Silicone polymers and network-materials have proven extremely useful in a variety of applications owing to their superb properties when compared to carbon-based polymers. Polysiloxanes containing functional groups other than simple alkyl moieties have allowed for further manipulations of pendant groups along the polymer backbone leading to a greater range of possible chemical transformations, as well as changes in physical/interfacial properties. One aspect of functional polymers that has yet to be explored with respect to primarily silicone-based systems is that of stimuli-responsive materials. In order for this unique application to work, silicones must be functionalized with a group or groups that can influence the polymer’s properties based on that group’s response to specific external stimuli. Boronic acids represent one such group, wherein the most common stimuli used to affect changes in ionization state and solubility are pH and diol-binding. Boronic acids are also capable of forming weak hydrogen-bonded dimers with other boronic acids, and dynamic covalent bonds with Lewis bases. It is proposed that the covalent attachment of boronic acids and their derivatives onto silicones could lead to stimuli-responsive silicone materials. Herein, the synthesis of silicone-boronic acids and their protected boronic esters is described. The simple two-step method involving boronic acid protection followed by hydrosilylation has led to a variety of molecules differing in molecular weight and three-dimensional geometry through the use of commercially available hydride-functional silicones. Initial results regarding saccharide binding selectivity and the impacts on silicone solubility are provided. The unique interfacial behaviour of silicone-boronic esters and their propensity to form self-assembled, crosslinked films at an air/water interface are also reported. Using several different diol protecting groups and a variety of aqueous sub-phases, the mechanism for changes in physical properties as well as crosslinking were revealed. Finally, the production of new thermoplastic silicone elastomers from silicone-boronic esters and amine-containing molecules is discussed. The Lewis acid/Lewis base complexation that occurs between nitrogen and boron can provide enough strength to produce robust, yet recyclable, silicone elastomers without the use of catalyst or solvent. Elastomers can be easily dissolved and reformed through the introduction and removal of a mono-functional Lewis base. The impact of crosslink density, controlled by the quantities and molecular weights of each polymer component used, on physical characteristics is reported. / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

Thesis (DSc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Examples of the use of NMR spectroscopy in the study of radical polymerization processes have been described. The studies presented have made a significant contribution to the understanding of the fundamental mechanistic processes in these polymerization systems. It is pointed out that NMR in conventional radical polymerization is of limited use due to the concurrent occurrence of all elementary reactions (initiation, propagation and termination). Conversely, for living radical polymerization, NMR has great value. In that case, the elementary reactions are somewhat more restricted to specific times of the polymerization process. This allows for example the detailed study of the early stages of chain growth in Reversible Addition-­‐Fragmentation Chain Transfer (RAFT) mediated polymerization. Two different studies are described. The first is related to the early stages of RAFT-­‐mediated polymerization. A process for which we coined the name initialization was studied via in situ 1H NMR spectroscopy. It is shown that in many cases, there is a selective reaction that converts the original RAFT agent into its single monomer adduct. A few different examples and their mechanistic interpretation are discussed. It is also shown that NMR spectroscopy can be a valuable tool for the assessment of a RAFT agent in conjunction with a specific monomer and polymerization conditions. In the second study, 15N NMR, 31P NMR and 1H NMR