Dans ce mémoire, il sera question de la formation de dérivés pipéridines en utilisant la fragmentation de Grob. Tout d’abord, une introduction sur les alcaloïdes ainsi que sur l’expertise du groupe Charette associée à leur formation démontrera l’importance de ces composés dans le domaine de la chimie organique. Cela sera suivi par un résumé de la fragmentation de Grob incluant les conditions de réactions utilisées, l’importance de la structure de la molécule initiale, les prérequis stéréoélectroniques ainsi que les modifications qui y ont été apportées. Le chapitre 2 sera dédié au développement de la méthodologie c’est-à-dire, à l’optimisation de tous les paramètres jouant un rôle dans la fragmentation de Grob. Par la suite, l’étendue de la réaction ainsi que des explications sur la régiosélectivité et la diastéréosélectivité de la réaction seront fournies. La méthodologie peut être exploitée dans un contexte de synthèse qui sera démontré dans le chapitre 3. De plus, elle servira pour une étude mécanistique qui est encore d’actualité à partir du concept d’effet frangomérique. Finalement, quelques projets futurs, notamment des améliorations possibles de la méthodologie, seront présentés dans le dernier chapitre. Le tout sera suivi d’une conclusion résumant l’ensemble des travaux effectués. / This thesis discusses the formation of piperidine derivatives using the Grob fragmentation. Firstly, an introduction of the important alkaloid family as well as previous work completed by the Charette group towards the synthesis of these compounds will be demonstrated. This will be followed by a summary of the Grob fragmentation including a discussion of the reaction conditions, molecular structures, stereoelectronic requirements and modifications of the Grob fragmentation. Chapter 2 will be dedicated to the development of the methodology and more precisely, to the optimization of all parameters necessary to the reaction. Furthermore, the scope of the reaction and some explanation of the regioselectivity and the diastereoselectivity of the reaction will be discussed. The developed methodology can be used in a total synthesis and will be demonstrated in Chapter 3. Moreover, using the frangomeric effect concept, a mechanistic study on the Grob fragmentation will be discussed. Finally, some future projects, especially possible improvement of the methodology, will be presented in the last chapter. This is followed by a conclusion and a summary of the work completed on this project.

For over a decade, diquaternary ammonium gemini surfactants have shown promise as non-viral gene delivery agents in both in vitro and in vivo systems. Their continued development, however, requires an understanding of their biological fate. The absence of identification and quantification methods that can achieve that goal is what drove the development of simple and rapid mass spectrometry (MS)-based methods; the focus of my Ph.D. dissertation. Prior to the development of these MS-based methods, an understanding of the gas phase behavior of diquaternary ammonium gemini surfactants is required. The development of a universal fragmentation pathway for gemini surfactants was achieved using low resolution and high resolution MS instruments. Single stage (MS), tandem stage (MS/MS and quasi-multi-stage (quasi MS3) mass spectrometry analysis allowed for the confirmation of the molecular composition and structure of each gemini surfactant through the identification of common and unique mass to charge values. Understanding the fragmentation behavior allowed for the specific identification and/or quantification of gemini surfactants by MS-based methods; including liquid chromatography low resolution tandem mass spectrometry (LC-LR-MS/MS), fast chromatography low resolution tandem mass spectrometry, fast chromatography high resolution mass spectrometry, desorption electrospray ionization low resolution mass spectrometry and matrix assisted laser desorption ionization high resolution mass spectrometry. We hypothesized that a LC-LR-MS/MS method would be the most effective quantitative method for the quantification of N,N-bis(dimethylhexadecyl)-1,3-propane-diammonium dibromide (G16-3) within PAM212 cellular lysate; achieving the lowest lower limit of quantification (LLOQ). Although the LC-LR-MS/MS method achieved a LLOQ suitable for analysis of G16-3 within PAM212 cell lysate, its limitations made it an inefficient method. In comparison, the four alternative mass spectrometry methods were faster, more efficient and less expensive than a conventional LC-LR-MS/MS method for the post transfection quantification of G16-3 within PAM212 cell lysate to be determined; 1.45 ± 0.06 μM. Future application of the universal fragmentation pathway and each MS-based quantification method will be beneficial for the future development of diquaternary ammonium gemini surfactants to further understand their post transfection fate.

