RIPK1 kinase inactive mice are resistant to TNF-induced shock and exhibit impaired upregulation of TNF-induced cytokines and chemokines in vitro and in vivo. By using bone marrow reconstitution experiments, we demonstrate that RIPK1 kinase activity in a non-hematopoietic lineage drives TNF-induced lethality. We establish that RIPK1 kinase activity is required for TNF-induced increases in intestinal and vascular permeability and clotting, and implicate endothelial cell necroptosis as an underlying factor contributing to TNF/zVAD-induced shock. Thus, work in this thesis reveals that RIPK1 kinase inhibitors may have promise in treating shock and sepsis.

This thesis proposes a mechanism for the induction of peripheral tolerance to protein antigens. I have investigated the mechanism of tolerance induction to soluble protein antigens by targeting an antigen to small, resting B cells. For this purpose I have used a rabbit antibody directed at the IgD molecule found on the surface of most small, resting B cells but missing or lowered on activated B cells. Intravenous injection of normal mice with 100 μg of an ultracentrifuged Fab fragment of rabbit anti-mouse IgD (Fab anti-δ) makes these mice profoundly tolerant to challenge with nonimmune rabbit Fab (Fab NRG) fragments. This tolerance is antigen specific since treated mice make normal responses to an irrelevant antigen, chicken immunoglobulin (Ig). Fab fragments of rabbit Ig (rabbit Fab) not targeted to B cells do not induce tolerance as well as Fab anti-δ. Evidence suggests that the B cells must remain in a resting state for tolerance to be induced, since injection of F(ab)'2 anti-δ does not induce tolerance. Investigation of the mechanisms of the tolerance, by adoptive transfer, have shown that rabbit Fab specific B cell function has been impaired. The major effect however is in helper T cell function, as shown by adoptive transfer and lack of help for a hapten response. In vitro proliferation experiments show that the T cell response has not been shifted toward activation of different T cell subsets which do not help Ig production, nor is there any change in the Ig isotypes produced. Suppression does not appear to be the major cause of the helper T cell defect as shown by cell mixing experiments. This work shows that an antigen targeted to small B cells can induce tolerance to a soluble protein antigen, and suggests a role for small B cells in tolerance to self-proteins not presented in the thymus.

Members of the Argonaute family of proteins, which interact with small RNAs, are the key players of RNAi and other related pathways. The C. elegans genome encodes 27 members of the Argonaute family. During this thesis research, we sought to understand the functions of the members of this gene family in C. elegans. Among the Argonaute family members, rde-1 and alg-1/2have previously been shown to be essential for RNAi and development, respectively. In this work, we wanted to assign functions to the remaining members of this large family of proteins. Here, we describe the phenotype of 31 deletion alleles representing all of the previously uncharacterized Argonaute members. In addition to rde-1, our analysis revealed that two other Argonaute members csr-1 and prg-1 are also essential for development. csr-1 is partially required for RNAi, and essential for proper chromosome segregation. prg-1, a member of PIWI subfamily of Argonaute genes, exhibits reduced brood size and temperature-sensitive sterile phenotype, implicating that it is required for germline maintenance. Additionally, we showed that RDE-1 interacts with trigger-derived sense and antisense siRNAs (primary siRNAs) to initiate RNAi, while several other Argonaute proteins, SAGO-1, SAGO-2, and perhaps others, functioning redundantly, interact with amplified siRNAs (secondary siRNAs) to mediate downstream silencing. Moreover, our analysis uncovered that another member of Argonaute gene family, ergo-1, is essential for the endogenous RNAi pathway. Furthermore, we built an eight-fold Argonaute mutant, MAGO8, and analyzed its developmental phenotype and sensitivity to RNAi. Our analysis revealed that the genes deleted in the MAGO8 mutant function redundantly with each other, and are required for RNAi and the maintenance of the stem cell totipotency.

Les lésions d’athérosclérose sont une des causes majeurs du développement de pathologies cardiovasculaires. Cette pathologie chronique à l’origine inflammatoire est caractérisée par des mécanismes moléculaires et cellulaires complexes. L’activité de minéralisation retrouvée au sein des lésions est un critère clé de l’avancée de la maladie. A l’aide d’un modèle murin d’athérosclérose accélérée et de travaux d’optimisation technique, nous avons exploré la faisabilité de l’exploitation de l’imagerie par tomographie à émission de positons au fluorure de sodium associée à l’imagerie à résonance magnétique de la pathologie dans un modèle murin d’athérosclérose accélérée. Dans ce travail nous avons mis en évidence une activité de minéralisation précoce et soutenue associée à un statut inflammatoire plus avancé chez les animaux insuffisants rénaux. Ajouté à cela, nous avons mis en place un nouveau modèle murin de rétrécissement aortique calcifié par irradiation localisée. / Atherosclerosis lesions are a leading cause of cardiovascular events. Atherosclerosis is a chronic inflammatory disease including complex molecular and cellular mechanisms. Mineralization process within the atherosclerosis lesions is a key feature of the disease development. Using a mouse model of accelerated atherosclerosis and imaging optimisation study, we showed the feasability of sodium fluoride positron emission tomography combined to magnetic resonance imaging to assess molecular activity in a mouse model of accelerated atherosclerosis. We showed that uremic animals had an early and sustained mineralization activity associated to an advanced inflammatory state. Furthermore, we developped a new mouse model of calcified aortic stenosis using targeted radiation exposure.

