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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Novel metal template strategies for the construction of rotaxanes and catenanes

McBurney, Roy T. January 2009 (has links)
The template synthesis of rotaxanes and catenanes has allowed a detailed study of their intrinsically novel and interesting properties. A key strategy has been the deployment of transition metal ions with their well-defined coordination geometries allowing high-yielding and facile preparation of interlocked architectures. Knowledge of how to exploit the coordination sphere of metal ions and the design of ligands for the creation of intermediates that are pre-disposed to undergo ‘stoppering’ or ‘clipping’ has been a crucial requirement for this approach. This Thesis is in three parts describing the use of three dimensional, two dimensional and one dimensional coordination geometries in the synthesis of interlocked architectures. Firstly, the octahedral coordination geometry of cobalt(III) was utilized to organize dianionic pyridine-2,6-dicarboxamido ligands in a mutually orthogonal arrangement such that ring closing metathesis macrocyclizations gave access to interlocked or entwined products. A ‘figure-of-eight’ complex was obtained from a double macrocyclizations, whereas a catenate was accessed through a single macrocyclization. The topology of the isomers was proved by X-ray crystallography. An analogous [2]rotaxane was synthesized and the interlocked nature of the rotaxane demonstrated by 1H NMR spectroscopy and mass spectrometry. Secondly, an “active” metal template strategy, in which the metal ion plays a dual role – acting to both organize ligands and catalyze mechanical bond formation – allowed rotaxanes be constructed using the square planar coordination geometry and Lewis acidic nature of a palladium(II) complex. The interlocked nature of the rotaxane was proved by X-ray crystallography, demonstrating that a nitrile group present in the thread acted as a “station” for the Pd(II)-macrocycle. This observation led to the construction of a two “station” degenerate molecular shuttle in which the dynamics of translocation were controlled by reagent addition and observed by 1H NMR techniques. Lastly, the linear coordination geometry of gold(I) was successfully used as a template for construction of rotaxanes and catenanes via a ‘clipping’ strategy. The linear coordination geometry and the interlocked nature of the gold(I)-catenate was proved by X-ray crystallography, the rotaxane architecture was proved by 1H NMR spectroscopy and mass spectrometry. Chapters Two, Three and Four are in the form of articles that have been published in peer-reviewed journals, and are reproduced, in their published format, in the Appendix. No attempt has been made to rewrite the published work; as a consequence the numbering of compounds, whilst consistent within each Chapter, is not consistent throughout this Thesis. Another consequence is that the many failed synthetic routes have been left out. I hope the reader will forgive these omissions as well as the slight repetition that occurs in the introduction and bibliography of each chapter. Additionally, preceding each Chapter is a brief synopsis that places the work in context and acknowledges the contributions of my fellow researchers.
2

Coordenação modular: acepções contemporâneas / Modular coordination: contemporary acceptations

