Optimized methods for the regioselective and stereospecific synthesis of both trisubstituted and tetrasubstituted olefins as single isomers from E-β-chloro-α-iodo-α,β-unsaturated esters have been developed from previous work done in the Ogilvie lab. These optimized methods have led to the synthesis of trans isomeric enediynes that can be photoisomerized to their respective cis isomers and subsequently undergo microwave-assisted Bergman cycloaromatizations. Furthermore, both cis and trans isomeric enediynes that have propargyl ether substituents have been found to be able to undergo photoactivated Bergman cyclizations without the need for an intermolecular hydrogen donor. A mechanism study has confirmed that the Bergman cyclization products that form without the presence of an intermolecular hydrogen donor undergo a series of 1,5-hydrogen shifts as intermediates. A series of optimizations to these reactions were carried out, in part by utilizing electron-donating or electron-withdrawing functional groups to help stabilize the resulting radicals that form on the intermediates, and thus increase the yield of the associated Bergman cyclization products.

One of the most essential objectives in WSNs is to determine the spatial coordinates of a source or a sensor node having information. In this study, the problem of range measurement-based localization of a signal source or a sensor is revisited. The main challenge of the problem results from the non-convexity associated with range measurements calculated using the distances from the set of nodes with known positions to a xed sen- sor node. Such measurements corresponding to certain distances are non-convex in two and three dimensions. Attempts recently proposed in the literature to eliminate the non- convexity approach the problem as a non-convex geometric minimization problem, using techniques to handle the non-convexity. This study proposes a new fuzzy range-free sensor localization method. The method suggests using some notions of Euclidean geometry to convert the problem into a convex geometric problem. The convex equivalent problem is built using convex fuzzy sets, thus avoiding multiple stable local minima issues, then a gradient based localization algorithm is chosen to solve the problem. Next, the proposed algorithm is simulated considering various scenarios, including the number of available source nodes, fuzzi cation level, and area coverage. The results are compared with an algorithm having similar fuzzy logic settings. Also, the behaviour of both algorithms with noisy measurements are discussed. Finally, future extensions of the algorithm are suggested, along with some guidelines.

Syfte: Syftet var att beskriva hur män upplever att de påverkats av miktionsproblem och erektil dysfunktion efter radikal prostatektomi. Metod: Examensarbetet utfördes som en litteraturöversikt med tio vetenskapliga studier. Resultat: Upplevelsen av förlorad kontroll vid miktionsproblem var det som främst påverkade männen samt medförde att det sociala livet blev lidande. Männen beskrev hur de var tvungna att planera inför olika sociala tillställningar, vilket upplevdes som stressande och ångestfyllt. Det framkom också att männen oroade sig för urinläckage, stark odör och upplevde möten med oförstående människor som frustrerande. Erektil dysfunktion var den vanligaste komplikationen efter behandling, men miktionsproblem var det som orsakade mest besvär. Det upplevdes som att männen förlorat sin självständighet. Det framkom även att erektil dysfunktion upplevdes av vissa män som den komplikation som gav störst besvär. Erektil dysfunktion påverkade männen och var mycket svårt att hantera. Det var svårt att finna en acceptans för att den erektila dysfunktion kunde vara bestående. Många av männen beskrev att en viktig del i deras liv förlorats, en del av deras maskulinitet. De kände sig ofullständiga och det fanns en rädsla för att förlora sin partner. Slutsats: Studier visar att erektil dysfunktion och miktionsproblem i samband med radikal prostatektomi ger upphov till stress, oro, ångest samt en känsla av ofullständighet.