Les équipementiers automobiles d’organes à hautes exigences sécuritaires travaillent sans cesse sur l’amélioration de la sûreté de fonctionnement de leurs systèmes et préparent leur insertion dans l’air du véhicule autonome. Dans ce cadre, nous avons travaillé sur la conception et le développement d’un capteur de force pour la direction à assistance électrique (DAE) avec le défi de proposer une solution sans fil, facile à fabriquer et à intégrer au système. Dans cette thèse, des travaux de modélisation et d’expérimentation ont porté principalement sur deux aspects : le capteur de force et son alimentation sans fil. Pour la mesure de force, une solution basée sur l'utilisation d'un matériau piézoélectrique a été proposée. L’utilisation d’un tel matériau pour la mesure de la composante dynamique de la force est largement répandu, cependant la mesure statique reste extrêmement réduite aux applications MEMS (mesure de pression). La technique repose sur l’onde acoustique de volume (Bulk Acoustic Wave). Un échantillon piézoélectrique inséré dans une structure, soumis à une force voit sa fréquence de résonance varier. Des travaux de modélisation analytique, éléments finis et multi-échelle ainsi que de l’expérimentation ont permis de comprendre les phénomènes physiques mis en jeux dans ce type de transducteur et de proposer des orientations pour la conception du transducteur de force optimal. Un démonstrateur a été mis en place permettant la mesure d’une force statique maximale de 1500 N. L'alimentation sans fil du capteur est assurée par la technique du couplage magnétique résonant. Vu le caractère conducteur et ferromagnétique de l’environnement du système de direction, une approche de modélisation basée sur la méthode des éléments finis et la méthode des constantes localisées a été mise en place afin d’étudier le comportement d’une telle technique dans cet environnement. Par la suite, une conception a été proposée et un prototype a été réalisé. Des mesures expérimentales ont montré que la conception répond au cahier des charges imposé par l’entreprise. / Original equipment manufacturer for automotive components with high safety requirements are continually working to improve the system safety and prepare their integration to the driverless car. Within this context, we worked on the design and development of a force sensor for the electric power steering (EPS) system with the challenge of providing a wireless solution, easy to manufacture and to integrate to the system. In this thesis, modeling and experimental activities have focused mainly on two aspects: the force sensor and its wireless power supply system. For force measurement, a solution based on piezoelectric material was proposed. The use of such material to measure the dynamic component of the force is widespread; however, static force measurement remains extremely limited to MEMS applications (pressure measurement). The technic utilizes the bulk acoustic wave (BAW). The resonance frequency of a piezoelectric specimen positioned within a mechanical structure varies with an externally applied force. Analytic modeling activities, finite element method based and multi-scale approach with experimentation activities allow the understanding of the physical mechanisms behind the observed behavior of the transducer and to propose guidance for optimal design of the force transducer. A demonstrator was set up and showed a static force measurement capability up to 1500N.The wireless power supply is achieved by the resonant magnetic coupling technique. In order to analyze the effect of the environment of the electric power steering system characterized by conductive and ferromagnetic parts, a modeling approach based on the finite element method and the lumped-element method was adopted. Afterwards, a design was proposed and a prototype was carried out. The experimental measurement shows that the design meets the company requirements.

