This thesis describes the synthesis and characterisation of new examples of meso-n1-organometallic porphyrins. These porphyrins were originally encountered as catalytic intermediates in the C-C bond forming reaction on the porphyrin periphery using palladium catalysts. They have now become a research topic in their own right and no other examples of this type of organometallic porphyrins had been reported at the outset of this work. In Chapter 2, several examples of meso-palladioporphyrins were prepared in high yield using oxidative addition of the porphyrin-bromine bond to a suitable Pd(0)phosphine precursor. These phosphine precursors were prepared from Pd(PPh3)4 or Pd2dba3 plus either PPh3 or a chelating diphosphine. Several new examples of mono- and di palladium complexes of chelating diphosphines were prepared. Chapter 3 looks at the preparation of meso-platinioporpyrins and the insertion of various central metal ions into the porphyrin ligand. Pairs of cis- and transisomers of the Pt(II) complexes were isolated from the oxidative addition of Pt(PPh3)3 to the free base and Ni(II) bromoporphyrins. The cis-isomer converted to the trans upon heating. At room temperature the two isomers are geometrically stable and survive unchanged through column chromatography and slow recrystallisation. The central metal ion can be introduced either before or after the oxidative addition to Pt(0). However, it is preferable to insert the metal ion last as the complexes of Br(MDPP) are rather insoluble (especially that of MnCl) and are more difficult to handle than the common intermediate trans- [PtBr(H2DPP)(PPh3)2]. The oxidative addition of Pt(dba)2 to meso-bromo-DPP in the presence of PPh3 has also been shown to be an effective method of synthesising n1-organo platinum porphyrins in high yield. However, this method was unsuccessful when using chelating diphosphines. In Chapter 4, the physical properties of meso- metalloporphyrins are reported including electrochemistry, fluorescence spectroscopy and crystal structure determinations. The fluorescence intensities of the meso-substituted porphyrins (freebase and zinc complexes) are dramatically reduced in comparison with the unsubstituted porphyrins. This fluorescence quenching is a dramatic example of the "heavy atom effect". Electrochemical measurements of freebase and Ni(II)porphyrins indicate that the organometallic fragment is a strong electron donor. The visible absorption spectra for all Pd(II) and Pt(II) complexes are typical for diarylporphyrins. All groups other than H in the 5- or 5- and 15-positions cause a red shift of the major absorption bands for both the free bases and central-metal complexes. The crystal structure studies of the Pt(II) complexes include the complexes, cis- [PtBr(MDPP)(PPh3)2] (M = H2, Ni), trans-[PtBr(MDPP)(PPh3)2] (M = H2, Ni, Zn and Co), trans-[PtCl(H2DPP)(PPh3)2] and trans-[PtBr(NiDPPBr)(PPh3)2]. In all these structures, the free bases are virtually planar while the metallo derivatives adopt a hybrid of the ruffled and saddled conformations. Chapter 5 contains the initial studies of chiral palladioporphyrins, using three different types of chiral chelating diphosphine ligands. These chiral palladioporphyrins are readily prepared by oxidative addition of the Pd(0) precursor with bromoporphyrin. The asymmetry of the chiral ligand is detectable at the remote B-pyrrole protons in all the chiral complexes as eight doublets are observed in 1H NMR spectra. The chirality of these ligands in the porphyrin complexes induces circular dichroism in the region of the porphyrin electronic absorption. High optical activity is observed for the BINAP complexes.

[Abstract]: China’s enormous size and stature as a new hub of economic growth in tandem with its military modernisation make China a rising power. The strategic consequences of China’s economic growth synergised with its military muscles are multiple and profound, especially, for the neighbours in its conflict-prone periphery. The aim of this dissertation is not only to assess the importance and complexities of conflicts in the periphery of China, but also about the necessity for the neighbours to coexist with a more powerful China. At the same time, in the Chinese geopolitical context, domestic stability and hence, the CCP’s legitimacy has been perpetually paramount, and external threats or conflicts are usually perceived in the context of aggravating domestic and international stability, thereby hampering its strategic aim of achieving global economic command and power-projection military capability.With the dawn of 21st century, China is grooving to an exuberant global beat, the intensity of conflicts along China’s periphery has dimmed to such an extent that its political, economic, and social order will probably not disintegrate into chaos in the near future. Instead, China’s rapidly growing economic capacity and its soaring prestige in faraway capitals like Washington and Paris has meant an expansion of Chinese “soft power”, i.e., an assertive China with an ability to get what it wants by attracting and persuading others to adopt its goals, instead of blunt economic and military coercion. And, China could reasonably be expected to manage most, if not all, the conflicts in its periphery to its own advantage. These include: efforts to augment its military capabilities in a manner commensurate with its increased economic muscle and acquire new allies and underwrite the protection of others in its periphery. It is unlikely that the PRC will actually acquire new or reclaim old territory for China’s resources or for symbolic reasons by penalizing, if necessary, any opponents or bystanders who resist such claims. While it may wish to redress past wrongs it believes to have suffered; or attempt to rewrite the prevailing international “rules of game” to better reflect its own geostrategic interests; or in the most extreme policy choice, perhaps even ready itself for preventive war or to launch predatory attacks on its foes on the pretext of the “cult of defence,” – all of which have been seen as the bedrock of the contemporary China’s strategic culture, however, it is iiprobable that China will not pursue these at the cost of its future economic and/or social security agenda.