are used for two different types of experiments. The first is a conventional radical copolymerization in which the growing chains are trapped by a 15N labeled nitroxide to yield a stable product. In the second experiment, a similar copolymerization is conducted under nitroxide-­‐mediated conditions. The nitroxide of choice contains phosphorous, which enables the quantification of the terminal monomer in the dormant chains. Each of the experiments individually provides interesting information on conventional radical copolymerization and nitroxide-­‐mediated copolymerization, respectively. Combination of the experimental data reveals an interesting discrepancy in the ratio of terminal monomer units in active chains and dormant chains. Although not unexpected, this result is interesting and useful from a mechanistic as well as a synthetic point of view. In terms of future perspectives, it is expected that the advanced analytical techniques as described here will remain crucial in polymer science. Present developments in radical polymerization, such as investigations into monomer sequence control, rely on accurate knowledge of kinetic and mechanistic details of elementary reactions. It is expected that such detailed studies will be a main challenge for the next decade of polymer research. / AFRIKAANSE OPSOMMING: Voorbeelde van die gebruik van KMR-­‐spektroskopie in die studie van radikaalpolimerisasies word beskryf. Hierdie studies het ʼn beduidende bydrae gelewer tot die verstaan van die fundamentele meganistiese prosesse in hierdie polimerisasiesisteme. Dit het daarop gewys dat KMR beperkte gebruike het in konvensionele radikaalpolimerisasies as gevolg van die gelyktydige voorkoms van alle basiese reaksies (afsetting, voortsetting en beëindiging). Aan die anderkant het KMR groot waarde vir lewende radikaalpolimerisasie. In hierdie geval is die elementêre reaksies ietwat meer beperk tot spesifieke tye van die polimerisasieproses. Gedetailleerde studies kan byvoorbeeld van die vroeë stadiums van die kettinggroei in Omkeerbare Addisie-­‐Fragmentasie-­‐ KettingOordrag (OAFO)-­‐bemiddelde polimerisasie gedoen word. Twee verskillende studies is beskryf. Die eerste het betrekking op die vroeë stadiums van die OAFO-­‐bemiddelde polimerisasie. 'n Proses wat “inisialisering” genoem is, is bestudeer deur middel van in situ 1H KMR-­‐spektroskopie. Dit is bewys dat daar in baie gevalle 'n selektiewe reaksie is wat die oorspronklike OAFO-­‐agent in sy enkelmonomeeradduk verander voor polimerisasie. 'n Paar ander voorbeelde en hul meganistiese interpretasie is bespreek. Dit is ook bewys dat KMR-­‐spektroskopie 'n waardevolle hulpmiddel kan wees vir die assessering van 'n OAFO-­‐agent in samewerking met 'n spesifieke monomeer en polimerisasie toestande. In die tweede studie is 15N KMR, 31P KMR en 1H KMR gebruik vir twee verskillende tipes van die eksperiment. Die eerste is 'n konvensionele radikaalkopolimerisasie waarin die groeiende kettings vasgevang word deur 'n 15N-­‐gemerkte nitroksied om 'n stabiele produk te lewer. In die tweede eksperiment is 'n soortgelyke kopolimerisasie gedoen onder nitroksied-­‐ bemiddelde toestande. Die gekose nitroksied bevat fosfor wat die kwantifisering van die terminale monomeer in die dormante kettings moontlik maak. Elkeen van die individuele eksperimente lewer interessante inligting oor konvensionele radikale kopolimerisasie en nitroksied-­‐bemiddelde kopolimerisasie, onderskeidelik. ʼn Kombinasie van die eksperimentele data toon 'n interessante verskil aan in die verhouding van die terminale monomeereenhede in die aktiewe en sluimerende kettings. Alhoewel dit nie onverwags is nie, is die resultate interessant en van waarde vanuit 'n meganistiese-­‐ sowel as 'n sintetiese oogpunt. In terme van toekomstige perspektiewe word daar verwag dat gevorderde analitiese tegnieke soos hier beskryf, belangrik sal bly in polimeerwetenskap. Huidige ontwikkelinge in radikaalpolimerisasie, soos ondersoeke na die beheer van monomeervolgorde, maak staat op akkurate kennis van kinetiese en meganistiese besonderhede van die basiese reaksies. Daar word verwag dat sulke gedetailleerde studies ʼn uitdaging sal bied vir die volgende dekade van polimeernavorsing.