L'objecte d'aquesta tesi és estudiar els efectes que provoquen diferents estressos radicals (hídric, fred, dèficit nutricional) aplicats a part del sistema radical en: l'intercanvi de gasos de la capçada (Pn, E, gs), el potencial hídric del brot i l'activitat radical (absorció iònica, respiració, càrrega xilemàtica). Per a tal finalitat s'han emprat plantes de gira-sol ("Helianthus annuus" cv. Solmax) crescudes en medi hidropònic líquid, emprant la tècnica de separació d'arrel en vàries parts regulades independentment.Es tracta de donar resposta a la pregunta de com modula la planta l'activitat de cada part de l'arrel en un medi heterogeni? S'ha estudiat que fan les arrels estressades, obtenint una davallada en la seva activitat (absorció iònica i respiració) provocada pels diferents estressos. També s'ha comprovat que la part aèria no es veia afectada en cap dels tractaments perque les arrels complementàries mostraven una clara resposta compensatòria a la disminució d'activitat de les arrels estressades, augmentant les seves taxes d'absorció iònica i respiració radical. / "Efectos compensatorios entre raíces de una misma planta de girasol sometida a estrés"RESUMEN:Estudiar los efectos que provocan diferentes estreses radiculares (hídrico, frío, déficit nutricional) aplicados a parte del sistema radical en: intercambio de gases de la parte aérea (Pn, E, gs), el potencial hídrico del brote y la actividad radicular (absorción iónica, respiración, carga xilemática). Para esta finalidad se han utilizado plantas de girasol ("Helianthus annuus" cv. Solmax) crecidas en medio hidropónico líquido, utilizando la técnica de separación radicular en varias partes reguladas independientemente.Se trata de dar respuesta a la pregunta de cómo modula la planta la actividad de cada parte de la raíz en un medio heterogéneo?. Se ha estudiado que hacen las raíces estresadas, obteniendo una disminución en su actividad (absorción iónica y respiración) provocada por los diferentes estreses. También se ha comprobado que la parte aérea no se vió afectada en ninguno de los tratamientos porque las raíces complementarias mostravan una clara respuesta compensatoria a la disminución de actividad de las raíces estresadas, aumentando sus tasas de absorción iónica y respiración radicular. / DISSERTATION TITLE:"Compensatory effects between roots of a sunflower plant subject to a stress"ABSTRACT:To study the effects promoted by root stresses (hydric, cooling, nutrient deficiency) provoqued to a part of the root system in: shoot gases exchange (Pn, E, gs), hydric potential and root activity (ionic absorption, respiration and xylem uptake). In order to this we used sunflower plants (Helianthus annuus cv. Solmax) grown in hydroponical liquid in split-root system.The fact is to answer the question, how the plant module the activity of each part of the root in a heterogeneous environment?. We studied the stressed roots and we saw a decrease in its activity (ionic absorption and respiration) lead to different stresses. We saw too that shoot is not affected by root stresses because complementary roots showed an evident compensatory answer to activity decrease of stressed roots, increasing its absorption taxes and root respiration.