This dissertation uses mixed methods to examine the role of the coal industry in the reproduction of Central Appalachia as an internal periphery within the United States and the economic, ecological, and human inequalities this entails. It also analyzes the related political economy and power structure of coal in a national context. Particularly important for analysis of the region's underdevelopment are the class relations involved in unequal ecological exchange and the establishment of successive "modes of extraction." I employ a historical comparative analysis of Appalachia to evaluate Bunker's thesis that resource dependent peripheries often become locked into a "mode of extraction" (with aspects parallel to Marxist concepts of mode of production) triggering economic and ecological path dependencies leading to underdevelopment. This historical comparative analysis establishes the background for a closer examination of the political economy of the modern US coal industry. After sketching the changes in the structure of monopoly and competition in the coal industry I employ network analysis of the directorate interlocks of the top twenty coal firms in the US within the larger energy policy-planning network to examine their connections with key institutions of the policy formation network of think tanks and business groups. My findings show the importance of the capacities of fossil fuel fractions of the capitalist class in formulating energy policy around issues such as the 2009 climate legislation. As a contribution to the growing literature applying the concept of metabolism as link between contemporary and classical theory, I examine the conflict at Coal River Mountain from the vantage points of ecology, political economy, and human development in dialectical rotation. Utilizing Marx's method of successive abstractions, the mountain is presented as a nexus of metabolic rifts in the human relationship to the earth's natural systems and an impediment to genuine human development. Finally, I conclude with some implications of this analysis for building a critical environmental sociology of extractive economies. This dissertation includes previously published materials. / 2016-09-29

No presente trabalho, o objeto de análise é a Literatura Marginal produzida por Ferréz e seus pontos de contato com um deslocamento do lugar da periferia. Partindo dessa ideia, esta pesquisa pensa Ferréz, em alguns momentos, e dialoga com outros escritores da periferia e suas preferências temáticas. Falando da periferia como tema do escritor da nova geração da Literatura Marginal e como possibilidade de que essa Literatura despontasse, esta pesquisa tem início com a discussão do conceito de periferia e, em seguida, coloca em perspectiva e realiza um sobrevoo entre os diferentes sentidos do termo marginalidade no contexto da Literatura e nas artes de uma maneira ampla. A partir das referidas observações, são discutidas as primeiras expressões de marginalidade na literatura, especialmente aqui no Brasil e verificadas quando se começou, de fato, a aplicar essa expressão marginal na Literatura. Assim, são apresentadas as três principais conotações de marginalidade: (i) aquela que se refere à cultura marginal das décadas de 1960 e 1970; (ii) aquela que diz respeito à poesia marginal do mesmo período; e (iii) a que se relaciona aos escritores que trazem a periferia como tema ou, ainda, aqueles que são oriundos dela. Em seguida, são apresentados os traços da marginalidade literária da nova geração e algumas ações político-culturais de alguns escritores. Nesse momento, há um aprofundamento no objetivo desta pesquisa, que é discutir as mutações na Literatura Marginal e no discurso de Férrez dentro de uma nova concepção de marginalidade literária, inseparável de novos sentidos e contextos da ideia de periferia.

No presente trabalho, o objeto de análise é a Literatura Marginal produzida por Ferréz e seus pontos de contato com um deslocamento do lugar da periferia. Partindo dessa ideia, esta pesquisa pensa Ferréz, em alguns momentos, e dialoga com outros escritores da periferia e suas preferências temáticas. Falando da periferia como tema do escritor da nova geração da Literatura Marginal e como possibilidade de que essa Literatura despontasse, esta pesquisa tem início com a discussão do conceito de periferia e, em seguida, coloca em perspectiva e realiza um sobrevoo entre os diferentes sentidos do termo marginalidade no contexto da Literatura e nas artes de uma maneira ampla. A partir das referidas observações, são discutidas as primeiras expressões de marginalidade na literatura, especialmente aqui no Brasil e verificadas quando se começou, de fato, a aplicar essa expressão marginal na Literatura. Assim, são apresentadas as três principais conotações de marginalidade: (i) aquela que se refere à cultura marginal das décadas de 1960 e 1970; (ii) aquela que diz respeito à poesia marginal do mesmo período; e (iii) a que se relaciona aos escritores que trazem a periferia como tema ou, ainda, aqueles que são oriundos dela. Em seguida, são apresentados os traços da marginalidade literária da nova geração e algumas ações político-culturais de alguns escritores. Nesse momento, há um aprofundamento no objetivo desta pesquisa, que é discutir as mutações na Literatura Marginal e no discurso de Férrez dentro de uma nova concepção de marginalidade literária, inseparável de novos sentidos e contextos da ideia de periferia.