Fragmentation, which often involves the division of one’s self into professional and personal domains that are insulated from each other, is a serious problem for soldiers in today’s Army. This type of professional-personal fragmentation arises organically in military service. Unfortunately, it also seems that the past 12 years of persistent conflict have exacerbated the problem of fragmentation for many soldiers. Given this, I argue that any program that the Army implements for moral development should recognize fragmentation and provide resources and practices to combat it. I contend that the Army Profession campaign, which is the Army’s primary program for moral development, fails to meet either of these requirements. Moreover, it seems to serve as a catalyst that further fragments soldier’s lives. I believe this follows from the manner in which the campaign limits moral aspiration to a domain-specific good, professionalism. Thus it seems that the Army Profession campaign is not sufficient for soldiers’ moral development. Some may point to the Comprehensive Soldier Fitness program as the resource that the Army uses to address this problem because of its emphasis on the emotional, social, familial, and spiritual domains of soldiers. I argue, however, that neither the Army Profession campaign nor the Comprehensive Soldier Fitness program construes these domains as constitutive of moral development. Furthermore, both programs rely on experts to train soldiers in their respective concepts. This is problematic because soldiers do not find these experts to be credible. I go on to claim that leaders and peers who have a relationship with their fellow soldiers, and have earned their trust and respect, should function as the center of gravity for character development in the Army. Unfortunately, many leaders and soldiers lack the resources to do so. Thus, they often refer fellow soldiers back to the experts. Instead, leaders and peers should use the resources that virtue ethics provides with respect to self-perception, virtue-relevant goals, and the emotions to promote soldiers’ moral development. Toward that end, chaplains are well-suited to help leaders and peers gather the resources and develop the practices that will contribute to these aims.

Chapter 1 Hydrocarbon autoxidation, a free radical chain reaction, is believed to play a key role in the onset and developments of most degenerative diseases and disorders. The two propagating steps: 1) H-atom abstraction from the hydrocarbon by a hydrocarbon-derived peroxyl radical, and 2) addition of oxygen to the resultant alkyl radical to form a new peroxyl, play a role in determining the rate of hydrocarbon autoxidation, as well as the regio- and stereochemistry of the product hydroperoxides. In the current study, we carried out a set of calculations to provide a detailed framework for understanding the mechanism of the first two steps of autoxidation. Chapter 2 Radical-trapping chain-breaking antioxidants inhibit hydrocarbon autoxidation. Phenols are the prototypical radical-trapping antioxidants and are employed in nature, as well as in industry, to inhibit the autoxidation of hydrocarbons. The mechanism of inhibiting radical chain propagation has recently been suggested to be a PCET on the basis of theoretical calculations. It has been demonstrated that the antioxidant activitiy of phenols is increased in the presence of either protic acids or alcohols, but the basis of this acceleration is not well understood. In the current study, we used computational methods to investigate the effects of acids and alcohols on the PCET pathway for the reaction of phenol with a peroxyl radical. Chapter 3 The antibiotic pyrrolnitrin [3-chloro-4-(2’-nitro-3’-chlorophenyl) pyrrole] (PRN) is biosynthesized from L-tryptophan in four steps, catalyzed by the enzymes PrnA, B, C and D encoded by the prn operon. Two of the four gene products, PrnA and PrnC, are flavin-dependent halogenases, a recently discovered and highly interesting class of enzymatic halogenation catalysts. Their activities have never been unequivocally demonstrated by reconstitution of the activity from a recombinant protein. Herein, we report the results of our efforts to clone the genes encoding PrnA and PrnC, and overexpress, isolate and purify the proteins from E. coli. We were able to successfully reconsistute halogenation activity of both and have obtained the first kinetic data for PrnC, which shows kinetics similar to other flavin-dependent halogenases, along with substrate inhibition. / Thesis (Master, Chemistry) -- Queen's University, 2010-02-03 15:42:39.67

<p>The objective of this project is to study the production of Li, Be and B isotopes emitted in the interaction of 12C with 12C at incident energies of 200 and 400 MeV.<br /> The energies of these produced fragments were measured with a detector telescope consisting of two silicon detectors at the incident energy of 200 MeV while a third silicon detector was added for the measurements at 400 MeV.</p>

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

