Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.

"Man of science, man of faith" : Lost, consumer agency and the fate/free will binary in the post-9/11 context

In 2004, Lost debuted on ABC and quickly became a cultural phenomenon. Its postmodem take on the classic Robinson Crusoe desert island scenario gestures to a variety of different issues circulating within the post-9II1 cultural consciousness, such as terrorism, leadership, anxieties involving air travel, torture, and globalization. Lost's complex interwoven flashback and flash-forward narrative structure encourages spectators to creatively hypothesize solutions to the central mysteries of the narrative, while also thematically addressing archetypal questions of freedom of choice versus fate. Through an examination of the narrative structure, the significance of technological shifts in television, and fan cultures in Lost, this thesis discusses the tenuous notion of consumer agency within the current cultural context. Furthermore, I also explore these issues in relation to the wider historical post-9/II context.

Unveiling the Influence of Consumer Wine Appreciation Dimension on Purchasing Behavior

Consumption values and different usage situations have received extensive interest from scholars; however, there is a lack of understanding regarding how these two constructs interact when it comes to the purchase decisions of consumers. This study examines the relationship between consumption values, consumption situations, and consumers’ purchasing decisions in terms of their willingness to pay and the purchase quantity. First of all, my model proposes that all four consumption values and different situations have a positive effect on consumers’ willingness to pay as well as the quantity they purchase. It also proposes that varying usage situations moderate the effect of consumption values on consumers’ purchasing decisions. In my conceptual model, I have also integrated the epistemic and conditional values where there is a gap in the existing literature. Prior literature has isolated the consumption values when studying how they affect consumer behavior and has not examined how consumption situations moderate the relationship between consumption values and purchasing decisions. Also, the existing literature has mostly focused on how consumption values affect purchase intentions, brand loyalty, or satisfaction, whereas my study focuses on purchasing decisions. For my study, the participants were randomly chosen from the general wine consumer population and the age range was between 20 and 75, which included 83 male respondents and 119 female respondents. The data received from my respondents support my hypotheses for the model. In my final chapter, I discuss the theoretical and managerial implications as well as suggestions for future research.

Gaining Insights About Water: The Value of Surveys in First Nations Communities to Inform Water Governance

Knowledge of how water is perceived, used and managed in a community is critical to the endeavour of water governance. Surveys of individuals residing in a community offer a valuable avenue to gain information about several of these aspects of water. This paper draws upon experiences in three First Nation communities to explore the values of surveys to illuminate water issues and inform water decision-making. Findings from experiences with surveys in Six Nations of the Grand River, Mississaugas of the New Credit, and Oneida First Nation of the Thames reveal rich information about how surveys can provide insights about: the connection of individuals to the land, water and their community; reasons for valuing water; perceptions of water quality and issues surrounding water-related advisories; and, degree of satisfaction with water management and governance at different scales. Community partners reflected upon the findings of the survey for their community. Dialogue was then broadened across the cases as the partners offer benefits and challenges associated with the survey. Community surveys offer an important tool in the resource managers’ toolbox to understand social perceptions of water and provide valuable insights that may assist in improving its governance.

Sustainability, Fashion Design, and Consumerism: Undergraduate Entry Level Fashion Students' Knowledge, Attitudes, and Habits

This qualitative inquiry explored 7 undergraduate students' attitudes, habits, and knowledge of consumerism, fashion design, and sustainability. The postmodern study employed crystallization as its methodological framework to gain insight into how participants' knowledge is manifested in their daily habits, and used 4 methods of data gathering: semistructured interviews, visual exercises, journal entries, and the researcher's own reflections. Four major themes emerged: Knowledge-Concepts Linked and Fragmented; Dissonance Between Knowledge Versus Attitudes and Consumer Habits; Surrendering to the Unsustainable Structures; Design Process and Caring Attitude. Findings indicate that participants possessed some knowledge of sustainability but lacked a well-rounded understanding of environmental and humanitarian implications of Western consumer society. Findings also reveal a dissonance between participants' knowledge and attitudes-affecting how their knowledge influences their behaviour-and how reflection, creative thinking, and drawing initiate change in participants' underlying attitudes. Recommendations are made to merge a variety of theoretical frameworks into the educational system in order to create curricula that offer a holistic overview and unique insights into sustainability challenges, particularly in specialized areas of the fashion industry.