abstract: Despite the vast research on language carried out by the generative linguistics of Noam Chomsky and his followers since the 1950s, for theoretical reasons (mainly their attention to the mental abstraction of language structure rather than language as a performed product), historical linguistics from the start lay outside their research interest. This study is an attempt to bridge the gap between the formalism and theoretical constructs introduced by generative grammar, whose ultimate goal is to provide not only a description but also an explanation to linguistic phenomena, and historical linguistics, which studies the evolution of language over time. This main objective is met by providing a formal account of the changes hwæðer undergoes throughout the Old English (OE) period. This seemingly inconspicuous word presents itself as a case of particular investigative interest in that it reflects the different stages proclaimed by the theoretical assumptions implemented in the study, namely the economy principles responsible for what has become known as the CP cycle: the Head Preference Principle and the Late Merge Principle, whereby pronominal hwæðer would raise to the specifier position for topicalization purposes, then after frequent use in that position, it would be base-generated there under Late Merge, until later reanalysis as the head of the Complementizer Phrase (CP) under Head Preference. Thus, I set out to classify the diverse functions of OE hwæðer by identifying and analyzing all instances as recorded in the diachronic part of the Helsinki Corpus. Both quantitative and qualitative analyses of the data have rendered the following results: 1) a fully satisfactory functional and chronological classification has been obtained by analyzing the data under investigation following a formal theoretical approach; and 2) a step-by-step historical analysis proves to be indispensable for understanding how language works at the abstract level from a historical point of view. This project is part of a growing body of research on language change which attempts to describe and explain the evolution of certain words as these change in form and function. / Dissertation/Thesis / Ph.D. English 2013

A presente dissertação verifica a abordagem dos espaços periféricos a partir da análise poética da canção Subúrbio, de Chico Buarque (Carioca, 2006), com o fito de analisar o lugar de enunciação do sujeito poético. Nossa hipótese é a de que na canção um enunciador cujo olhar se distancia dos objetos que tematiza e que esta abordagem é um aspecto que prevalece em boa parte da obra cancional do referido poeta. / The current dissertation aims to verify the approach of the outlying areas through the analysis of the poetic song Subúrbio, by Chico Buarque (Carioca, 2006), in order to analyze the poetic subjects enunciative place. Our hypothesis is that in the song there is an enunciator whose look distances itself from the themed matters and this approach is an aspect that prevails in almost of the reffered poet`s songbook

A arte é resultado do desenvolvimento histórico-social e sempre esteve ligada às transformações sociais de modo geral. Compreender esse processo de formação e seus desdobramentos é de fundamental importância para entender como e quais os caminhos a arte dramática tem trilhado em cada tempo histórico. E mais, como essas mudanças tem, de certa forma, impulsionado novas formas de expressão em um contexto internacional marcado pelo aprofundamento das políticas neoliberais, os avanços da chamada globalização e a consecutiva disputa por discursos e espaços de representação a partir das periferias. Dentre esses grupos protagonistas que lutam por reconhecimento, o movimento teatral tem se posicionado de maneira contundente na busca por espaços e afirmação das identidades periféricas. No entanto, o teatro em comunidade tem suscitado grandes interesses, em especial, na América Latina onde tem ampliado as perspectivas dos grupos e coletivos teatrais e das comunidades a partir da ideia de empoderamento, da justiça social e do trabalho em rede. É a partir desse universo, do desenvolvimento histórico-social do teatro, suas transformações e a consecutiva apropriação dos grupos das regiões periféricas das cidades diante de uma prática denominada teatro em comunidade que nos debruçamos para tentar explicar o importante caráter desse trabalho realizado nas periferias das cidades da América Latina. Direcionando esse olhar para a periferia da Cidade de São Paulo, no bairro Cidade Tiradentes para o grupo Pombas Urbanas, suas histórias e suas ações, procurou-se apresentar, ao longo desse processo, as transformações significativas que ocorreram na forma-teatro ao longo de sua trajetória, os possíveis desdobramentos na busca por uma concepção estética até o surgimento da prática de Teatro em Comunidade. O contato do Pombas Urbanas com essa prática e os resultados obtidos nos últimos anos, tendo como ponto de partida uma contextualização radical à luz das teorias dos Estudos Culturais e do pensamento crítico latino-americano, buscou-se compreender de que forma a atuação na periferia, a partir da prática de teatro em comunidade, pode operar transformações sociais significativas / The art is the result of historical and social development, overall it has always been combined to the social transformations, especially the theater and its expression forms. Understand this process of formation and itself unfoldings, is essential to understand, how and what are the ways the dramatic art, which pursued in each historic time and how these changes have impelled new expression forms somehow, tightly in an international context marked by deepening of neoliberal politics, the advances of the named globalization and its consecutive dispute for speeches and space of performance from the peripheries. Amongst these protagonists groups which fight for acknowledgement, the theatrical movement has placed itself in a bruising way seeking out acknowledgement spaces and affirmation of the peripherical identities. Many are the proposals of artistic groups, however, the theater practice in community which presupposes to build and conceive a space that valorize the social, the reinsertion, the team labor, the communal practice and the social justice have raised large interests, specially, on Latin American groups, because have increased the perspectives of groups from empowerment idea and networking labor. From this sphere, the historic and social development of theater, its transformations and the consecutive appropriation of the groups from peripherical regions, from towns before a practice denominated theater in community that we lean over trying to explain the important character of this labor accomplished on towns peripheries in Latin American, to direct this sight to the São Paulo City periphery, in Cidade Tiradentes district for Pombas Urbanas Group, its history and actions, seeking out to perform along this process the significant transformations occurred on theater shape along the history, the possible unfoldings, seeking out for aesthetics concept until the appearance of the theater in community practice; the Pombas Urbanas touch to this practice and the results obtained in last years, as of a radical contextualization lightened of Cultural Studies Theories and the Latin American critic thought, seeking out to understand how the peripherical perfoming can make significant social transformations from theater in community practice