Ce travail de thèse porte sur la synthèse de copolymères greffés à squelette 1,4-polybutadiène (PBu) et polyoxanorbornène par combinaison de ROMP et chimie click et/ou polymérisation RAFT selon la méthode grafting through. Une gamme de macromonomères symétriques et non symétriques originaux poly(oxyde d'éthylène) (POE), poly(acrylate d'éthyle), poly(acrylamide de N-isopropyle) (PNIPAM) et POE-b-PNIPAM ont été synthétisés à partir de précurseurs oxanorbornène et cyclobutène fonctionnalisés présentant un ou deux groupements clickables et/ou un agent RAFT par chimie click et polymérisation RAFT. Une série de PBu-g-POE et polyoxanorbornène-g-POE bien définis ont été obtenus par ROMP en solution en utilisant des amorceurs de Grubbs et de Schrock. Les tests de ROMP en milieu aqueux dispersé ont montré que la mini-émulsion était efficace pour la polymérisation des macromonomères POE à extrémité cyclobutényle et oxanorbornényle.

Parkinson’s disease (PD) is an age-related neurodegenerative disorder. The degeneration of the neurons of the substantia nigra in the midbrain leads to the loss of dopamine from the striatum, which is responsible for the motor symptoms of PD. In the brain, the enzyme, monoamine oxidase B (MAOB), An analysis of the Lineweaver-Burk plots indicated that 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)- quinolinone inhibits MAO-B with a Ki value of 2.7 nM. An analysis of the structure-activity relationships for MAO-B inhibition shows that substitution on the C7 position of the 3,4-dihydro- 2(1H)-quinolinone moiety leads to significantly more potent inhibition compared to substitution on C6. In this regard, a benzyloxy substituent on C7 is more favourable than phenylethoxy and phenylpropoxy substitution on this position. In spite of this, C6-substituted 3,4-dihydro-2(1H)-quinolinone with potent MAO-B inhibitory activities were also identified. An analyses of selected properties of the 3,4-dihydro-2(1H)- quinolinones showed that the compounds are highly lipophilic with logP values in the range of 3.03- 4.55. LogP values between 1 and 3 are, however, in the ideal range for bioavailability. The compounds synthesised have logP values higher than 3, which may lead to lower bioavailability. Laboratory data further showed that none of the 3,4-dihydro-2(1H)-quinolinones are highly toxic to cultured cells at the concentrations, 1 μM and 10 μM, tested. For example, the most potent MAO-B inhibitor, 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)-quinolinone, reduced cell viability to 88.11% and 86.10% at concentrations of 1 μM and 10 μM, respectively. These concentrations are well above its IC50 value for the inhibition of MAO-B. At concentrations required for MAO-B inhibition, the more potent 3,4-dihydro-2(1H)-quinolinones are thus unlikely to be cytotoxic. It may thus be concluded that C7-substituted 3,4-dihydro-2(1H)-quinolinones are promising highly potent and selective MAO-B inhibitors, and thus leads for the therapy of Parkinson’s disease. represents a major catabolic pathway of dopamine. Inhibitors of MAO-B conserve the depleted supply of dopamine and are thus used in the therapy of PD. In the present study, a series of 3,4- dihydro-2(1H)-quinolinone derivatives were synthesized and evaluated as inhibitors of recombinant human MAO-A and MAO-B. These quinolinone derivatives are structurally related to a series of coumarin (1-benzopyran-2-one) derivatives, which has been reported to act as MAO-B inhibitors. C6- and C7-substituted 3,4-dihydro-2(1H)-quinolinone derivatives were synthesized by reacting 6- or 7- hydroxy-3,4-dihydro-2(1H)-quinolinone with an appropriately substituted alkyl bromide in the presence of base. To evaluate the MAO inhibitory properties (IC50 values) of the quinolinone derivatives the recombinant human MAO-A and MAO-B enzymes were used. The reversibility of inhibition of a representative 3,4-dihydro-2(1H)-quinolinone derivative was examined by measuring the recovery of enzyme activity after the dilution of the enzyme-inhibitor complexes, while the mode of MAO inhibition was determined