CENTRAL NORTH ATLANTIC PALEOCEANOGRAPHY DURING THE MIDDLE PLEISTOCENE (ca. 726–603 ka): INSIGHTS FROM THE DINOFLAGELLATE CYST RECORD

Integrated Ocean Drilling Program (IODP) Site U1313, located at the northern boundary of the subtropical gyre in the central North Atlantic, lies within the southern part of the ice-rafted debris belt. Seventy-three palynological samples were studied from an uninterrupted interval ca. 726–603 ka (upper Marine Isotope Stage [MIS] 18 through lower MIS 15) to resolve conflicting paleoceanographic interpretations. Glacial stages were characterized by high productivity surface waters reflecting a southward shift of the Arctic Front. Sea surface salinities (SSSs) and sea surface temperatures (SSTs) were obtained by transfer functions using the Modern Analogue Technique. The lowest SSTs of 9ºC (±1.3) and 10ºC (±1.3) were recorded in glacial MIS 16 and MIS 18 respectively. However, these reconstructions are influenced by abundant heterotrophic taxa and may reflect elevated nutrient levels rather than lowered temperatures. Reworked palynomorphs uniquely indicate a Cretaceous as well as Paleozoic provenance for the first Heinrich-like events.

Insights Into the Remembered Educational Experiences of Male Caribbean Immigrants to Canada: Literacy and Identity in the Canadian Classroom

Abstract Past research has addressed the issue of male underachievement in literacy as an issue of global concern. This qualitative study focused on one subgroup of males which the literature highlighted as most at risk of educational underachievement in the Canadian educational landscape: male Caribbean immigrants to Canada. The research questions that framed the study sought to gain insight into the educational experiences of this group of learners so that ways through which their literacy achievement as measured by academic performance and classroom engagement could be projected. New literacy studies view literacy as socioculturally bound in social, institutional, and cultural relationships (Gee 1996). Literacy can therefore be thought of as an extension of self that Lankshear and Knobel (2006) assert is always connected to social identities. Central to the research questions as a result of this perspective was the discovery of the ideologies of reading held by the participants and their connections to literacy practice. Supplementary questions delved into socially valued literacy practices and ways in which learners saw themselves as Black males reflected in the Canadian educational framework. In this qualitative study with an interview design, data were collected through individual semistructured interviews with the 4 participants and through a focus group session with all the participants. The findings depicted that identity, interests, and ideologies of reading all influenced the literacy practices and engagement of Caribbean males. The findings documented are valuable as they provide a fresh perspective surrounding the educational experiences of the male Caribbean learner and can present insights which can lead to enhanced academic engagement and improved student achievement for this group of learners.

Is Brand Equity an Asset or a Liability in Brand Harm Crisis? Buffering and Amplifying Effects and Contingent Conditions

Brand harm crisis often result in negative consumer responses. This thesis addresses the buffering and amplifying theoretical perspectives of brand equity effects. We theorize that brand equity may interplay with the nature of brand-harm crisis in shaping consumer reactions. Results from focus group studies provide interesting insights into the amplifying and buffering effects. Moreover, research findings from two experiment studies show that brand equity amplifies consumer negative responses in a performance-related crisis but only when the crisis is extremely severe. When the crisis becomes less severe, the amplifying effect diminishes from outset. However, in a value-related crisis, the amplifying effect of brand equity is pervasive regardless of the level of crisis severity. The current thesis adds to the extant literature by demonstrating that brand equity can have very complex effects on consumer responses, which are contingent on the severity and domain of a crisis. Theoretical and managerial implications are discussed.

A Theory of Random Consumer Demand

This paper presents a new theory of random consumer demand. The primitive is a collection of probability distributions, rather than a binary preference. Various assumptions constrain these distributions, including analogues of common assumptions about preferences such as transitivity, monotonicity and convexity. Two results establish a complete representation of theoretically consistent random demand. The purpose of this theory of random consumer demand is application to empirical consumer demand problems. To this end, the theory has several desirable properties. It is intrinsically stochastic, so the econometrician can apply it directly without adding extrinsic randomness in the form of residuals. Random demand is parsimoniously represented by a single function on the consumption set. Finally, we have a practical method for statistical inference based on the theory, described in McCausland (2004), a companion paper.

Bayesian Analysis for a Theory of Random Consumer Demand: The Case of Indivisible Goods

McCausland (2004a) describes a new theory of random consumer demand. Theoretically consistent random demand can be represented by a \"regular\" \"L-utility\" function on the consumption set X. The present paper is about Bayesian inference for regular L-utility functions. We express prior and posterior uncertainty in terms of distributions over the indefinite-dimensional parameter set of a flexible functional form. We propose a class of proper priors on the parameter set. The priors are flexible, in the sense that they put positive probability in the neighborhood of any L-utility function that is regular on a large subset bar(X) of X; and regular, in the sense that they assign zero probability to the set of L-utility functions that are irregular on bar(X). We propose methods of Bayesian inference for an environment with indivisible goods, leaving the more difficult case of indefinitely divisible goods for another paper. We analyse individual choice data from a consumer experiment described in Harbaugh et al. (2001).

