Studies in the mass spectra of perfluoroaromatic derivatives of phosphorus and some selected transition metals

The mass spectra and fragmentation of a variety of fluoroaromatic compounds of Group V and some selected transition elements are discussed in some detail, aided by data from metastable defocussed experiments. Results of ,studies on the coupling reaction using unstable organotitanium chloride intermediate species are reported. The preparation of some 5-substituted octafluorodibenzophospho1es is also discussed. Rearrangements under electron bombardment resulting in the loss of heteroatom-fluoride fragments are discussed in the light of presently accepted mechanisms for these processes as are rearrangements observed in compounds involving thionophosphoryl bonds ( p=s ).

Electrocortical indices of cognitive control in working memory : exploring the effects of proactive interference, cognitive load, and aging

Cognitive control involves the ability to flexibly adjust cognitive processing in order to resist interference and promote goal-directed behaviour. Although frontal cortex is considered to be broadly involved in cognitive control, the mechanisms by which frontal brain areas implement control functions are unclear. Furthermore, aging is associated with reductions in the ability to implement control functions and questions remain as to whether unique cortical responses serve a compensatory role in maintaining maximal performance in later years. Described here are three studies in which electrophysiological data were recorded while participants performed modified versions of the standard Sternberg task. The goal was to determine how top-down control is implemented in younger adults and altered in aging. In study I, the effects of frequent stimulus repetition on the interference-related N450 were investigated in a Sternberg task with a small stimulus set (requiring extensive stimulus resampling) and a task with a large stimulus set (requiring no stimulus resampling).The data indicated that constant stimulus res amp ling required by employing small stimulus sets can undercut the effect of proactive interference on the N450. In study 2, younger and older adults were tested in a standard version of the Sternberg task to determine whether the unique frontal positivity, previously shown to predict memory impairment in older adults during a proactive interference task, would be associated with the improved performance when memory recognition could be aided by unambiguous stimulus familiarity. Here, results indicated that the frontal positivity was associated with poorer memory performance, replicating the effect observed in a more cognitively demanding task, and showing that stimulus familiarity does not mediate compensatory cortical activations in older adults. Although the frontal positivity could be interpreted to reflect maladaptive cortical activation, it may also reflect attempts at compensation that fail to fully ameliorate agerelated decline. Furthermore, the frontal positivity may be the result of older adults' reliance on late occurring, controlled processing in contrast to younger adults' ability to identify stimuli at very early stages of processing. In the final study, working memory load was manipulated in the proactive interference Sternberg task in order to investigate whether the N450 reflects simple interference detection, with little need for cognitive resources, or an active conflict resolution mechanism that requires executive resources to implement. Independent component analysis was used to isolate the effect of interference revealing that the canonical N450 was based on two dissociable cognitive control mechanisms: a left frontal negativity that reflects active interference resolution, , but requires executive resources to implement, and a right frontal negativity that reflects global response inhibition that can be relied on when executive resources are minimal but at the cost of a slowed response. Collectively, these studies advance understanding of the factors that influence younger and older adults' ability to satisfy goal-directed behavioural requirements in the face of interference and the effects of age-related cognitive decline.

Anachronistic Me: An Autoethnographic Account of Recovery through Volunteerism

The purpose of this autoethnography was to reflect upon the ways in which my recovery was aided by the personal connections made while volunteering in a homeless shelter. Congruent with autoethnographic best practice, data were collected through a variety of means, including: journaling, field notes, participant observation, and collection of artifacts. An autoethnographic narrative emerged out of the analysis of data detailing my recuperative journey. Results indicated that my time spent volunteering at the shelter: (a) fostered a sense of Community, (b) made me aware of Realizations that broadened my perspective, and (c) aided in motivating me to be Intentional about Improving my Life. These three themes proved to be important factors in my recovery process. This thesis will inform social science researchers and health advocates by making a contribution to the growing body of literature regarding recovery.