Crespo, Marina Rosa 23 May 2017 (has links)
A coordenação modular é um sistema para ordenação relativa de dimensões, espaços e componentes construtivos. Sua aplicação tem manifestações remotas por princípios que controlam a composição e fixam escalas convenientes para as partes e o todo, todavia foi a produção seriada industrial que determinou o papel que a disciplina teria no século XX. No Brasil, seu desenvolvimento aconteceu entre as décadas de 1950 e 1970, quando foi determinada a formatação fundamental da disciplina. Identifica-se a partir da década de 1980 um intervalo nas discussões específicas que durou até a virada do século, quando foi recuperado o interesse pela área. É consenso entre os autores que ainda não houve no Brasil sucesso na implantação de modelos abrangentes da coordenação modular, mas faltam análises atualizadas. O objetivo da dissertação - examinar o desenvolvimento da disciplina no Brasil após 1986 - está fundamentado em indícios de que as discussões recentes não se aprofundam em temas atuais e de que há um enfraquecimento de uma visão integrada do problema. As principais conclusões indicam que o desenvolvimento da construção civil vem sendo acompanhado do afastamento da arquitetura de etapas da produção, o que afeta o exercício da coordenação modular e que o programa habitacional e as ações políticas de financiamento foram determinantes para a retomada das pesquisas. Entretanto, há ecos dos modelos estabelecidos pelo setor privado, com ênfase à racionalização e à aplicação de componentes industriais. Diante disso, destaca-se que a coordenação modular, como campo da coordenação dimensional, está ligada às necessidades humanas. / Modular coordination is a system for relative ordering of dimensions, spaces, and building components. Its application presents remote manifestations through principles that control the design and set suitable scales for the parts and the whole. Nevertheless, the industrial mass production defined the role that the subject would play during the 20th century. In Brazil, its development took place between the 1960s and the 1970s; period that several authors consider decisive in what regards the subject\'s fundamental formatting. From the 1980s on, the specific debates about the matter went through a gap that lasted until the turn of the century when the interest in the field resurfaced. It is consensual among authors that Brazil still has not been successful to implement comprehensive modular coordination standards, but there is a lack of up-to-date analysis as well. The objective of the dissertation - to examine the discipline\'s development in Brazil after 1986 - is based on indications that recent discussions are leaving aside current issues and that there is a weakening of an integrated view of the matter. The main conclusions indicate that a dissociation between architecture and construction has accompanied the building industry\'s development, which affects the application of modular coordination. Moreover, the housing program and the research funding were decisive for the resumption of the field; nonetheless, there are echoes from the models established by the private sector, with emphasis on the rationalization and application of industrial components. In this context, it should be noted that modular coordination, as a field of dimensional coordination, is linked to human needs.
3

Coordenação modular: acepções contemporâneas / Modular coordination: contemporary acceptations

Marina Rosa Crespo 23 May 2017 (has links)
A coordenação modular é um sistema para ordenação relativa de dimensões, espaços e componentes construtivos. Sua aplicação tem manifestações remotas por princípios que controlam a composição e fixam escalas convenientes para as partes e o todo, todavia foi a produção seriada industrial que determinou o papel que a disciplina teria no século XX. No Brasil, seu desenvolvimento aconteceu entre as décadas de 1950 e 1970, quando foi determinada a formatação fundamental da disciplina. Identifica-se a partir da década de 1980 um intervalo nas discussões específicas que durou até a virada do século, quando foi recuperado o interesse pela área. É consenso entre os autores que ainda não houve no Brasil sucesso na implantação de modelos abrangentes da coordenação modular, mas faltam análises atualizadas. O objetivo da dissertação - examinar o desenvolvimento da disciplina no Brasil após 1986 - está fundamentado em indícios de que as discussões recentes não se aprofundam em temas atuais e de que há um enfraquecimento de uma visão integrada do problema. As principais conclusões indicam que o desenvolvimento da construção civil vem sendo acompanhado do afastamento da arquitetura de etapas da produção, o que afeta o exercício da coordenação modular e que o programa habitacional e as ações políticas de financiamento foram determinantes para a retomada das pesquisas. Entretanto, há ecos dos modelos estabelecidos pelo setor privado, com ênfase à racionalização e à aplicação de componentes industriais. Diante disso, destaca-se que a coordenação modular, como campo da coordenação dimensional, está ligada às necessidades humanas. / Modular coordination is a system for relative ordering of dimensions, spaces, and building components. Its application presents remote manifestations through principles that control the design and set suitable scales for the parts and the whole. Nevertheless, the industrial mass production defined the role that the subject would play during the 20th century. In Brazil, its development took place between the 1960s and the 1970s; period that several authors consider decisive in what regards the subject\'s fundamental formatting. From the 1980s on, the specific debates about the matter went through a gap that lasted until the turn of the century when the interest in the field resurfaced. It is consensual among authors that Brazil still has not been successful to implement comprehensive modular coordination standards, but there is a lack of up-to-date analysis as well. The objective of the dissertation - to examine the discipline\'s development in Brazil after 1986 - is based on indications that recent discussions are leaving aside current issues and that there is a weakening of an integrated view of the matter. The main conclusions indicate that a dissociation between architecture and construction has accompanied the building industry\'s development, which affects the application of modular coordination. Moreover, the housing program and the research funding were decisive for the resumption of the field; nonetheless, there are echoes from the models established by the private sector, with emphasis on the rationalization and application of industrial components. In this context, it should be noted that modular coordination, as a field of dimensional coordination, is linked to human needs.

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