Comment le visage est-il devenu un organe, objet de don et de transplantation ? En partant de ce questionnement, cette thèse investit le milieu de celles et ceux qui ont porté et débattu des projets de transplantation faciale au cours des années 2000 et 2010 en France et au Royaume-Uni. Elle éclaire les conditions sociales selon lesquelles la transplantation faciale a été rendue acceptable, pour les patients opérés et les équipes chirurgicales, les coordinateurs du don d’organes et les proches des donneurs défunts qui permettent le prélèvement. L’enquête a impliqué un investissement approfondi de l’ensemble de la chaîne de la transplantation,reposant sur la collecte d’archives (scientifiques, institutionnelles, médiatiques), sur la réalisation d’entretiens (avec les chirurgiens, les patients, les acteurs du don d’organes et de la régulation médicale, les membres d’associations de personnes défigurées), ainsi que sur une ethnographie des services hospitaliers qui réalisent ces opérations (du bloc jusqu’aux réunions de service). En suivant au plus près ces acteurs, l’enquête éclaire les tensions quel’expérimentation révèle sur son passage.Cette recherche aborde la greffe comme un objet qui articule des questionnements au croisement des institutions, des mouvements associatifs et des expériences du don. La greffe du visage bouscule, tout d’abord, les prétentions des chirurgiens à s’autoréguler. La confrontation des équipes chirurgicales aux institutions sanitaires et éthiques, qui évaluent l’opportunité de cette expérimentation, révèle des rapports distincts à l’objectivité médicale e tà l’encadrement des pratiques hospitalières. L’émergence de la greffe du visage travaille,ensuite, les collectifs de personnes défigurées qui oscillent entre soutien au progrès médical et dénonciation de la chirurgie comme oppression. Les réactions des associations françaises et anglaises sont révélatrices de conceptions distinctes de la défiguration, et contribuent à façonner la trajectoire de la greffe du visage. La greffe du visage interroge, enfin, les conditions sociales de disponibilité des corps des défunts et les tensions à l’oeuvre dans la réception d’un don anonyme d’organes. Les patients greffés au visage sont soumis à une double contrainte qui peut-être vécue comme contradictoire : d’un côté, celle de remercier le donneur, de l’autre, celle de l’oublier pour accepter la greffe. La thèse révèle ainsi l’assemblage hétérogène, mais néanmoins cohérent, de ces niveaux d’analyse, qui est en jeu dans chaque déplacement d’une partie de corps d’une personne à une autre. Elle éclaire, en d’autres termes, ce que charrie la chair. / How has the face become an organ, object of donation and transplantation? Starting from thisquestioning, this thesis invests the environment of those who have carried facial transplantprojects, and those who have debated about them, during the years 2000 and 2010 in Franceand the United Kingdom. It illuminates the social conditions according to which facialtransplantation has been made acceptable, for transplanted patients and surgical teams, organdonation coordinators and relatives of deceased donors who allow the retrieval. The enquiryinvolved an in-depth investment of the whole chain of transplantation, based on the collectionof archives (scientific, institutional, media), on conducting interviews (with surgeons, patients,organ donation and medical regulation’s actors, members of associations of disfigured people),as well as doing an ethnography of hospital services that carry out these operations (from theoperating rooms to the service meetings). By closely following these actors, the surveyilluminates the tensions that experimentation reveals in its passage.This research addresses face transplant as an object that articulates questions at the crossroadsof institutions, social movements and experiences of donation. Face transplant upsets, first ofall, the claims of the surgeons to self-regulate. The confrontation of surgical teams with healthand ethical institutions, which evaluate the appropriateness of this experiment, reveals distinctrelationships to medical objectivity and to the supervision of hospital practices. The emergenceof face transplant, then, poses a challenge to the collectives of disfigured people who oscillatebetween support for medical progress and denunciation of surgery as oppression. The reactionsof the French and English associations are indicative of distinct conceptions of disfigurement,and help to shape the trajectory of face transplant. Lastly, face transplant questions the socialconditions of the dead bodies' availability and the tensions at work in the reception of ananonymous donation of organs. Transplanted patients are subject to a double constraint that canbe experienced as contradictory: on the one hand, that of thanking the donor, on the other, thatof forgetting the donor in order to accept the transplant. The thesis thus reveals theheterogeneous – and at the same time coherent – assembly of these levels of analysis, which isat stake every time a body part is transferred from one person to another. It illuminates, in otherwords, what the flesh carries.

Animals as Laboratory Objects: Analysis of the Power Discourse PhDr. Tereza Vandrovcová Abstract This dissertation thesis encompasses a critical discourse analysis of the power correlates of expert knowledge and other factors that can hinder the open and unbiased discussion concerning the ethical aspects of the use of nonhuman animals in biomedical experiments. A brief history of "the animal" is first provided before the issue is positioned within the theoretical framework of Animal Studies. The fourth chapter is composed of an overview of the most frequent arguments both for and against the use of animals in biomedicine. The author draws upon her research as she analyzes scientific texts to reveal how laboratory animals are socially constructed as scientific objects and subsequently describes the effects this has on the perception of their moral value. A series of semi-structured interviews with critics and advocates of animal experimentation, such as animal rights activists and laboratory workers who conduct experiments on animals, is the pivotal section of the paper. It is established that lab workers in the sample are convinced of the necessity and legitimacy of current practices, that lab workers have a tendency to suppress animals' individuality when describing their work, that lab workers deem their...