During the case of a hypothetical severe accident in a light water reactor, core damage may occur and molten fuel may interact with water resulting in explosive interactions. A Fuel-Coolant Interactions (FCI) consists of many complex phenomena whose characteristics determine the energetics of the interactions. The fuel melt initially undergoes fragmentation after contact with the coolant which subsequently increases the melt surface area exposed to coolant and causes rapid heat transfer. A substantial amount of research has been done to understand the phenomenology of FCI, still there are gaps to be filled in terms of the uncertainties in describing the processes such as breakup/fragmentation of melt and droplets. The objective of the present work is to substantiate the understanding in the premixing phase of the FCI process by studying the deformation/pre-fragmentation of melt droplets and also the mechanism of melt jet breakup. The focus of the work is to study the effect of various influential parameters during the premixing phase that determine the intensity of the energetics in terms of steam explosion. The study is based on numerical analysis starting from smaller scale and going to the large scale FCI. Efforts are also taken to evaluate the uncertainties in estimating the steam explosion loads on the reactor scale. The fragmented core is expected to form a porous debris bed. A part of the present work also deals with experimental investigations on the coolability of prototypical debris bed. Initially, the phenomenology of FCI and debris bed coolability is introduced. A review of the state of the art based on previous experimental and theoretical developments is also presented. The study starts with numerical investigation of molten droplet hydrodynamics in a water pool, carried out using the Volume Of Fluid (VOF) method in the CFD code ANSYS FLUENT. This fundamental study is related to single droplets in a preconditioning phase, i.e. deformation/pre-fragmentation prior to steam explosion. The droplet deformation is studied extensively also including the effect of the pressure pulse on its deformation behavior. The effect of material physical properties such as density, surface tension and viscosity are investigated. The work is then extended to 3D analysis as a part of high fidelity simulations, in order to overcome the possible limitations of 2D simulations. The investigation on FCI processes is then continued to the analysis on melt jet fragmentation in a water pool, since this is the crucial phenomenon which creates the melt-coolant pre-mixture, an initial condition for steam explosion. The calculations are carried out assuming non-boiling conditions and the properties of Wood’s metal. The jet fragmentation and breakup pattern are carefully observed at various Weber numbers. Moreover, the effect of physical and material properties such as diameter, velocity, density, surface tension and viscosity on jet breakup length, are investigated. After the fundamental studies, the work was extended to reactor scale FCI energetics. It is mainly oriented on the evaluation of uncertainties in estimating the explosion impact loads on the surrounding structures. The uncertainties include the influential parameters in the FCI process and also the code uncertainties in calculations. The FCI code MC3D is used for the simulations and the PIE (propagation of input errors) method is used for the uncertainty analysis. The last part of the work is about experimental investigations of debris coolability carried out using the POMECO-HT facility at KTH. The focus is on the determination of the effect of the bed’s prototypical characteristics on its coolability, in terms of inhomogeneity with heap like (triangular shape) bed and the radial stratified bed, and also the effect of its multi-dimensionality. For this purpose, four particle beds were constructed: two homogeneous, one with radial stratification and one with triangular shape, respectively. The effectiveness of coolability-enhanced measures such as bottom injection of water and a downcomer (used for natural circulation driven coolability, NCDC) was also investigated. The final chapter includes the summary of the whole work. / Under ett svårt haveri i en kärnkraftsreaktor kan en härdsmälta bildas och smältan växelverka på ett explosivt sätt med kylvattnet. En sådan FCI (Fuel-Coolant-Interaction) inbegriper flera fysikaliska processer vilkas förlopp bestämmer hur stor den frigjorda energin blir. Vid kontakt med vattnet fragmenteras först härdsmältan vilket i sin tur leder till att en större yta exponeras för kylvattnet och att värmeöverföringen från smältan snabbt ökar. Mycket forskning har ägnats åt att förstå vad som sker under en FCI men det finns fortfarande luckor att fylla vad beträffar t ex osäkerheter i beskrivningen av fragmentering av såväl smälta som enskilda droppar av smält material. Syftet med detta arbete är främst att underbygga en bättre förståelse av den inledande delen av en FCI genom att studera dels hur enskilda droppar av smält material deformeras och splittras och dels hur en stråle av smält material fragmenteras. Vi studerar särskilt vilka parametrar som mest påverkar den energi som frigörs vid ångexplosionen. Problemet studeras med numerisk analys med början i liten skala och sedan i full skala. Vi söker också uppskatta de laster