by constructing Lineweaver-Burk plots. To determine the lipophilicity of the 3,4-dihydro-2(1H)-quinolinone derivatives, the logP values were measured. The toxicity of the 3,4-dihydro-2(1H)-quinolinone derivatives towards cultured cells (cytotoxicity) was also measured. The results document that the 3,4-dihydro-2(1H)-quinolinone derivatives are highly potent and selective MAO-B inhibitors with most homologues exhibiting IC50 values in the nanomolar range. The most potent MAO-B inhibitor, 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)-quinolinone, exhibits an IC50 value of 2.9 nM with a 2750-fold selectivity for MAO-B over the MAO-A isoform. As a MAO-B inhibitor, this compound is approximately equipotent to the most potent coumarin derivative (IC50 = 1.14 nM) reported in literature. Since MAO-B activity could be recovered after dilution of enzyme-inhibitor mixtures, it may be concluded that 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)- quinolinone is a reversible MAO-B inhibitor. The Lineweaver-Burk plots constructed for the inhibition of MAO-B by 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)-quinolinone were linear and intersected on the y-axis. These data indicated that this compound also is a competitive MAO-B inhibitor. / MSc (Pharmaceutical Chemistry), North-West University, Potchefstroom Campus, 2014

L’imagerie hyperspectrale est très largement employée en télédétection pour diverses applications, dans le domaine civil comme dans le domaine militaire. Une image hyperspectrale est le résultat de l’acquisition d’une seule scène observée dans plusieurs longueurs d’ondes. Par conséquent, chacun des pixels constituant cette image est représenté par un vecteur de mesures (généralement des réflectances) appelé spectre. Une étape majeure dans l’analyse des données hyperspectrales consiste à identifier les composants macroscopiques (signatures) présents dans la région observée et leurs proportions correspondantes (abondances). Les dernières techniques développées pour ces analyses ne modélisent pas correctement ces images. En effet, habituellement ces techniques supposent l’existence de pixels purs dans l’image, c’est-à-dire des pixels constitué d’un seul matériau pur. Or, un pixel est rarement constitué d’éléments purs distincts l’un de l’autre. Ainsi, les estimations basées sur ces modèles peuvent tout à fait s’avérer bien loin de la réalité. Le but de cette étude est de proposer de nouveaux algorithmes d’estimation à l’aide d’un modèle plus adapté aux propriétés intrinsèques des images hyperspectrales. Les paramètres inconnus du modèle sont ainsi déduits dans un cadre Bayésien. L’utilisation de méthodes de Monte Carlo par Chaînes de Markov (MCMC) permet de surmonter les difficultés liées aux calculs complexes de ces méthodes d’estimation. / Hyperspectral imagery has been widely used in remote sensing for various civilian and military applications. A hyperspectral image is acquired when a same scene is observed at different wavelengths. Consequently, each pixel of such image is represented as a vector of measurements (reflectances) called spectrum. One major step in the analysis of hyperspectral data consists of identifying the macroscopic components (signatures) that are present in the sensored scene and the corresponding proportions (concentrations). The latest techniques developed for this analysis do not properly model these images. Indeed, these techniques usually assume the existence of pure pixels in the image, i.e. pixels containing a single pure material. However, a pixel is rarely composed of pure spectrally elements, distinct from each other. Thus, such models could lead to weak estimation performance. The aim of this thesis is to propose new estimation algorithms with the help of a model that is better suited to the intrinsic properties of hyperspectral images. The unknown model parameters are then infered within a Bayesian framework. The use of Markov Chain Monte Carlo (MCMC) methods allows one to overcome the difficulties related to the computational complexity of these inference methods.

