Submitted by Chaylane Marques (chaylane.marques@ufpe.br) on 2015-03-05T16:27:52Z No. of bitstreams: 2 Dissertacão Caroline .pdf: 2146574 bytes, checksum: 0265be74158f795b1dde4ffcf9abd31b (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) / Made available in DSpace on 2015-03-05T16:27:52Z (GMT). No. of bitstreams: 2 Dissertacão Caroline .pdf: 2146574 bytes, checksum: 0265be74158f795b1dde4ffcf9abd31b (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Previous issue date: 2006-05-16 / Um centro dentro de uma rede descentralizada. A estrutura do site Centro de Mídia Independente brasileiro revela o quão paradoxal pode ser o fenômeno de novos movimentos sociais que surgiram nos anos 90, quando houve um acesso em massa à internet no mundo. Esta pesquisa estuda precisamente a manifestação de um grupo cujo caráter transnacional faz de sua prática uma constante revisão de paradoxos sobre conceitos de Novos Movimentos Sociais, comunidade e mídia radical. É pela interseção das teorias a respeito desses três eixos que esta pesquisa é realizada, na proposta de identificar até que ponto um grupo que se proclama mídia pode ser, ao mesmo tempo, uma mediação, uma ação direta e uma comunidade com características próprias.

In this project cyclisation chemistry using palladium and radical methodologies has been developed. The aim was to compare palladium and radical mediated cyclisations. Initially small molecules containing amine and amide functional groups were synthesised to screen the methodology. Later the design of these molecules was changed to be based on the imidoyl functional group. A series of N-benzyl protected aliphatic amine and amides were synthesised in the hope (with the aim of cyclisation) that they could be cyclised using both palladium and radical conditions. When these examples failed, which was attributed to the strain of the cyclic molecules, alternative precursors were sought. Initially, the N-protecting group was changed to a tosyl-group. However, when this had no positive effect, the size of the precursor molecules were examined. Two alternative amine precursors were designed which would remove the strain element in the cyclised molecules. The lengthy synthesis of these two molecules was not favourable for the development of methodology. Although it appeared that the cyclisations were now occurring it did not prove favourable to carry on down this path. The final part of this research project utilises imines and imidoyl selenides as radical and palladium cyclisation precursors respectively. A series of aromatic imines and imidoyl selenides were synthesised. The irnines were synthesised from amino-biphenyl and a range of p-substituted benza1dehydes. The corresponding imidoyl selenides were synthesised from amino-biphenyl and a range of p-substituted benzoyl chlorides to give the amides which in tum were converted to the target molecules via the imidoyl chlorides. The successful cyclisations using both methodologies resulted in a series of phenanthridines. This success of these cyclisations led to further precursors being developed which included bisphenanthridine, alkyne, alkyl and heteroaromatic precursors. However, most of the cyclisations of these molecules proved problematic and require further development of methodology.

Lipid peroxidation is well established to contribute to the etiology of many deteriorative conditions including neurodegeneration, cardiovascular disease, cancer, aging, and recently in ferroptosis—a regulated, necrotic modality of cell death that results from the accumulation of lipid hydroperoxides. Recent high-throughput screening efforts have uncovered ferrostatin-1 (Fer-1) and liproxstatin-1 (Lip-1) as two premiere inhibitors of ferroptosis. We propose that these compounds function as radical trapping antioxidants. We employ a systematic methodology of evaluating inherent radical trapping antioxidant (RTA) activity of Lip-1, Fer-1, and various aryl amine and aryl nitroxide analogues to put forward a biologically relevant mechanism of action based on our previous work in the field. Joining these observations with the efficacy of tetrahydronaphthyridinols (THNs), the results support a clear role of autoxidation in the execution of ferroptosis. Next, we expand the THN repertoire by targeting the payload towards the engine of our cells, the mitochondria. Decades of research have implicated mitochondrial dysfunction brought about by the peroxidation of mitochondrial membranes and the leaking of downstream oxidants, in the death of their symbiotic host cells. Isolated successes in the field have been demonstrated academically, though viable drugs remain to be developed, partially due to the lack of effective diagnostic tools. We endeavor to address some of these issues by investigating mitochondrially-targeted THNs (MitoTHNs) as a targeted chain-breaking antioxidant of unparalleled potency. Furthermore, we advance development of the THNs towards therapeutic applications by demonstrating their biodistribution in mice.