Développement de nouveaux outils de contrôle conformationnel utilisant des interactions non-covalentes pour effectuer des macrocyclisations

Les macrocycles ont longtemps attiré l'attention des chimistes. Malgré cet intérêt, peu de méthodes générales et efficaces pour la construction de macrocycles ont été développés. Récemment, notre groupe a développé un programme de recherche visant à développer de nouvelles voies vers la synthèse de paracyclophanes et ce mémoire présente l pluspart des efforts les plus récents dans ce domaine. Traditionnellement, la synthèse de paracyclophanes rigides est facilitée par l'installation d'un groupe fonctionnel capable de contrôler la structure de la molécule en solution (ex un élément de contrôle de conformation (ECC)). Cependant, cette approche utilisant des auxiliaires exige que le ECC soit facilement installé avant macrocyclisation et facilement enlevé après la cyclisation. Le présent mémoire décrit une méthode alternative pour guider la macrocyclisations difficile à travers l'utilisation d'additifs comme ECC. Les additifs sont des hétérocycles aromatiques N-alkylé qui sont bon marché, faciles à préparer et peuvent être facilement ajoutés à un mélange de réaction et enlevés suite à la macrocyclisation par simple précipitation et de filtration. En outre, les ECCs sont recyclables. L'utilisation du nouveau ECC est démontré dans la synthèse des para-et métacyclophanes en utilisant soit la métathèse de fermeture de cycle (RCM) ou couplage de Glaser-Hay.

Size invariant measures of association: characterization and difficulties

A measure of association is row-size invariant if it is unaffected by the multiplication of all entries in a row of a cross-classification table by a same positive number. It is class-size invariant if it is unaffected by the multiplication of all entries in a class (i.e., a row or a column). We prove that every class-size invariant measure of association as-signs to each m x n cross-classification table a number which depends only on the cross-product ratios of its 2 x 2 subtables. We propose a monotonicity axiom requiring that the degree of association should increase after shifting mass from cells of a table where this mass is below its expected value to cells where it is above .provided that total mass in each class remains constant. We prove that no continuous row-size invariant measure of association is monotonic if m ≥ 4. Keywords: association, contingency tables, margin-free measures, size invariance, monotonicity, transfer principle.

La genèse et le développement des partis politiques au Bas-Canada (1791-1840)

Ce mémoire s’intéresse à la formation des partis politiques et l’origine de la loyauté partisane à la Chambre d’assemblée du Bas-Canada entre 1791 et 1840. Pour ce faire, le présent mémoire fait une analyse systématique de tous les votes tenus en Chambre grâce à l’indice de loyauté et à la méthode de la Classification optimale (Optimal Classification) développée par Poole (2005). Il soutient la thèse selon laquelle l’ethnicité est la principale source de division entre les députés lors des votes tenus à la Chambre d’assemblée du Bas-Canada lors des premières législatures et que c’est plutôt l’opposition entre les réformistes constitutionnels et les conservateurs favorables à l’ancien régime qui explique les divisions entre les députés lors des deux dernières législatures. Il soutient également que le statut social des députés, le type de comté dans lequel ils sont élus, l’occupation civile des députés ou leur expérience parlementaire n’expliquent pas l’opposition entre les députés lors des votes au Parlement. Ce mémoire émet également l’hypothèse selon laquelle les partis politiques ont peu d’impact sur le comportement législatif de leurs membres : les députés sont libres de voter selon leurs préférences individuelles sans véritable discipline partisane.

