Investigation of the catalytic formation, reactivity and synthetic scope of sp³-gem-organodimetallic palladio(II)/main group metal (main group metal = tributylstannyl, dialkylalumino) alkane species has been carried out. Insight was expanded regarding the inter- and intramolecular reactivity of vinylmetallic reagents in presence of transition metal catalysts. New Pd-catalysed methodologies for carbon-carbon bond formation were developed, such as cyclopropanation of strained olefins, as well as tandem vinylalane arylation/1,2-methyl transfer and 1,2-diarylation. On the one hand, geminal π-allylpalladio(II)/tributylstannylalkane intermediates are produced by oxidative addition of Pd(0) catalysts to α-tributylstannylpropenyl acetate derivatives. They adopt ambiphilic behaviour depending on the transition metal pre-catalyst, presence or absence of phosphine ligands, and reaction temperature. In presence of tetrakis(triphenylphosphine)palladium(0) with additional bidentate ligand, the carbenoid reactivity of these gem-organobismetallic species is exposed by reaction with dimethyl malonate. Deuterium-labeling studies demonstrated sequential functionalisation of the C-Sn and C-Pd bonds. Conversely, phosphine-free catalyst bis(dibenzylideneacetone)palladium(0) uncovers metal-carbene reactivity, and dimerisation and strained alkene cyclopropanation reactions are observed. The nature of the palladium catalyst controls the reactivity of the carbenoid species. Finally, bis(cyclooctadienerhodium(I) chloride) catalytically activates the alkenylstannane moiety, leaving the allylic acetate leaving group available for further transformations. On the other hand, gem-disubstituted trifluoromethanesulfonyloxy- and iodopalladio(II)/ dialkylaluminoneopentane species are generated by intramolecular migratory insertion of 2,2-disubstituted-1-butenyldialkylalanes with σ-arylpalladium(II) triflate and iodide intermediates. Using excess Lewis-basic 1,4-diazabicyclo[2.2.2]octane, electron-rich tris(para-methoxyphenyl)phosphine ligand and acetonitrile as solvent, tandem arylation/1,2-alkyl migration from aluminum to carbon affords 7-substituted-1-ethyl-1-methylindanes containing an all-carbon quaternary stereogenic centre in good yields. This reaction is tolerant of 6-aryl methyl ethers, thioethers and trimethylsilanes. Deuterium labeling established that protiodealumination of the key neopentyl(methyl)aluminum triflate intermediate is caused by the acetonitrile solvent. The organodimetallic species in that study were shown to be configurationally stable, hence the stereospecificity of the process that proceeds via carbopalladation, transmetalation and reductive elimination of an alkylpalladium(II) intermediate. When applied to 1-naphthyl triflate-tethered vinylalanes, the same reaction conditions mediate stereospecific 1,2-diarylation, leading to 2,3,3a,4-tetrahydro-1H-cyclopenta[def]phenanthrenes in excellent yields. The influence of DABCO, tether length and solvent polarity was studied. Selective tandem arylation/1,2-methyl migration could also be achieved in non-polar solvent in absence of Lewis base. While steric properties took precedence over electronic considerations when inducing product selection, preagostic C-H···Pd interactions were postulated to facilitate 1,3-metal migration in the production of 1H-cyclopenta[def]phenanthrene derivatives.