Se han obtenido una serie de conjugados de flavanoles a partir de un extracto vegetal mediante un proceso de despolimerización ácida en presencia de derivados de cisteína. Los monómeros de flavanoles derivatizados se separaron eficientemente del crudo de extracción mediante cromatografia de intercambio iónico en medio ácido, debido a la carga neta introducida al derivatizar. Posteriormente fueron purificados por cromatografia en fase reversa C18 obteniendo los correspondientes derivados de epicatequina, catequina y epicatequin 3-O-galato conjugados con L-cisteína, O-etilcisteína y N-acetilcisteína. Dichos compuestos presentaron una mayor capacidad antiradicalaria que la correspondiente epicatequina mediante ensayos con los radicales libres DPPH (el cual se reduce via donación de hidrogenos y/o por transferencia electrónica) y el nuevo radical estable HNTTM sintetizado en el Departamento de Materiales Orgánicos Halogenados del IIQAB-CSIC (el cual se reduce solo por transferencia electrónica). Todos los compuestos conjugados presentaron una mayor capacidad antiradicalária que el monómero de epicatequina y los compuestos que contenian el éster de galato fueron los que generaron una mayor capacidad antiradicalária en ambos estudios. También se realizaron estudios in vitro con líneas tumorales humanas de melanoma (A375 y M21) y de colon (HT29) y con una línea no tumoral de queratinocitos humanos (HaCaT), observándose una moderada inhibición en la viabilidad celular, siendo los compuestos que contenian un éster galato los que presentaron mayor efectividad. A nivel de ciclo celular, solo los derivados que contenian el éster galato presentaron una alteración en el ciclo a concentraciones dobles de su respectiva IC50, con un aumento de la distribución en la fase S. Igualmente se observó una inducción en la apoptosis en las linias tumorales tratadas con los compuestos (siendo los conjugados con el éster galato los que presentaron una mayor inducción), pero no en la linea no tumoral de queratinocitos. Dicha inducción a la apoptosis se corroboró con otras técnicas en las que se observó condensación de cromatina y la fragmentación del ADN. Sorprendentemente, uno de los derivados que contenia un éster de galato no presentó alteración en el ciclo celular ni indujo apoptosis en las células tumorales. Igualmente, su poder antiradicalario mediante transferencia electrónica (HNTTM) fue inusitadamente bajo aun conteniendo el grupo galato. Con dichos resultados se hipotetizó la posible relación entre la transferencia electrónica y su efecto en la maquinaria celular. Asimismo, el radical estable HNTTM nos permitiria predecir de forma sencilla la capacidad pro-apoptótica de los compuestos según su capacidad de transferencia electrónica. / It has been obtained a serie of flavanol conjugates from grape byproduct through acid depolimerisation with cysteine derivatives. The conjugates were separated efficiently form the crude extract using ion exchange chromatography. The conjugates of epicatechin, catechin and epicatechin 3-O-gallate with L-cysteine, O-ethylcysteine and N-acetylcysteine were purificated by reverse phase chromatography. These conjugates showed an enhanced antiradical power using the free radical DPPH (through electron transfer and/or hydrogen atom donation) and the recently synthetized free radical HNTTM (reduced only by electron transfer). All the conjugates showed higher antiradical power than the monomeric epicatechin and the conjugates containing the gallate group were the most active compounds against free radicals. Studies about tumoral human melanoma (A375 and M21) and adenocarcinoma (HT29) cell lines and non-tumoral keratinocyte cell line (HaCaT) were also performed. It was observed a moderate effect in cell viability inhibition, being the conjugates containing the gallate group the most effective ones. Regarding cell cycle, only the conjugates containing the gallate group showed S-phase arrest to concentrations double of its IC50. Moreover, it was observed an induction of apoptosis in the tumoral cell lines treated with the conjugates, but not in the keratinocyte cell line. Surprisingly, just only one of the conjugates containing a gallate group showed a normal cell cycle distribution and it did not induce apoptosis to the tumoral cell line. Thus, its antiradical power agaisnt HNTTM (electron transfer) was lower than expected for a galloylated compound. With these results, a possible relationship between electron transfer and the cellular mechanism was proposed.

Depuis le Sommet des Amériques de Québec en 2001, un mouvement d'écologie radicale a émergé dans la province. Entre 2001 et 2007, quatorze groupes écologistes radicaux ont vu le jour. Dix des quatorze groupes ont participé à l'étude. Pour chacun de ces dix groupes, un répondant a été interviewé. Cette étude est la première au Québec à se pencher sur le sujet. Ces groupes, organisés de façon décentralisée, non hiérarchique et autonome, perçoivent le rapport entre la société et la nature comme étant problématique. Leur radicalisme se veut une tentative d'aller aux racines (causes) du problème et de se rapprocher d'un mode de vie égalitaire, tant écologique que social. Le mouvement est fortement influencé par la pensée libertaire. Ces groupes lient la lutte pour l'environnement à celles contre les inégalités sociales et la domination, s'opposant à l'État, au capitalisme et à l'anthropocentrisme. En pratiquant l'action directe, la réappropriation de lieux et l'éducation, les groupes visent à acquérir une plus grande autonomie, à devenir autosuffisants et à subvertir les bases du système dominant. Leurs enjeux sont multiples, mais les groupes se concentrent sur les thématiques de l'alimentation, la cruauté faite aux animaux et la coupe forestière. Chacune de leurs pratiques est considérée comme outil d'une lutte sociale plus large. En étudiant leurs discours, stratégies et pratiques il apparaît évident que les écologistes radicaux sont en quête de cohérence, ils en sont cependant conscients et démontrent une praxis complète ou en voie de complétion. Le mouvement écologiste radical du Québec tente de passer de la résistance symbolique à la transgression ouverte. Cependant, la répression (structurelle et policière) dont ils sont vIctimes les contraint à modifier leurs stratégies et pratiques. De plus, les écologistes radicaux accusent le mouvement vert, plus institutionnalisé, de ne pas remettre en question les causes réelles de la crise écologique et de marginaliser leur existence. Ils les accusent de légitimer l'État par le lobbying. Aussi, ils affirment que les organisations environnementales institutionnalisées sont généralement inefficaces et infantilisantes. Leurs pratiques et représentations sociospatiales laissent croire que les groupes écologistes radicaux priorisent deux échelles: le global et le local (avec un emphase sur le résidentiel). Ils n'ont peu ou pas d'identité territoriale, sont critiques des milieux urbains et ruraux et veulent repenser la façon d'habiter le territoire. Ils affichent une conscience géographique soutenue qui comporte l'avantage de l'expérience immédiate et sensible de l'espace construit socialement. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Écologie, Écologie radicale, Mouvement vert, Anarchisme, Radicalisme, Environnementalisme, Géographie critique, Révolution, Représentation sociospatiale.