The Lack of Credibility on the Web and its Ramifications Under Quebec’s Consumer Protection Act

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Addressing Adherence to Antiretroviral Therapy in Ouagadougou, Burkina Faso: Insights from hospital ethnography

L'épidémie de l'infection au virus de l'immunodéficience humaine (VIH) constitue une crise majeure en santé publique de nos jours. Les efforts de la communauté internationale visent à rendre les traitements antirétroviraux (TARV) plus accessibles aux personnes vivant avec le VIH, particulièrement dans les contextes à ressources limitées. Une observance quasi-parfaite aux TARV est requise pour tirer le maximum de bénéfices thérapeutiques à l'échelle individuelle et à l'échelle populationnelle. Cependant, l’accroissement de la disponibilité des TARV s'effectue dans des pays africains qui disposent de systèmes de santé fragiles et sous-financés. Ceux-ci souffrent également d'une pénurie de personnel de santé, lequel joue un rôle central dans la mise en oeuvre et la pérennité des interventions, notamment celle du soutien à l'observance thérapeutique. La présente étude ethnographique relate l'expérience de personnel de santé dans la fourniture des services de soutien à l'observance dans un contexte de ressources limitées et d'accroissement de l'accès aux TARV. L'étude a été menée dans deux centres hospitaliers de la capitale du Burkina Faso, Ouagadougou. Trois conclusions principales sont mises au jour. Tout d'abord, une bonne organisation – tant logistique que matérielle – dans la provision de services de soutien à l'observance est capitale. L’infrastructure d’observance doit aller au-delà des unités de prise en charge et s’intégrer au sein du système de santé pour assurer un impact durable. De plus, la provision des TARV dans le cadre d'une prise en charge médicale exhaustive est essentielle pour un soutien à l'observance efficace. Ceci implique la présence de professionnelles de santé en nombre suffisant et disposant d‘outils pour soutenir leur pratique clinique (tests de laboratoire, traitements pour infections opportunistes), ainsi que des mécanismes pour leur permettre d’aider les patients à gérer la vie quotidienne (gratuité des services, programmes d’alphabétisation et soutien psychosociale). Enfin, une amélioration de la coordination des programmes VIH au niveau national et international est nécessaire pour assurer une prise en charge cohérente au niveau local. La programmation conçue dans les pays étrangers qui est incomplète et de courte durée a un impact majeur sur la disponibilité de ressources humaines et matérielles à long terme, ainsi que sur les conditions de travail et de prestation de services dans les unités de soins.

Cosmopolitanism and confrontation : realizing consumer responsibility in a globalized marketplace

Ce mémoire explore des façons de conceptualiser la responsabilité dans des cas où des individus contribuent de façon peu significative à des torts collectifs éloignés. Pour contextualiser la discussion, la relation entre des actes de consommation et la perpétuation des « sweatshops » dans l’industrie des textiles et des chaussures est utilisée. Une approche basée sur les droits humains est déployée pour définir le tort qui est présent dans les usines de textiles et une conceptualisation de la connection est proposée selon la notion de la structure sociale. Guidé par la notion de « unstructured collective harms » proposée par Christopher Kutz, et en comparaison avec des notions de responsabilité qui mettent la responsabilité nationale en premier plan, les conclusions qui sont offertes ici sont centrées sur l’importance de la confrontation du consommateur pour remédier aux effets du problème d’action collective qui est au coeur de la création des torts collectifs lointains. Finalement, l’importance du cosmopolitanisme comme une façon de stabiliser des théories de responsabilité à travers les frontières est mis en évidence.

MARCH1 : new insights in the activation of B cells

L’implication des cellules B dans le développement de l’auto-immunité ne cesse d’être illustrée par de récentes publications. Les cellules présentent des peptides du soi aux cellules T auto-réactives ce qui mène à la production de cytokines pro-inflammatoires et d’anticorps auto-réactifs. Dans le présent document, nous explorons la présentation antigénique et la modification post-traductionnelle du complexe majeur d’histocompatibilité II (CMH-II). MARCH1 est une E3 ubiquitine ligase qui cible le CMH-II et le relocalise le complexe vers les endosomes de recyclage. Ainsi, MARCH1 est un inhibiteur de la présentation d’antigènes exogènes. Ici, nous démontrons que MARCH1 est exprimé seulement dans la sous-population des cellules B folliculaires et que cette expression est perdue lors de l’entrée dans les centres germinatifs. Nous proposons que MARCH1 établie une barrière de formation de centres germinatifs. Nous démontrons le lien entre MARCH1 et la hausse de CMH-II à la surface des cellules B à la suite d’un traitement à l’IL-10. De plus, nous avons testé plusieurs stimuli activateurs des cellules B et démontrons que MARCH1 est régulé à la baisse dans tous les cas. De plus, nous mettons en valeurs le rôle de la voie canonique d’activation de NF-κB dans cette régulation de MARCH1. Finalement, nous avons développé un système de lentivirus exprimant MARCH1 qui nous permet de forcer l’expression de MARCH1 dans des cellules réfractaires à la transfection. Nous discutons de l’implication de cette régulation du CMH-II par MARCH1 dans le développement de maladies auto-immunes.

Insights into the function of short interspersed degenerated retroposons in the protozoan parasite Leishmania

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