som explosionen utsätter reaktorns komponenter för. En annan viktig fråga gäller kylbarheten hos den slaggansamling som bildas under reaktorhärden efter en FCI. Slagghögen förväntas ha en porös struktur och en del av avhandlingen redogör för experimentella försök som genomförts för att utvärdera kylbarheten i olika prototypiska slaggformationer. I avhandlingens inledning beskrivs de fysikaliska processerna under en FCI och kylningen av en slaggansamling. Det aktuella kunskapsläget på dessa områden presenteras också utgående från tidigare experimentella och teoretiska studier. Studierna i avhandlingen inleds med numerisk analys av hydrodynamiken för en enskild droppe smälta i en vattentank där VOF-metoden i CFD-programmet ANSYS FLUENT används. Denna grundläggande studie rör en enskild droppe under förstadiet till fragmentering och ångexplosion då droppen deformeras alltmer. Deformationen studeras ingående också med hänsyn tagen till inverkan av en tryckpuls. Inverkan av olika egenskaper hos materialet, som densitet, ytspänning och viskositet studeras också. Arbetet utvidgas sedan till en beskrivning i 3D för att undvika de begränsningar som finns i en 2D-simulering. Studierna av FCI utvidgas sedan till en analys av fragmentering av en stråle smälta i vatten. Detta är en kritisk del av förloppet då smälta och vatten blandas för att ge utgångstillståndet för ångexplosionen. Beräkningarna genomförs under antagande att kokning inte sker och med materialegenskaper som för Wood´s metall. Mönstret för fragmentering och uppsplittring studeras ingående för olika Weber-tal. Dessutom studeras effekten på strålens uppsplittringslängd av parametrar som diameter och hastighet för strålen samt densitet, ytspänning och viskositet hos materialet. Efter dessa grundläggande studier utvidgas arbetet till FCI-energier i reaktorskala. Här ligger tonvikten på utvärdering av osäkerheter i bestämningen av den inverkan explosionen har på omgivande konstruktioner och komponenter. Osäkerheterna inkluderar eventuell bristande noggrannhet hos såväl de viktiga parametrarna i FCI-processen som i själva beräkningarna. Den sista delen av arbetet handlar om experimentella undersökningar av slaggformationens kylbarhet som genomförts i uppställningen POMECO-HT vid avdelningen för kärnkraftsäkerhet på KTH. Vi vill bestämma effekten av formationens prototypiska egenskaper på kylbarheten. För detta ändamål konstruerades fyra olika formationer: två homogena, en med radiell variation i partikelstorlek och en med triangulär variation. Vi undersökte också hur förbättrad kylning kan uppnås genom att tillföra kylvatten underifrån respektive via ett fallrör (kylning genom naturlig cirkulation). I det avslutande kapitlet ges en sammanfattning av hela arbetet. / <p>QC 20150507</p>

Habitat loss and fragmentation have been identified as the main drivers of biodiversity loss. These drivers increase the proportion of habitat edges and change the configuration of landscapes. Habitat edges are known to affect ecological patterns and processes, however, is still unknown how these boundaries affect the assemblage of interactions among species within a community, and particularly its structure. Food webs depict not only the composition of the community, but also the feeding links, which represent a measure of energy flow. Therefore, they can inform about the relationships among community diversity, stability, and ecosystem functions. This thesis explores the effects of habitat edges across native vs. managed forests on the food web of a tri-trophic system comprising plants, herbivores (Lepidoptera larvae) and predators (parasitoids). Particularly, it addresses three main objectives: 1) how food webs at habitat edges are assembled from the species and interactions present in the adjoining habitats; 2) how phylogenetic diversity and the coevolutionary signal among interacting species change across a habitat edge gradient; and 3) whether the mechanisms driving community-wide consumption rates and the ecosystem service of pest control are related to structural characteristics of the food webs. The key findings of this thesis are that, despite the composition of species and interactions of native and managed habitats merging at their interface, food-web structure did not arise as a simple combination of its adjacent habitat webs, potentially due to differential responses of organisms to habitat edges. Moreover, beyond taxonomic composition, the phylogenetic diversity and signal of coevolution among interacting species also change between habitat types, even though this did not translate to changes in consumption rates. Consumption rates and their stability increased with complementarity and redundancy in resource-use among predators. This reflects how environmental changes such as habitat fragmentation can have an effect beyond composition per se, affecting the assemblage of species interactions and even potentially interfering with natural evolutionary processes. Therefore, using interaction-network approaches for determining the impacts of changes may shed light on the underlying mechanisms driving such changes, and help to develop landscape management plans that reduce negative effects on species assemblages.