The purpose of this project is to reexamine established free-radical polymerization theories and build a mechanistic reactor model for multi-component (up to six monomers) bulk and solution polymerizations under batch/semi-batch reactor configurations. The six-monomer system of interest is: Styrene (Sty), n-Butyl acrylate (BA), Butyl methacrylate (BMA), Hydroxyethyl acrylate (HEA), Hydroxybutyl acrylate (HBA), and Acrylic acid (AA). In order to develop a flexible, comprehensive, and user-friendly model, not only a physical/kinetic database of individual monomers and ingredients such as solvents, initiators, and chain transfer agents, but also a co-polymer database of reactivity ratios, and glass transition temperatures were built and combined with the modeling steps. Through an extensive literature search for polymerization models and kinetics, the simulation model was developed in a general way to cover the range from homo- to hexa-polymerization at both regular and elevated temperature levels, and explain various polymerization kinetics and characteristics. Model testing was conducted with experimental data as much as possible to check the model’s reliability. Due to limited experimental data for higher multi-component polymerizations, the simulation model was tested with homo-polymerizations and other available cases of combinations of two to four monomers. Very reasonable agreement was found between model predictions and experimental data on rate of polymerization, molecular weight, polymer composition, sequence length, etc. through the entire conversion. This multi-component modeling study continuously requires experimental checkups and parameter fine-tuning for better predictions. Further literature search or experimental studies still remain necessary for the hydroxyalkyl acrylate kinetic database and model testing of the depropagation feature. Sensitivity analysis also could be performed to locate critical parameters. This model should find use in industry for analyzing and optimizing reactor conditions as well as in the academic field as a research and educational tool.

External world skeptics argue that we have no knowledge of the external world. Contextualist theories of knowledge attempt to address the skeptical problem by maintaining that arguments for skepticism are effective only in certain contexts in which the standards for knowledge are so high that we cannot reach them. In ordinary contexts, however, the standards for knowledge fall back down to reachable levels and we again are able to have knowledge of the external world. In order to address the objection that contextualists confuse the standards for knowledge with the standards for warranted assertion, Keith DeRose appeals to the knowledge account of warranted assertion to argue that if one is warranted in asserting p, one also knows p. A skeptic, however, can maintain a context-invariant view of the knowledge account of assertion, in which case such an account would not provide my help to contextualism.

This thesis examines current radical liberal Christian activism in the Southern United States through focusing upon a particular intentional community located in Atlanta, Georgia, The Open Door Community. Through praxis and reflection, this community has developed its own unique practice and theology that I have termed “Liberation Gospel.” This thesis analyzes and describes a unique community in order to understand where the community succeeds, and where it does not, in putting its theological beliefs into practice. This very liberal community does not distinguish between their politics and their theology.

A relatively well established literature already proffers explanations for the persistence of Euroskeptic Radical Right Parties (ERRPs) in Western Europe and for their emergence in the new democracies of the East. The purpose of this study is not to replicate those existing studies; instead, the argument advanced here is that there may be an important intervening factor as yet unexplored in the extant literature. Drawing upon aggregate survey data from select Western European EU member states and a focused case study of Slovakia, this paper seeks to assess the impact of information, in this case information about the European Union, on voting for ERRPs. The argument presented here is that EU information mitigates the support for ERRPs, more so in the East than in the West.