Begging as a phenomenon has again become a hot topic of debate both in the public and the media. Actions have been discussed and motions have been given to social authorities in the country. During the last two years people from other parts of Europe who engage in street begging have been seen on the streets of Kristianstad. The purpose of this paper is to find out the individuals, certain authorities and other participants experiences of people begging in public places in Kristianstad. We have used a combination of qualitative, quantitative and literature review method and we have a social constructionist perspective as a basis. The participants and authorities we have included in the study are the police, the social services, security guards, a shop owner and two other assistance agencies. Interviews have been carried out with participants and authorities, and a survey has been done by individuals. A series of articles and history books have been reviewed since the begging is a historical phenomenon as well as a contemporary. The results show a clear division into two camps regarding experiences and opinions about street beggars and begging as a phenomenon. The majority expresses dissatisfaction and many propose measures and actions. Our final discussion is marked by our own thoughts and values ​​that emerged during the work, which we tried to moderate through the rest of the essay. / Tiggeri som fenomen har på nytt blivit ett hett ämne för debatt både för allmänhet och i media. Åtgärder har diskuterats och motioner om förbud lämnas till socialnämnder i landet. I Kristianstad har det under de senaste två åren kommit personer hit från andra delar av Europa som ägnar sig åt gatutiggeri. Syftet med denna uppsats är att ta reda på privatpersoners, vissa myndigheters och andra aktörers uppfattning av personer som tigger på offentlig plats i Kristianstad. Vi har använt oss av en kombination av kvalitativ, kvantitativ och litteraturstudie som metod och vi har ett socialkonstruktionistiskt perspektiv som grund. De aktörer och myndigheter vi tagit med i undersökningen är polis, socialtjänst, vakter, butiksägare och två andra biståndsverksamheter. Intervjuer har gjorts med aktörerna och myndigheterna och en enkätundersökning har gjorts med privatpersoner. En rad artiklar och historieböcker har gåtts igenom då tiggeri ju är ett historiskt fenomen såväl som ett nutida. Resultatet visar på en klar uppdelning i två läger gällande uppfattningar och åsikter om gatutiggare och tiggeri som fenomen. Majoriteten uttrycker ett missnöje och många föreslår åtgärder och insatser. Vår slutdiskussion präglas av våra egna tankar och värderingar som framkommit under arbetets gång, vilka vi försökt tona ner i resten av uppsatsen.

Investigation of the catalytic formation, reactivity and synthetic scope of sp³-gem-organodimetallic palladio(II)/main group metal (main group metal = tributylstannyl, dialkylalumino) alkane species has been carried out. Insight was expanded regarding the inter- and intramolecular reactivity of vinylmetallic reagents in presence of transition metal catalysts. New Pd-catalysed methodologies for carbon-carbon bond formation were developed, such as cyclopropanation of strained olefins, as well as tandem vinylalane arylation/1,2-methyl transfer and 1,2-diarylation. On the one hand, geminal π-allylpalladio(II)/tributylstannylalkane intermediates are produced by oxidative addition of Pd(0) catalysts to α-tributylstannylpropenyl acetate derivatives. They adopt ambiphilic behaviour depending on the transition metal pre-catalyst, presence or absence of phosphine ligands, and reaction temperature. In presence of tetrakis(triphenylphosphine)palladium(0) with additional bidentate ligand, the carbenoid reactivity of these gem-organobismetallic species is exposed by reaction with dimethyl malonate. Deuterium-labeling studies demonstrated sequential functionalisation of the C-Sn and C-Pd bonds. Conversely, phosphine-free catalyst bis(dibenzylideneacetone)palladium(0) uncovers metal-carbene reactivity, and dimerisation and strained alkene cyclopropanation reactions are observed. The nature of the palladium catalyst controls the reactivity of the carbenoid species. Finally, bis(cyclooctadienerhodium(I) chloride) catalytically activates the alkenylstannane moiety, leaving the allylic acetate leaving group available for further transformations. On the other hand, gem-disubstituted trifluoromethanesulfonyloxy- and iodopalladio(II)/ dialkylaluminoneopentane species are generated by intramolecular migratory insertion of 2,2-disubstituted-1-butenyldialkylalanes with σ-arylpalladium(II) triflate and iodide intermediates. Using excess Lewis-basic 1,4-diazabicyclo[2.2.2]octane, electron-rich tris(para-methoxyphenyl)phosphine ligand and acetonitrile as solvent, tandem arylation/1,2-alkyl migration from aluminum to carbon affords 7-substituted-1-ethyl-1-methylindanes containing an all-carbon quaternary stereogenic centre in good yields. This reaction is tolerant of 6-aryl methyl ethers, thioethers and trimethylsilanes. Deuterium labeling established that protiodealumination of the key neopentyl(methyl)aluminum triflate intermediate is caused by the acetonitrile solvent. The organodimetallic species in that study were shown to be configurationally stable, hence the stereospecificity of the process that proceeds via carbopalladation, transmetalation and reductive elimination of an alkylpalladium(II) intermediate. When applied to 1-naphthyl triflate-tethered vinylalanes, the same reaction conditions mediate stereospecific 1,2-diarylation, leading to 2,3,3a,4-tetrahydro-1H-cyclopenta[def]phenanthrenes in excellent yields. The influence of DABCO, tether length and solvent polarity was studied. Selective tandem arylation/1,2-methyl migration could also be achieved in non-polar solvent in absence of Lewis base. While steric properties took precedence over electronic considerations when inducing product selection, preagostic C-H···Pd interactions were postulated to facilitate 1,3-metal migration in the production of 1H-cyclopenta[def]phenanthrene derivatives.

