Berlin, Freie Universiẗat, Diss., 2000. / Dateiformat: zip, Dateien in unterschiedlichen Formaten.

No description available.

No description available.

This thesis describes studies into the ring opening metathesis polymerisation (ROMP) of some monocyclic alkenes, the living polymerisation of cyclopentene and the preparation of novel block copolymers and novel polyethylene architectures using having poly(1 -pentenylene) as the precursor polymer. Chapter 1 reviews general aspects of ring opening metathesis polymerisation of relevance to die themes of this diesis. Chapter 2 describes the ROMP of cw,cw-cycloocta-l,5-diene, cyclopentene, cycloheptene, cyclooctene, cyclodecene and cyclododecene using a series of well- defined initiators of general formula M(N-2,6-i-Pr(_2)-C(_6)H(_3))(CHR)(OR')(_2) where M=Mo or W, the characterisation of the resulting polymers using (^1)H-, (^13)c-NMR and IR spectroscopy, differential scanning calorimetry and gel permeation chromatography and an analysis of their (^13)C-NMR spectroscopic data in terms of the γ-gauche effect. Chapter 3 reports on a (^1)H-NMR study of the synthesis of poly(bis(trifluoromethyl)norbomadiene)-block-poly(l-octenylene) and the synthesis and characterisation of poly(l-pentenylene)-block-polyacetylene-block-poly(1-pentenylene). Chapter 4 describes the synthesis of narrow molecular weight distribution linear and three-branched star polyethylenes via ROMP of cyclopentene initiated by a well-defined tungsten based initiator at low temperature and subsequent capping with mono-, di- and trifunctional aldehydes. Chapter 5 presents an investigation on routes to a well-defined difunctional ROMP initiator which could potentially be used for the synthesis of polyethylene networks. Finally, Chapter 6 summarises the conclusions and outlines some suggestions for future work.

Polyacetylene glycosides are natural products isolated from a variety of natural sources, primarily terrestrial plants and fungi. Polyacetylene glycosides isolated to date feature a linear and conjugated polyacetylene chain and a mono di-, or trisaccharide group in their structures. These compounds have been shown to possess a host of different biological activities, including anti-inflammatory effects, inhibition of nitric oxide production and histamine release, anti-bacterial activity, and the ability to inhibit the enzyme 12-lipoxygenase. The project described in this thesis focuses on polyacetylene glycosides and polyacetylene thioglycosides by glycosylating or thioglycosylating mono-, di-, or triyne alcohols, which have been synthesized using the Cadiot-Chodkiewicz reaction and Fritcsh-Buttenberg-Wiechell rearrangement. Twenty-seven polyacetylene glycosides and thioglycosides have been synthesized. Given the structural similarity of these compounds to bioactive natural products, we expected the molecules should have interesting biological activities. Thirty compounds have thus been assayed for cytotoxicity against MCF-7 breast lines, as well as anti-bacterial activity.

Techn. University, Diss., 2004--Dresden.

É bem conhecido que os intervalos proibidos de energia (gaps) de sólidos semicondutores e isolantes calculados resolvendo-se a equação de Kohn-Sham (KS) com alguma aproximação ao funcional de troca e correlação (XC) da teoria do funcional da densidade (density-functional theory, DFT) são geralmente muito pequenos quando comparados com os valores de gap obtidos experimentalmente. Estes erros, que podem atingir 100%, indicam uma falha nos funcionais de troca e correlação aproximados usados na DFT. Em particular, encontrou-se que o potencial XC, obtido através da derivada do funcional de energia XC, apresenta uma descontinuidade (xc ) quando um elétron extra é adicionado. Portanto, mesmo o gap KS exato não é idêntico ao gap verdadeiro, pois pode haver uma descontinuidade no funcional XC que tem de ser adicionado ao gap KS. Este trabalho propõe uma nova abordagem matemática para o cálculo da descontinuidade do funcional XC e a correção do gap. Inicialmente, as conseqüências desta nova abordagem foram estudadas para os 36 primeiros átomos da tabela periódica (do átomo de hidrogênio, H, ao átomo de criptônio, Kr), utilizando-se para isso os funcionais LDA, GGA e também funcionais híbridos, em combinação com diversos conjuntos de base. A partir da comparação entre valores da descontinuidade calculados teoricamente e resultados prévios da descontinuidade obtidos na literatura para os átomos de lítio (Li) e berílio (Be), foram escolhidos os melhores funcionais em combinação com as melhores bases. Num segundo passo, a nova metodologia para o cálculo da descontinuidade, com os melhores funcionais e bases eleitos, foi aplicada ao cálculo de fragmentos de poliacetileno. / It is well-known that the energy gaps of insulators and semiconductors calculated via the Kohn-Sham (KS) scheme with some approximation to the exchange-correlation (XC) functional of density-functional theory (DFT) are in general too small when compared to experimental gaps. These errors, which can be up to 100%, indicate a fault in the approximate exchange-correlation functionals currently available in DFT. Specifically, it was found that the XC potential, the functional derivative of the XC energy, shows a discontinuity (xc ) when an electron is added. Therefore, the exact KS gap is not identical to true gap, since there can be a discontinuity in the XC functional which should be added to KS gap. The present work proposes a new mathematical approach to the calculation of the discontinuity of the XC functional and the correction of the gap. In a first step, the consequences of this new approach were studied for the first 36 atoms of the periodic table (from Hydrogen, H, to Krypton, Kr), with the LDA and GGA functionals and also some hybrids, in combination with several kinds of basis set. From the comparison between calculated discontinuity values and previous results for the discontinuity reported in the literature for the Lithium (Li) and Beryllium (Be) atoms, the best functionals in combination with the best basis set were selected. In a second step, the new methodology with the best functionals/basis set was applied to the calculation of energy gaps of polyacetylene fragments.