La silylmétallation d'alcynes représente une méthode très répandue pour la préparation de vinylsilanes, et offre de façon plus générale la possibilité d'accéder à des alcènes substitués de façon stéréosélective. Diverses méthodologies de silylmétallation permettant d'obtenir un excellent contrôle de la régiosélectivité ont été décrites. En revanche, il est difficile de jouer sur la stéréosélectivité dans la mesure où la plupart des processus rapportés opèrent selon une addition syn, et conduisent donc à des alcènes silylmétallés de configuration cis. Ainsi, le travail décrit dans ce manuscrit de thèse rapporte une nouvelle approche complémentaire permettant d'effectuer des silylzincations anti sur des alcynes, ayant lieu selon un processus radicalaire de transfert d'atome de zinc. Pour ce faire, deux méthodes ont été développées.Dans un premier temps, une méthode impliquant la combinaison du silane (Me3Si)3SiH et de Et2Zn a été mise au point et a permis d'effectuer des silylzincations sur des ynamides de façon parfaitement régio- et stéréosélective. Dans un deuxième temps, une autre méthode impliquant le complexe [(Me3Si)3Si]2Zn comme source de radicaux silylés a été développée. Cette méthode a permis d'effectuer des silylzincations sur des ynamides, et de façon plus générale sur des alcynes hétéro-substitués, ainsi que sur des arylacétylènes. / Silylmetalation of alkynes is a widespread method for the preparation of vinylic silanes, and more generally offers the possibility to access stereoselectively substituted alkenes. Existing methods for silylmetalation offer a range of options to control the sense of regiochemistry. By contrast, tuning of stereochemistry is rarely feasible, because these are usually syn-addition processes and, hence, provide access to cis-silylmetalated alkenes. As a complementary anti-selective approach, the work described in this thesis is devoted to a new possible entry to silylzincation based on a radical zinc-atom transfer process. In this context, two different methods have been considered.In a first step, a method using a combination of (Me3Si)3SiH and Et2Zn has been developed and allowed to achieve the complete regio- and stereoselective silylzincation of ynamides. In a second step, a method using the reagent [(Me3Si)3Si]2Zn as organosilyl radical source has been developed. This method allows to achieve the silylzincation of ynamides, and more generally of hetero-substituted alkynes, as well as aryl- and heteroaryl-substituted alkynes.

Piezotech, une start-up rachetée en 2010 par le leader français de la chimie, Arkema, développe et commercialise des copolymères fluorés électroactifs (EAPs). Ces copolymères présentent un grand intérêt pour des applications dans l’électronique imprimée, les capteurs, les actionneurs, les muscles artificiels, et le stockage de l’énergie. Les copolymères à base de fluorure de vinylidène (VDF) et de trifluoroéthylène (TrFE) possèdent les meilleures propriétés piézoélectriques et ferroélectriques (FE) parmi les polymères existants. L’introduction d’un termonomère, tel que le 1,1-chlorotrifluoroéthylène (CFE) ou le chlorotrifluoroéthylène (CTFE), modifie la conformation de la chaine polymère et change le comportement du matériau en relaxeur ferroélectrique (RFE). Le travail de thèse s’inscrit dans la recherche de nouveaux EAPs fluorés et la compréhension des relations structure-propriétés de ces matériaux. Après l’étude de la cinétique de copolymérisation avec le VDF et le TrFE de différents termonomères porteurs de groupements CF3, les terpolymérisations ont été examinées. Dans une première partie, le trans-1,3,3,3-tetrafluoropropène (1234ze), un termonomer qui n’homopolymérise pas, a été étudié. Des terpolymères de composition homogène ont été synthétisés. Ensuite, le 3,3,3-trifluoropropène (TFP) et le 2,3,3,3-tetrafluoropropène (1234yf) ont été terpolymérisés avec le VDF et le TrFE. Bien que les terpolymérisations batch amènent à une forte dérive de composition, un procédé de polymérisation en suspension en semi-continu a permis d’obtenir une meilleure homogénéité. Les propriétés thermiques et électroactives de tous les terpolymères ont été caractérisées. Dans une dernière partie, l’introduction d'une faible quantité d’un monomère fonctionnel (2-(trifluorométhyl) acide acrylique, MAF), dans les chaines du copolymère poly(VDF-co-TrFE), a permis une amélioration des propriétés d’adhésion sur le verre et le métal sans altérer les propriétés électroactives. L’étude des terpolymérisations avec le VDF, le TrFE et un termonomère porteur d’un groupement CF3 a contribué l’amélioration de la compréhension des relations structure-propriété dans les EAPs fluorés. En particulier, il a été montré que la réduction de la taille des cristaux n’est pas une condition suffisante pour obtenir un caractère RFE. / Piezotech, a start-up acquired in 2010 by the French leader in Chemistry, Arkema, develops and commercializes fluorinated electroactive copolymers (EAPs). These copolymers arouse a significant interest in printed electronics, printed memories, sensors, actuators, artificial muscles, and energy storage devices. Vinylidene fluoride (VDF) and trifluoroethylene (TrFE) -based copolymers are the polymers exhibiting the highest piezoelectric and ferroelectric (FE) properties. The introduction of a third slightly bulkier termonomer such as 1,1-chlorofluoroethylene (CFE) or chlorotrifluoroethylene (CTFE) was shown to modify the polymer chain conformation and change their electroactive behaviors into those of relaxor ferroelectric (RFE) materials. This PhD work aimed to discover new fluorinated EAPs and to better understand their structure-properties relationships. After the study of the kinetics of copolymerization of various CF3-bearing termonomers with VDF and TrFE; the terpolymerizations were investigated. First trans-1,3,3,3-tetrafluoropropene (1234ze), a non-homopolymerizable termonomer, was studied. Terpolymers with homogeneous compositions were synthesized. Then, 3,3,3-trifluoropropene (TFP) and 2,3,3,3-tetrafluoropropene (1234yf) were terpolymerized with VDF and TrFE. Although batch terpolymerizations resulted in terpolymers with strong compositional drift, the semi-continuous suspension process afforded better homogeneity. The thermal and electroactive properties of all the terpolymers were characterized. Finally, the introduction into poly(VDF-co-TrFE) copolymer chains of small amounts of a functional monomer (2-(trifluoromethyl)acrylic acid, MAF) allowed an increase of the adhesion properties onto glass and metal substrates without altering the electroactive properties. The study of the terpolymerizations of VDF, TrFE and a CF3-bearing termonomer contributed to a better understanding of the structure-properties relationships in fluorinated EAPs. Notably, the reduction of the crystal size was shown to be insufficient to afford RFE properties.