In this thesis, an algorithm for visual detecting and tracking of very low SNR targets, i.e. dim targets, is developed. Image processing of single frame in time cannot be used for this aim due to the closeness of intensity spectrums of the background and target. Therefore / change detection of super pixels, a group of pixels that has sufficient statistics for likelihood ratio testing, is proposed. Super pixels that are determined as transition points are signed on a binary difference matrix and grouped by 4-Connected Labeling method. Each label is processed to find its vector movement in the next frame by Label Destruction and Centroids Mapping techniques. Candidate centroids are put into Distribution Density Function Maximization and Maximum Histogram Size Filtering methods to find the target related motion vectors. Noise related mappings are eliminated by Range and Maneuver Filtering. Geometrical centroids obtained on each frame are used as the observed target path which is put into Optimum Decoding Based Smoothing Algorithm to smooth and estimate the real target path. Optimum Decoding Based Smoothing Algorithm is based on quantization of possible states, i.e. observed target path centroids, and Viterbi Algorithm. According to the system and observation models, metric values of all possible target paths are computed using observation and transition probabilities. The path which results in maximum metric value at the last frame is decided as the estimated target path.

Pseudoexfoliation (PEX) syndrome is an age-related condition characterized by the production and accumulation of extracellular fibrillary material in the anterior segment of the eye. PEX predisposes for several pathological conditions, such as glaucoma and complications during and after cataract surgery. The pathogenesis of PEX is not yet fully understood. It is multifactorial with genetics and ageing as contributing factors. We aimed to study the proteome in aqueous humor (AH) in PEX in order to increase the knowledge about its pathophysiology. Therefore, we developed sampling techniques and evaluated separation methods necessary for analyzing small sample volumes. Other objectives were to study the lens capsule in eyes with PEX regarding small molecules, and to investigate the association between PEX and cataract surgery in a population-based 30-year follow-up study. Samples of AH from eyes with PEX and control eyes were collected during cataract surgery. In pooled, and individual samples, various liquid based separation techniques and high resolution mass spectrometry were utilized. For quantitation, various methods for labeling, and label free techniques were applied. Lens capsules were collected from some of the patients, and analysed by imaging mass spectrometry. A cohort of 1,471 elderly individuals underwent a comprehensive ophthalmological examination at baseline. Medical information was obtained by questionnaires, and from medical records. Incident cases of cataract surgery were identified by review of medical records. In the initial study, several techniques were explored for protein detection, and a number of proteins were identified as differentially expressed. In the individually labelled samples, changes in the proteome were observed. Eyes with PEX contained higher levels of proteins involved in inflammation, oxidative stress, and coagulation, suggesting that these mechanisms are involved in the pathogenesis in PEX. The levels of β/γ-crystallins were significantly increased in PEX, which is a novel finding. In the lens capsules from individuals with PEX, changes in the lipid composition was observed with time-of-flight secondary ion mass spectrometry. These changes remain to be elucidated. By multivariate analysis, lens opacities were the first, and PEX the second most important predictor for cataract surgery, the later accounting for a 2.38-fold increased risk for cataract surgery.