Agricultural expansion has transformed and fragmented natural forest habitats at an alarming rate, and dramatic increases in agricultural intensification have since taken place in order to keep pace with human population growth and food demands. This simultaneously poses a considerable threat to biodiversity in agricultural landscapes, as production land is now one of the largest terrestrial biomes on the planet. Therefore, its contribution to biodiversity conservation is critical. Links between the intensification of agricultural systems and ‘in situ’ declines of biodiversity on farmland have been well documented. However, despite growing recognition that system inputs such as fertiliser and livestock can move or ‘spillover’ into adjacent natural habitats, there has been no direct quantification of the extent of impacts in recipient ecosystems. These abiotic and biotic pathways can cause dramatic impacts on the diversity, composition, and functioning of remaining natural ecosystems, and on their ability to provide a variety of essential ecosystem services. Due to concerns regarding future food security, balancing trade-offs between agriculture and conservation has subsequently become a hot topic in ecological research. However, without any direct quantification of the off-site ecological impacts of agricultural intensification in mosaic landscapes, it is inherently difficult to fully evaluate strategies aimed at balancing production and conservation. Using New Zealand farming systems as a case study, this thesis aims to address gaps in our current understanding of how increasing agricultural intensification impacts biodiversity in native forest remnants embedded within production landscapes. The first main chapter explores whether the magnitude of ecological impact in forest remnants (for a suite of 26 response measures) and severity of edge effects, scale with the degree of land-use intensity in surrounding agricultural pastures. This chapter also examines whether ecological responses differ in remnants ‘spared’ for conservation purposes (i.e. where livestock are excluded by fencing). The second chapter uses a model food-chain approach native to New Zealand, to test whether nutrient spillover from agricultural pastures influences plant-herbivore and herbivore-parasitoid interactions in forest remnants. This chapter also includes a large-scale common garden fertilisation experiment using the same tri-trophic system, which was established to examine bottom-up multi-trophic responses to the independent and combined effects of Nitrogen (N), Phosphorus (P) and cow dung and urine. The third main chapter uses a novel stable isotope approach for quantifying community-wide incorporation of resources into trophic structure. I test for the first time whether increasing intensity of farming systems drives greater nutrient spillover spatially into adjacent forest remnant soils and examine scaling effects of 15N (as a marker for anthropogenic N) through multiple trophic levels. Beyond finding that agricultural land-use intensity generally has negative off-site effects on biodiversity, the key findings of this thesis were (i) spillover of nitrogen and phosphorus from agricultural systems into adjacent remnant soils is exacerbated by increases in land-use intensity, with (ii) percolating bottom-up effects on plant and insect community dynamics. (iii) The magnitude of ecological impacts in forest remnants scales linearly with increasing land-use intensity, as does (iv) direct anthropogenic N enrichment across multiple trophic levels, which has the potential to severely jeopardise the stability of ecologically important remnant habitats. (v) Although there were stark structural differences in remnants with and without livestock exclusion, impacts of land-use intensity on ecological response metrics were actually comparable across all sites. (vi) Livestock exclusion should be a priority first step towards conserving native forest remnants, however it should be recognised that fencing does not prevent abiotic channels of nutrient spillover (fertiliser drift, overland flow, leaching) in land characteristic of land spared for nature. (vii) Consequently, increasing land-use intensity compromises the effectiveness of the land-sparing trajectory for conserving native biodiversity, which is currently undertaken in New Zealand production systems. Given the overall strength of these findings and the novel, ecosystem-wide and landscape-scale approaches taken to address fundamental questions, the work in this thesis greatly enhances our knowledge of the relationships between agricultural productivity and ecological impacts in spatially-coupled ecosystems. This is highly important, not only in New Zealand but worldwide, as it is anticipated that unstoppable human population growth and food security pressures will cause ecological impacts both on the farm and in adjacent natural ecosystems to become even more severe. Therefore, determining the relationship between land-use intensification and biodiversity loss represents the cornerstone of sustainable agricultural development in the future.