Este trabalho aprofunda o estudo da paisagem na periferia da metrópole de modo interdisciplinar, valendo-se de uma perspectiva teórico-prática aplicada ao estudo de caso Jardim Celeste e entorno, São Paulo. O termo composto paisagem dos lugares foi circunscrito e utilizado a fim de enfocar o estudo da paisagem por um viés criativo e crítico, propositivo e transformador, atentando para a totalidade dos processos sociais, culturais e ambientais intrinsecamente relacionados ao objeto de estudo e seu campo empírico. Os conceitos e métodos foram criados ao longo da pesquisa e objetivaram, em última instância, a expansão do conhecimento e a emancipação dos envolvidos; para tanto, uma variedade de métodos e atividades práticas foram organizadas e aplicadas, sendo estas: a observação participante, o mapeamento do substrato do objeto de estudo, entrevistas, questionários, mutirões e oficinas. Em suma, esta dissertação versa sobre novos entendimentos e perspectivas da paisagem na metrópole através do prisma da paisagem dos lugares, as quais convidam a uma postura visual-estético-sensorial sobre o espaço da esfera pública de todos os dias. / This research sought to deepen the study of the landscape in the periphery of the metropolis through an interdisciplinary approach, making use of theories and practices applied to the case study of Jardim Celeste and its surroundings, Sao Paulo. The compound term landscape of places was defined and utilized as a means to focus the study of the landscape on the importance of proposing social transformations through creative and critical thinking. Moreover, the social, cultural and environmental processes inherently related to the study object and its empirical field have been fully considered. The concepts and methods were created as the research progressed and they aimed ultimately at expanding the knowledge and empowerment of those involved in the research. To this end, a variety of methods and practical activities were organized and implemented, such as: participant observation, mapping of the study object and is substrate, interviews, questionnaires, community work and workshops, all of them being participatory. In short, this dissertation examines new understandings and perspectives of the landscape in the metropolis through the prism of the landscape of places, which proposes a visual, sensorial and aesthetic stance on the public spaces of everyday life.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The purpose of this dissertation is to analyse the representations and social practices of manual workers that live in the periphery of Santa Maria, RS. For this, we seek to understand how these men constitute themselves as subjects in this context, through their narratives and work practices, the interpersonal relationships that are formed and the knowledge acquired in the workplace. From the participant observation and ethnographic writing, we sought to reflect how this particular type of worker wich apparently lives in a situation of disadvantage in brazilian society, perpetuates his knowledge. / O objetivo desta dissertação busca analisar as representações e práticas sociais de trabalhadores manuais moradores da periferia de Santa Maria, Rio Grande do Sul, Brasil. Para isso, procurou-se compreender como estes homens constituem-se como sujeitos neste contexto, através de suas narrativas e práticas de trabalho, das relações interpessoais formadas e dos conhecimentos adquiridos no ambiente laboral. A partir da observação participante e da escrita etnográfica, buscou-se refletir como este determinado tipo de trabalhador, que aparentemente vivencia uma situação de desvantagem na sociedade brasileira, perpetua seus saberes.