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

Blood oxygen level-dependent (BOLD) magnetic resonance (MR) imaging enables non-invasive spatial mapping of changes in cerebral blood flow (CBF). By applying a vasodilatory stimulus (such as inhaled CO2) during BOLD MR imaging, one can measure cerebral vasodilatory capacity. "Cerebrovascular reactivity" (CVR) is defined as the change in CBF per unit of vasodilatory stimulus. Vasodilatory capacity is clinically important as vasodilatation is a mechanism by which the brain maintains constant CBF despite reductions in cerebral perfusion pressure.ii Patients with arterial narrowing commonly demonstrate a paradoxical response: vasodilatory stimulus-induced reduction of BOLD MR signal. BOLD MR depends on CBF but on other factors too. Does a reduction of BOLD MR signal indicate a decrease in flow? Does BOLD MR CVR correlate with CVR measured using arterial spin labeling (ASL) MR? I studied thirty-eight patients with stenosis of brain-supplying arteries and found that the BOLD CVR and ASL CVR results correlate strongly (R=0.83, P<0.0001 for cerebral hemispheric gray matter). The second study aimed to determine whether preoperative CVR predicts the hemodynamic effect of extracranial-intracranial bypass surgery. Whereas prior studies relied on right-left interhemispheric CVR asymmetry indices, this study used “absolute” CVR from each hemisphere. I studied twenty-five patients with intracranial arterial stenosis. I found that the group with normal pre-operative CVR showed no change in CVR following bypass surgery (0.22% ± 0.05% to 0.22% ± 0.01% (mean ± SD)(P=0.881)), the group with reduced pre-operative CVR demonstrated an improvement (0.08% ± 0.05% to 0.21 ± 0.08% (mean ± SD)(P<0.001)), and the group with paradoxical pre-operative CVR demonstrated the greatest improvement (-0.04% ± 0.03% to 0.27% ± 0.03% (P=0.028)). ii Patients with arterial narrowing commonly demonstrate a paradoxical response: vasodilatory stimulus-induced reduction of BOLD MR signal. BOLD MR depends on CBF but on other factors too. Does a reduction of BOLD MR signal indicate a decrease in flow? Does BOLD MR CVR correlate with CVR measured using arterial spin labeling (ASL) MR? I studied thirty-eight patients with stenosis of brain-supplying arteries and found that the BOLD CVR and ASL CVR results correlate strongly (R=0.83, P<0.0001 for cerebral hemispheric gray matter). The second study aimed to determine whether preoperative CVR predicts the hemodynamic effect of extracranial-intracranial bypass surgery. Whereas prior studies relied on right-left interhemispheric CVR asymmetry indices, this study used “absolute” CVR from each hemisphere. I studied twenty-five patients with intracranial arterial stenosis. I found that the group with normal pre-operative CVR showed no change in CVR following bypass surgery (0.22% ± 0.05% to 0.22% ± 0.01% (mean ± SD)(P=0.881)), the group with reduced pre-operative CVR demonstrated an improvement (0.08% ± 0.05% to 0.21 ± 0.08% (mean ± SD)(P<0.001)), and the group with paradoxical pre-operative CVR demonstrated the greatest improvement (-0.04% ± 0.03% to 0.27% ± 0.03% (P=0.028)). The third study arose from an unexpected observation: paradoxical reactivity in the white matter of young healthy subjects. I evaluated healthy subjects using BOLD CVR and ASL CVR, transformed all CVR maps into a common brain space, and generated composite maps of CVR. Composite maps confirmed regions of significant paradoxical iii reactivity in the white matter. These regions may represent the physiological correlate of previously anatomically defined border-zones (watershed zones). The regions match the locations where elderly patients develop white matter rarefaction, so-called leukoaraiosis.