Les actions de groupes en géométrie symplectique et l'application moment

Ce mémoire porte sur quelques notions appropriées d'actions de groupe sur les variétés symplectiques, à savoir en ordre décroissant de généralité : les actions symplectiques, les actions faiblement hamiltoniennes et les actions hamiltoniennes. Une connaissance des actions de groupes et de la géométrie symplectique étant prérequise, deux chapitres sont consacrés à des présentations élémentaires de ces sujets. Le cas des actions hamiltoniennes est étudié en détail au quatrième chapitre : l'importante application moment y est définie et plusieurs résultats concernant les orbites de la représentation coadjointe, tels que les théorèmes de Kirillov et de Kostant-Souriau, y sont démontrés. Le dernier chapitre se concentre sur les actions hamiltoniennes des tores, l'objectif étant de démontrer le théorème de convexité d'Atiyha-Guillemin-Sternberg. Une discussion d'un théorème de classification de Delzant-Laudenbach est aussi donnée. La présentation se voulant une introduction assez exhaustive à la théorie des actions hamiltoniennes, presque tous les résultats énoncés sont accompagnés de preuves complètes. Divers exemples sont étudiés afin d'aider à bien comprendre les aspects plus subtils qui sont considérés. Plusieurs sujets connexes sont abordés, dont la préquantification géométrique et la réduction de Marsden-Weinstein.

First results of experimental and theoretical investigations on sextet states of doubly-excited five-electron ions

In continuation of our previous work on doubly-excited ions with three and four electrons we present the first results on optical transitions in the term system of doubly-excited ions with five electrons. Transitions between such sextet states were identified in beam-foil spectra of the ions nitrogen, oxygen and fluorine. Assignments were first established by comparison with Multi-Configuration Dirac-Fock calculations. Later assignments were aided by Multi-Configuration Hartree-Fock calculations (see the contribution by G. Miecznik et al. in this issue). Decay curves were recorded for all six candidate lines. The lifetime results are compared to theoretical values which confirm most of the assignments qualitatively.

‘Ethical’, but Gender-Biased?

The migration of healthcare professionals from developing to developed countries, often aided by recruitment agencies, is a phenomenon of great international concern, as reflected in the construction of numerous ethical recruitment codes, which aim to govern the process. In an attempt to provide an overview of the situation, dealing specifically with the migration of nurses, as well as a critical and gender sensitive analysis of the codes, this paper follows three broad steps: first, it reviews the literature dedicated to the migration of nurses from developing to developed countries, adding a gendered account to more conventional push-pull explanations; second, it delineates the positive and negative effects that nurse migration has at the stakeholders levels of the individual, institutional, national and international level, paying particular attention to the role of gender; and third, it reviews and compares numerous codes for the ethical recruitment of nurses, highlighting the gendered rationale and consequences they may have. In showing that nurse migration is a gendered phenomenon, the paper questions whether the codes, written in gender neutral language, will come to bear unintended consequences that will effectively work to uphold gender stereotypes and inequalities.

How are Three-Deminsional Objects Represented in the Brain?

We discuss a variety of object recognition experiments in which human subjects were presented with realistically rendered images of computer-generated three-dimensional objects, with tight control over stimulus shape, surface properties, illumination, and viewpoint, as well as subjects' prior exposure to the stimulus objects. In all experiments recognition performance was: (1) consistently viewpoint dependent; (2) only partially aided by binocular stereo and other depth information, (3) specific to viewpoints that were familiar; (4) systematically disrupted by rotation in depth more than by deforming the two-dimensional images of the stimuli. These results are consistent with recently advanced computational theories of recognition based on view interpolation.

Análisis estructural del sector estratégico de vehículos automotores

Esta investigación se realizo con el fin de conocer el comportamiento y dinámica del sector automotriz en Colombia, haciendo especial énfasis en el sector de los vehículos de gama media, debido a que son el segmento de mayor movimiento del mercado automotriz en Colombia. El estudio se llevo a cabo utilizando el periodo de estudio entre 2004 y 2009 para identificar la situación actual del sector, en el que participaron las cuatro principales ensambladoras del país según la clasificación CIIU utilizada por la Superintendencia de Sociedades.