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology)) -- Vaal University of Technology, 2011. / “Never before in peacetime have we faced such serious and widespread shortage of energy” according to John Emerson, an economist and power expert for Chase Manhattan Bank. Many analysts believe that the problem will be temporary, but others believe the energy gap will limit economic growth for years to come. A possible solution to this problem can be fuel cell technology. Fuel cells (FCs) are energy conversion devices that generate electricity from a fuel like hydrogen. The FC however, could also be used in the reverse or regenerative mode to produce hydrogen. The reversible fuel cell (RFC) can produce hydrogen and oxygen by introducing water to the anode electrode chamber, and applying a potential across the anode and cathode. This will cause the decomposition of the water to produce oxygen at the anode side and hydrogen at the cathode side. In order to make this process as efficient as possible several aspects need to be optimised, for example, the operation temperature of the RFC, water management inside the RFC and supply voltage to the RFC. A three cell RFC and its components were constructed. The three cell RFC was chosen owing to technical reasons. The design factors that were taken into consideration were the different types of membranes, electrocatalysts, bipolar plates and flow topologies. A water trap was also designed and constructed to eliminate the water from the hydrogen water mixture due to water crossover within the MEA. In order to optimise the operation of the RFC a number of experiments were done on the RFC. These experiments included the optimal operating voltage, the effect that the temperature has on the production rate of hydrogen, and the effect that the water flow through the RFC has on the production rate of hydrogen. It was found that there is no need to control the water flow through the RFC because it had no effect on the production rate of hydrogen. The results also showed that if the operating temperature of the RFC were increased, the energy it consumes to warm the RFC significantly decreases the efficiency of the whole system. Thus the RFC need not be heated because it consumes significantly more energy to heat the RFC compared to the energy available from the hydrogen produced for later use. The optimised operating voltage for the three cell RFC was found to be 5.05 V. If the voltage were to be increased or decreased the RFC efficiency would decrease.

Na análise global e local de sistemas dinâmicos assumimos, em geral, que as equações estão numa forma normal. Em presença de simetrias, as equações e o domínio do problema são invariantes pelo grupo formado por estas simetrias; neste caso, o campo de vetores é equivariante pela ação deste grupo. Quando, além das simetrias, temos também ocorrência de anti-simetrias - ou reversibilidades - as equações e o domínio do problema são ainda invariantes pelo grupo formado pelo conjunto de todas as simetrias e anti-simetrias; neste caso, o campo de vetores é reversível-equivariante. Existem muitos modelos físicos onde simetrias e anti-simetrias aparecem naturalmente e cujo efeito pode ser estudado de uma forma sistemática através de teoria de representação de grupos de Lie. O primeiro passo deste processo é colocar a aplicação que modela tal sistema numa forma normal e isto é feito com a dedução a priori da forma geral dos campos de vetores. Esta forma geral depende de dois componentes: da base de Hilbert do anel das funções invariantes e dos geradores do módulo das aplicações reversíveis-equivariantes. Neste projeto, nos concentramos principalmente na aplicação de resultados recentes da literatura para a construção de uma lista de formas gerais de aplicações reversíveisequivariantes sob a ação de diferentes grupos. Além disso, adaptamos ferramentas algébricas da literatura existentes no contexto equivariante para o estudo sistemático de acoplamento de células idênticas no contexto reversível-equivariante / In the global and local analysis of dynamical systems, we assume, in general, that the equations are in a normal form. In presence of symmetries, the equations and the problem domain are invariant under the group formed by these symmetries; in that case, the vector field is equivariant by the action of this group. When, in addition to the symmetries, we have the occurrence of anti-symmetries - or reversibility - the equations and the problem domain are still invariant by the group formed by the set of all symmetries and anti-symmetries; in this case, the vector field is reversible-equivariant. There are many physical models where both symmetries and anti-symmetries occur naturally and whose effect can be studied in a systematic way through group representation theory. The first step of this process is to put the mapping that model the system in a normal form, and this is done with the deduction of the general form of the vector field. This general form depends on two components: the Hilbert basis of the invariant function ring and also the generators of the module of the revesible-equivariants. In this work, we mainly focus on the applications of recent results of the literature to build a list of general forms of reversible-equivariant mappings under the action of different groups. We also adapt algebraic tools of the existing literature in the equivariant context to the systematic study of coupling of identical cells in the reversible-equivariant context