Blood oxygen level-dependent (BOLD) magnetic resonance (MR) imaging enables non-invasive spatial mapping of changes in cerebral blood flow (CBF). By applying a vasodilatory stimulus (such as inhaled CO2) during BOLD MR imaging, one can measure cerebral vasodilatory capacity. "Cerebrovascular reactivity" (CVR) is defined as the change in CBF per unit of vasodilatory stimulus. Vasodilatory capacity is clinically important as vasodilatation is a mechanism by which the brain maintains constant CBF despite reductions in cerebral perfusion pressure.ii Patients with arterial narrowing commonly demonstrate a paradoxical response: vasodilatory stimulus-induced reduction of BOLD MR signal. BOLD MR depends on CBF but on other factors too. Does a reduction of BOLD MR signal indicate a decrease in flow? Does BOLD MR CVR correlate with CVR measured using arterial spin labeling (ASL) MR? I studied thirty-eight patients with stenosis of brain-supplying arteries and found that the BOLD CVR and ASL CVR results correlate strongly (R=0.83, P<0.0001 for cerebral hemispheric gray matter). The second study aimed to determine whether preoperative CVR predicts the hemodynamic effect of extracranial-intracranial bypass surgery. Whereas prior studies relied on right-left interhemispheric CVR asymmetry indices, this study used “absolute” CVR from each hemisphere. I studied twenty-five patients with intracranial arterial stenosis. I found that the group with normal pre-operative CVR showed no change in CVR following bypass surgery (0.22% ± 0.05% to 0.22% ± 0.01% (mean ± SD)(P=0.881)), the group with reduced pre-operative CVR demonstrated an improvement (0.08% ± 0.05% to 0.21 ± 0.08% (mean ± SD)(P<0.001)), and the group with paradoxical pre-operative CVR demonstrated the greatest improvement (-0.04% ± 0.03% to 0.27% ± 0.03% (P=0.028)). ii Patients with arterial narrowing commonly demonstrate a paradoxical response: vasodilatory stimulus-induced reduction of BOLD MR signal. BOLD MR depends on CBF but on other factors too. Does a reduction of BOLD MR signal indicate a decrease in flow? Does BOLD MR CVR correlate with CVR measured using arterial spin labeling (ASL) MR? I studied thirty-eight patients with stenosis of brain-supplying arteries and found that the BOLD CVR and ASL CVR results correlate strongly (R=0.83, P<0.0001 for cerebral hemispheric gray matter). The second study aimed to determine whether preoperative CVR predicts the hemodynamic effect of extracranial-intracranial bypass surgery. Whereas prior studies relied on right-left interhemispheric CVR asymmetry indices, this study used “absolute” CVR from each hemisphere. I studied twenty-five patients with intracranial arterial stenosis. I found that the group with normal pre-operative CVR showed no change in CVR following bypass surgery (0.22% ± 0.05% to 0.22% ± 0.01% (mean ± SD)(P=0.881)), the group with reduced pre-operative CVR demonstrated an improvement (0.08% ± 0.05% to 0.21 ± 0.08% (mean ± SD)(P<0.001)), and the group with paradoxical pre-operative CVR demonstrated the greatest improvement (-0.04% ± 0.03% to 0.27% ± 0.03% (P=0.028)). The third study arose from an unexpected observation: paradoxical reactivity in the white matter of young healthy subjects. I evaluated healthy subjects using BOLD CVR and ASL CVR, transformed all CVR maps into a common brain space, and generated composite maps of CVR. Composite maps confirmed regions of significant paradoxical iii reactivity in the white matter. These regions may represent the physiological correlate of previously anatomically defined border-zones (watershed zones). The regions match the locations where elderly patients develop white matter rarefaction, so-called leukoaraiosis.

La thèse analyse un document intitulé Record Labeling Hearing (RLH) (1985), qui reprend dans son intégralité une séance qui s’est tenue au Congrès des États-Unis à propos du contenu jugé problématique de certains albums de musique. Au cœur de cette séance, se retrouve le Parents Music Resource Centre (PMRC), un groupe de pression qui voit le jour en 1984. D’après le PMRC, les albums avec des paroles traitant de sexe, de violence, d’occulte, de drogues et d’alcool méritent l’autocollant du « Parental Advisory : Explicit Lyrics » afin d’avertir les parents des thématiques abordées. La séance réunit des sénateurs du Congrès américain, les membres du PMRC et des alliés de ces derniers, dont la National Parent/Teacher Association (NPTA), ainsi que des représentants de l’industrie de la musique et trois artistes. Nous verrons dans la thèse qu’en fait, c’est le heavy metal que le PMRC et ses alliés visaient lors du RLH et non par exemple certains contenus transversaux à divers types d’albums de musique. A cette époque, la sous-culture du heavy metal était encore en émergence et pour tout dire bien fragile. En 1985, elle était même menacée de fragmentation en raison de la popularité de certains de ses sous-genres. Or, en présentant le heavy metal comme une contre-culture, le RLH a aidé ce genre musical à se constituer en véritable sous-culture.

No description available.