Depredación organizacional

El concepto de depredación en el ámbito de la organización es comúnmente asociado al deterioro de sus recursos, pero al abordarlo desde la ecología de poblaciones, el resultado es un enfoque centrado en las relaciones entre los actores de la organización y la interacción de tres variables principales: el poder de los actores, la intimidad entre ellos y la letalidad de sus actuaciones; estas dos últimas solicitadas en préstamo desde la clasificación funcional propuesta por la ecología de poblaciones y claves en la relación presa-depredador. El documento presenta una aproximación para aprovechar estos conocimientos disponibles en la ecología y argumenta que su estudio facilita la comprensión de los estilos de estrategia y dirección en la organización.

Análisis estratégico del sector automotriz en Colombia

Esta investigación se desarrolló con el fin de conocer de conocer detalladamente el comportamiento del sector automotriz de Colombia en los últimos años, haciendo énfasis en el segmento de vehículos de gama media del mercado, los cuales son los más comprados en volumen por los colombianos. El estudio se realizó en un periodo comprendido entre 2.006 y 2.011 para tener identificación y valoración real del sector hasta la situación actual, donde se evaluaron las ensambladoras presentes en el país que pertenecen a la división o clasificación arancelaria dada por Código Industrial Internacional Uniforme - CIIU. El trabajo se fundamenta en la metodología del Análisis Estructural de Sectores Estratégicos por medio del cual es necesario desarrollar un examen histórico del comportamiento del sector en los últimos años con el cual se presenta el desarrollo en términos económicos, ventas, estado de hacinamiento, manchas blancas, principales participantes del mercado, TLC´s y demás rubros que caracterizan el segmento. De igual manera, el trabajo de investigación refleja una vista general de las estrategias utilizadas por las principales marcas del estudio, evaluando como estas son imitadas o no por sus competidores, y de igual manera, determinar que hace a una empresa ser líder en el mercado no tan solo tomando el ámbito económico como pilar.

Factores relacionados con la tasa de hospitalización en pacientes con enfermedades cardiovasculares en tres instituciones de salud. Bogotá, 2011 – 2013

Introducción: Las enfermedades cardiovasculares constituyen uno de los principales obstáculos para el desarrollo del siglo XXI, según la OMS en el año 2008 fueron responsables del 30% de las muertes registradas en todo el mundo. Aunque la diabetes mellitus no se encuentra dentro de la clasificación establecida por la OMS de este grupo de enfermedades, consideramos importante su mención e inclusión dentro de nuestro estudio por el alto número de pacientes con esta enfermedad que cursa con complicaciones cardiovasculares asociadas. Metodología: Estudio de casos y controles seleccionados con un muestreo aleatorio simple con 80 casos y 80 controles apareados por edad y género, entre los cuales se encuentran 91 hombres y 60 mujeres, realizando un análisis estadístico univariado y multivariado para este tipo de estudios. Resultados: Los años de consumo de cigarrillo tuvieron una asociación con la ocurrencia del evento con un OR de 0.95 (intervalo de confianza (IC) del 95%, 0.91 – 0.99) y la asistencia a controles con especialidades de competencia cardiovascular la asociación del evento reporto un OR de 6,49 con un IC del 95%, 2.38 – 17.6. Conclusiones: De acuerdo a los resultados se encuentra que los años de consumo de cigarrillo tiene una asociación con la hospitalización en paciente con ECV y la asistencia a consultas con especialidades de competencia cardiovascular una asociación positiva con la hospitalización en este grupo de pacientes, lo que nos indica que los paciente que más se hospitalizan podrían estar relacionados con una mayor complejidad de sus patologías.

Key competences in the new ventures: a model for evaluating

This research studies from an internal view based on the Competency-Based Perspective (CBP), key organizational competencies developed for small new business. CBP is chosen in an attempt to explain the differences characterizing the closed companies from the consolidated ones. The main contribution of this paper is the definition of a set of key organizational competencies for new ventures from services and low technology based sectors. Using the classification proposed by [1] and a review of the entrepreneurship literature, the main competencies were defined and classified as: managerial, input-based, transformation-based, and output-based competencies. The proposed model for evaluating new ventures organizational competence is tested by means of Structural Equation