The aim of this dissertation is to reconstruct the concept of radical evil (das radikale Böse) treated by Kant in his writing On the radical evil in human nature (Über das radicale Böse in der menschlichen Natur), which was published in 1792. Starting from the data provided by this text, the terms in which Kant discusses both the problem of moral evil in the proper sense (conceived as radical), and the possibility of a human progress with regard to morality, are explicated. In that thematic, Kant introduces some concepts which pertain exclusively to the question of evil, among them, the concept on intention (Gesinnung), the concepts of inclination towards the evil (Hang zum Bösen) and of disposition to the good (Anlage zum Guten), also the ideas of revolution and gradual reform (as means to realize moral progress), and finally a new definition of nature. Even if it uses its proper terms, the writing on the evil keeps many basic concepts which Kant had introduced in earlier writings. For this reason, the dissertation does not limitate itself to the writing On the radical evil, but also treats of other kantian works, which serves two purposes: first, an explicative one, clarifying questions already well established in kantian philosophy; and secondly, a comparative one, both in relation with terms which receive a different meaning, and with regard to changes of the claims made, which reflect the new context and follow a different configuration. This is the horizon which the present dissertation is itended to reconstruct and within which it locates itself. Regarding the question of the evil (and its qualification as radical), various other questions are discussed in a specific manner, for instance, the origin of evil, the responsibility of man for its existence, the notions of virtue (both in the moral and in the legal sphere), the concept of evil action, the idea of moral education, and finally, the function of religion as supporting and stabilizing good moral conduct. These questions were harmonized as far as possible, and reconstructed from the point of view which caracterizes kantian philosophy: the critical-systematic point of view. / A presente Dissertação é uma reconstrução do conceito de mal radical (Radicale Böse) tratado por Kant em seu artigo Sobre o mal radical na natureza humana (Über das radicale Böse in der menschlichen Natur), publicado em 1792. A partir dos dados desse texto o que se fez foi explicitar em que termos Kant aborda tanto a questão do mal moral propriamente dito (concebido posteriormente como radical), como também a da possibilidade de um progresso humano no que tange à moralidade. Nessa tratativa, Kant introduz algumas noções que são exclusivas à problemática do mal, entre elas, o conceito de intenção (Gesinnung), as noções de propensão para o mal (Hang zum Bösen) e de disposição para o bem (Anlage zum Guten), também as idéias de revolução e de reforma gradual (como meios de se alcançar o progresso moral), e, enfim, uma nova definição de natureza. Embora se sirva de termos exclusivos, o artigo sobre o mal mantém muitas das noções básicas desenvolvidas por Kant em obras anteriores. Daí porque a Dissertação não se restringe ao artigo Sobre o mal radical, mas se estende por outras obras em busca de recorrências feitas com dois objetivos bem precisos: um, elucidativo, em que se apresenta questões já plenamente consolidadas na filosofia kantiana; outro, comparativo, seja em relação a termos que adquiriram um sentido distinto, seja em vista de alterações propositivas, repensadas diante de um novo contexto e submetidas a uma nova configuração. Esse é o horizonte que esta Dissertação busca reconstruir e dentro do qual se insere. Relativo à questão do mal (e de seu qualificativo de radical), várias outras questões são tratadas de modo específico, por exemplo, a origem do mal, a imputabilidade do homem pela sua existência, as noções de virtude (concebidas tanto no domínio moral quanto no campo legal), o conceito de ação viciosa, a idéia de uma educação moral e, além dela, a função da religião como fomentadora e mantenedora de uma boa conduta moral. Essas questões, na medida do possível, foram harmonizadas entre si e reconstruídas pelo ponto de vista próprio da filosofia de Kant: o crítico-sistemático.