A produção de grãos e outros caracteres de importância econômica para a cultura do milho, tais como a altura da planta, o comprimento e o diâmetro da espiga, apresentam herança poligênica, o que dificulta a obtenção de informações sobre as bases genéticas envolvidas na variação desses caracteres. Associações entre marcadores e QTLs foram analisadas através dos métodos de mapeamento por intervalo composto (CIM) e mapeamento por intervalo Bayesiano (BIM). A partir de um conjunto de dados de produção de grãos, referentes à avaliação de 256 progênies de milho genotipadas para 139 marcadores moleculares codominantes, verificou-se que as metodologias apresentadas permitiram classificar marcas associadas a QTLs. Através do procedimento CIM, associações entre marcadores e QTLs foram consideradas significativas quando o valor da estatística de razão de verossimilhança (LR) ao longo do cromossomo atingiu o valor máximo dentre os que ultrapassaram o limite crítico LR = 11; 5 no intervalo considerado. Dez QTLs foram mapeados distribuídos em três cromossomos. Juntos, explicaram 19,86% da variância genética. Os tipos de interação alélica predominantes foram de dominância parcial (quatro QTLs) e dominância completa (três QTLs). O grau médio de dominância calculado foi de 1,12, indicando grau médio de dominância completa. Grande parte dos alelos favoráveis ao caráter foram provenientes da linhagem parental L0202D, que apresentou mais elevada produção de grãos. Adotando-se a abordagem Bayesiana, foram implementados métodos de amostragem através de cadeias de Markov (MCMC), para obtenção de uma amostra da distribuição a posteriori dos parâmetros de interesse, incorporando as crenças e incertezas a priori. Resumos sobre as localizações dos QTLs e seus efeitos aditivo e de dominância foram obtidos. Métodos MCMC com saltos reversíveis (RJMCMC) foram utilizados para a análise Bayesiana e Fator calculado de Bayes para estimar o número de QTLs. Através do método BIM associações entre marcadores e QTLs foram consideradas significativas em quatro cromossomos, com um total de cinco QTLs mapeados. Juntos, esses QTLs explicaram 13,06% da variância genética. A maior parte dos alelos favoráveis ao caráter também foram provenientes da linhagem parental L02-02D. / Grain yield and other important economic traits in maize, such as plant heigth, stalk length, and stalk diameter, exhibit polygenic inheritance, making dificult information achievement about the genetic bases related to the variation of these traits. The number and sites of (QTLs) loci that control grain yield in maize have been estimated. Associations between markers and QTLs were undertaken by composite interval mapping (CIM) and Bayesian interval mapping (BIM). Based on a set of grain yield data, obtained from the evaluation of 256 maize progenies genotyped for 139 codominant molecular markers, the presented methodologies allowed classification of markers associated to QTLs.Through composite interval mapping were significant when value of likelihood ratio (LR) throughout the chromosome surpassed LR = 11; 5. Significant associations between markers and QTLs were obtained in three chromosomes, ten QTLs has been mapped, which explained 19; 86% of genetic variation. Predominant genetic action for mapped QTLs was partial dominance and (four QTLs) complete dominance (tree QTLs). Average dominance amounted to 1,12 and confirmed complete dominance for grain yield. Most alleles that contributed positively in trait came from parental strain L0202D. The latter had the highest yield rate. Adopting a Bayesian approach to inference, usually implemented via Markov chain Monte Carlo (MCMC). The output of a Bayesian analysis is a posterior distribution on the parameters, fully incorporating prior beliefs and parameter uncertainty. Reversible Jump MCMC (RJMCMC) is used in this work. Bayes Factor is used to estimate the number of QTL. Through Bayesian interval, significant associations between markers and QTLs were obtained in four chromosomes and five QTLs has been mapped, which explained 13; 06% of genetic variation. Most alleles that contributed positively in trait came from parental strain L02-02D. The latter had the highest yield rate.