Humboldt-Universiẗat, Diss., 1997--Berlin.

Understanding the fundamental chemistry of conjugated polymers and fullerenes has been the subject of intense research for the last three decades, with the last ten years seeing increased research toward the application of these materials into functional organic electronic devices such as organic photovoltaic devices (OPVs). This field has seen significant advances is cell efficiency in just the last few years (to >10%), in large part due to the development of new donor and acceptor materials, the fine tuning of fabrication parameters to control material nanostructure, as well as the introduction of new interfacial materials such as ionically functionalized conjugated polymers, also known as conjugated polyelectrolytes (CPEs). This dissertation aims to further understand the fundamental chemistry associated with charge injection processes in CPEs and ionically functionalized fullerenes. The role of ionic functionality on electrochemical, chemical, and interfacial charge injection processes is explored. The results presented demonstrate the use of ionic functionality to control the spatial doping profile of a bilayer structure of anionically and cationically functionalized CPEs to fabricate a p-n junction (Chapter II). The role of ionic functionality on chemical charge injection processes is explored via the reaction of polyacetylene and polythiophene based CPEs with molecular oxygen (Chapters III and IV). The results show the dramatic effect of ionic functionality, as well as the specific role of the counterion, on the photooxidative stability of CPEs. The control of reaction pathway via counterion charge density is also explored (Chapter IV) and shows a continuum of reaction pathways based on the charge density of the counter cation. Finally, the role of ionic functionality on interfacial charge injection processes in a functional OPV is explored using a cationically functionalized fullerene derivative (Chapters V and VI). Cell performance increases due to an increase in open-circuit voltage and substantial reduction in series resistance resulting from the high conductivity of the interfacial fullerene layer. The chemical origin of this high conductivity is explored in Chapter VI and shown to likely be the result of chemical reactions occurring between the counter anion and the fullerene core. This dissertation contains coauthored, previously published and unpublished work.

É bem conhecido que os intervalos proibidos de energia (gaps) de sólidos semicondutores e isolantes calculados resolvendo-se a equação de Kohn-Sham (KS) com alguma aproximação ao funcional de troca e correlação (XC) da teoria do funcional da densidade (density-functional theory, DFT) são geralmente muito pequenos quando comparados com os valores de gap obtidos experimentalmente. Estes erros, que podem atingir 100%, indicam uma falha nos funcionais de troca e correlação aproximados usados na DFT. Em particular, encontrou-se que o potencial XC, obtido através da derivada do funcional de energia XC, apresenta uma descontinuidade (xc ) quando um elétron extra é adicionado. Portanto, mesmo o gap KS exato não é idêntico ao gap verdadeiro, pois pode haver uma descontinuidade no funcional XC que tem de ser adicionado ao gap KS. Este trabalho propõe uma nova abordagem matemática para o cálculo da descontinuidade do funcional XC e a correção do gap. Inicialmente, as conseqüências desta nova abordagem foram estudadas para os 36 primeiros átomos da tabela periódica (do átomo de hidrogênio, H, ao átomo de criptônio, Kr), utilizando-se para isso os funcionais LDA, GGA e também funcionais híbridos, em combinação com diversos conjuntos de base. A partir da comparação entre valores da descontinuidade calculados teoricamente e resultados prévios da descontinuidade obtidos na literatura para os átomos de lítio (Li) e berílio (Be), foram escolhidos os melhores funcionais em combinação com as melhores bases. Num segundo passo, a nova metodologia para o cálculo da descontinuidade, com os melhores funcionais e bases eleitos, foi aplicada ao cálculo de fragmentos de poliacetileno. / It is well-known that the energy gaps of insulators and semiconductors calculated via the Kohn-Sham (KS) scheme with some approximation to the exchange-correlation (XC) functional of density-functional theory (DFT) are in general too small when compared to experimental gaps. These errors, which can be up to 100%, indicate a fault in the approximate exchange-correlation functionals currently available in DFT. Specifically, it was found that the XC potential, the functional derivative of the XC energy, shows a discontinuity (xc ) when an electron is added. Therefore, the exact KS gap is not identical to true gap, since there can be a discontinuity in the XC functional which should be added to KS gap. The present work proposes a new mathematical approach to the calculation of the discontinuity of the XC functional and the correction of the gap. In a first step, the consequences of this new approach were studied for the first 36 atoms of the periodic table (from Hydrogen, H, to Krypton, Kr), with the LDA and GGA functionals and also some hybrids, in combination with several kinds of basis set. From the comparison between calculated discontinuity values and previous results for the discontinuity reported in the literature for the Lithium (Li) and Beryllium (Be) atoms, the best functionals in combination with the best basis set were selected. In a second step, the new methodology with the best functionals/basis set was applied to the calculation of energy gaps of polyacetylene fragments.