Based on eighteen months of fieldwork amongst anarchist and anti-authoritarian groups in Athens this thesis focuses on the December 2008 Greek revolt. It is an ethnographic exploration of collective self-organised practices in the public spaces of Athens and the occupied buildings of that period. It posits that these sets of processes were developed in the revolt as politics of subversion of the everyday life which in the thesis is considered both the site of alienation and emancipation. Based on Bourdieu, this study suggests that the everyday practices of subversion in radical politics are habitual dispositions of action that have been developed, based on past events which go as far back as the Greek civil war (1946-49), to establish a political living in the present, a process that is explored based on what Friedman calls ‘mythologisation' . Drawing on De Certeau, Lefebvre and Vaneigem it is argued that these collective dispositions are the productive factors of tactics of the subversion which emerge in the context of everyday situations defined by the particularities of public space, imagination and public memory.This suggests that the revolt was not an organised process to create a counter-hegemony but rather, a multitude of micro-processes which used everyday situations as sites of subversion. This argument is explored based on the notion of the social imaginary as defined by Taylor and Castoriadis. In this thesis imagination is considered to be constitutive of the politics of subversion. Fuelled by past events and habitual dispositions of actions radical political practices in the revolt were formative of an ontological process which imagines and explains the political as personal and the private as public. According to that interpretation the event of the death of Alexandros Grigoropoulos generated sites where official power could be challenged, escaped and confronted by tactics of subversion.

No description available.

This dissertation is an attempt to use the radical political economy approach, which assumes that there is a connection between a state’s strategic interests and the interests of dominant multinational corporations (MNCs) located within a state’s territory, to explain continuity in the USAID development agenda and lending patterns during the past 30 years of development aid to Haiti. Employing the qualitative method of "process-tracing," my study concludes that the radical political economy approach has an explanatory power when it comes to understanding continuity in the USAID development agenda and lending patterns during the past 30 years of development aid to Haiti. The evidence shows that USAID has implemented in Haiti, from the 1980s through the post-9/11 Washington Consensus period, neoliberal policies that conform to the political economy of US multinational corporations (US MNCs). Contrary to the claim that the USAID-sponsored post-earthquake development paradigm has departed from previous development strategies, the study has shown that USAID has used the occurrence of the January 2010 earthquake tragedy to accelerate in Haiti the implementation of a neoliberal agenda congenial to the business promotion of multinational investors, particularly US multinational corporations. In terms of the way ahead, the study argues for the implementation of a new development approach articulated by a legitimate Haitian state and primarily intended to promote the socioeconomic development of the poorest Haitians.

An improved second generation approach to pestalotiopsin A and 6-epitaedolidol has been developed. A silicon group bonded directly to carbon has been used as a stereocontrol element in cyclisation substrates for a SmI2 – mediated 4-exo-trig radical cyclisation. The silicon groups acts as a steric block to set up three new stereocentres in high to complete diastereocontrol. Several approaches to the cyclisation substrates are outlined, including a silyl transfer/aldol cascade and a novel C2-symmetric N-heterocyclic carbene – copper catalyst to asymmetrically install a C-Si bond. The silicon group is a versatile handle for further manipulation and has been oxidised using Fleming oxidation conditions to install the hydroxyl functionality required in the target compounds. The silicon group also simplifies the alcohol protecting group strategy in the approach to pestalotiopsin A and 6‐epitaedolidol. The first application of N-heterocyclic carbene – copper catalysed silyl transfer in natural product synthesis and the first use of a SmI2 – mediated cyclisation directed by a C-Si stereocontrol element are described.