Free radical cyclization methodology has been used extensively in synthesis for manipulation of complex molecules such as alkaloids, terpenes, carbohydrates, peptides and nucleic acids. The methodology has emerged as a result of work by physical organic chemists who determined rate constants for the most common radical reactions used in organic synthesis. A novel route to cyclic imines based on 5-exo radical cyclization was explored. The radical precursors were imines prepared from allylamine and readily available a-phenylselenenyl ketones. The synthesis of conformationally constrained bicyclic nucleosides is also reported using 5-exo and 6-exo cyclizations of hexenyl and heptenyl radicals in thymidine nucleosides. The nucleosides were incorporated in a 15mer antisense oligonucleotide via solid-phase oligonucleotide synthesis. The AONs with the modifications were tested for target affinity and stability and compared with the well known LNA modified AONs. The thesis discusses the unique qualities of these novel molecules and presents them as potential candidates for antisense therapeutic agents. Keeping up with the theme of intramolecular carbon-carbon bond formation, microwave induced carbodechalcogenation of chalcogenoanhydrides was explored. Poor generality in these reactions made us turn to transition metal catalysis for Sonogashira cross-coupling reactions using alkyl aryl and diaryl tellurides as coupling partners.

Det svenska biståndet inriktat mot demokratisering uppgick 2008 till ca 4 miljarder kr. Det civila samhällets roll i demokratiseringsprocesser har fått ökad uppmärksamhet de senaste 15 åren och är numera ett av de vanligaste fokusområdena inom demokratibistånd. Syftet med denna uppsats är att undersöka det svenska demokratibiståndet inriktat på det civila samhället och dess effekter och dess möjligheter att påverka demokratiseringsprocesser Genom att undersöka utvärderingar av olika projekt, vars syfte varit att stärka det civila samhället, har biståndets egentliga effekter kunnat redovisas. De länder som undersöks i denna uppsats är Moldavien, Etiopien, Zimbabwe och fyra län-der i Latinamerika; Bolivia, Guatemala, Peru, Nicaragua. De resultat som redovisas i upp-satsen ligger först och främst i attityd- och beteendeförändringar på individnivå hos de som varit inblandade i organisationer, men även bland vanliga medborgare. Människor har blivit mer medvetna om deras politiska och civila rättigheter. I vissa fall har även förändringar skett främst på lokalnivå, där kommunalpolitiker blivit mindre rädda för det civila samhäl-let, och dialoger kunnat föras och där organisationer och vanliga medborgare vågat ställa krav på vissa av deras rättigheter. På detta plan har biståndet alltså kunnat påverka det civila samhället.Vad som dock utgör ett hinder för det civila samhällets möjligheter att påverka på nationell nivå är den bristande respekt som de statliga institutionerna visar. För att det civila samhäl-let ska kunna påverka beslut och öka demokratin i de länder som undersöks behöver en ömsedig respekt utvecklas mellan staten och det civila samhället. / The Swedish aid focused on democratization amounted to approximately 4 billion SEK in 2008. The role of civil society in democratization processes have received increased atten-tion in the last 15 years and is now one of the most common focus areas of democracy as-sistance. The aim of this thesis is to examine the Swedish democracy assistance focused on civil society and its effects and its ability to influence the processes of democratization. By examining evaluations of different projects, which aim was to strengthen civil society, the actual effects have been possible to show.The countries examined in this thesis is Moldova, Ethiopia, Zimbabwe and four countries in Latin America, Bolivia, Guatemala, Peru, Nicaragua. The results shown in the thesis is primarily in attitude and behavior change at the individual level among those who have been involved in organizations, but also among ordinary citizens. People have become more aware of their political and civil rights. In some cases, even changes primarily at the local level, where local politicians have become less fearful of civil society, and dialogue, and where organizations and ordinary citizens dared to make demands on some of their rights. On this level, the aid has been able to influence civil society.What, however, is an obstacle to civil society's ability to influence at the national level is the lack of respect which the state institutions show. For civil society to be able to influence decisions and increase democracy in the countries under study there need to be a reciprocal respect developed between the state and civil society.

Fertility rates in sub Saharan Africa (SSA) have been identified to be depicted by a  unique demographic scenario, that sets  the region  apart from other regions in the world. Demographers are particularly keen on comprehending the dynamics surrounding the demographic transition of the sub continent especially with respect to its shift from high fertility rates to low fertility rates.  The decline in fertility embodies the second phase of the demographic transition process. The discourse on fertility rates in the sub continent has been coined to be an anomaly based on its prevalence being an exception in the world. Discussion pertaining to fertility levels in the region in this paper was made  with the purpose of illuminating the factors that account for the region’s high fertility rates, as well as on  fertility discourse in the region, and the variation that characterize its prevalence amongst the countries in the sub continent. Information on the fertility rates revealed that social organization and cultural setting in the region play pivotal roles in forging high fertility rates in the region.

The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.

The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.

Presented are case studies of two children as they make the transition from Mexican immigrant homes to kindergarten in an English-dominant school in the United States. In the first case, Victor adapts by keeping his attention focused on the teacher, which allows him to avoid disorientation and take on the role of exemplary student. In the second, Natalie adapts to kindergarten through her relationships with peers and the teacher. She often participates in class activities, however, without understanding the narrative or rationale behind them. Cross-case comparisons suggest that each student adapted in a way suited to his or her own needs and resources. The journey from disorientation to adaptation is described through the application of the holistic, systems-oriented, interactionalistic developmental approaches of Werner, Wapner, and Koizumi.

Bone marrow transplantation (BMT) is the treatment of choice for many malignancies and other childhood disorders. Acknowledging that the entire family is affected when a child undergoes a BMT, increasing research attention has been given to understanding this experience from the perspectives of recipients, parents and the family as a whole. Yet, minimal attention has been directed at understanding the experience of healthy siblings as they transition through the BMT experience. Before intervention studies can be undertaken that will help healthy siblings transition through the BMT experience, knowledge about the impact of the experience on siblings is needed. Accordingly, a qualitative study guided by the philosophy of hermeneutic phenomenology was conducted to elicit detailed descriptions of the lived experience of siblings. Participants were children, adolescents and young adults with a sibling who had undergone a BMT during childhood. Participants were recruited from a pediatric BMT clinic in Western Canada. Semi-structured, open-ended interviews that explored siblings’ memories about what it is like to be a sibling of a child who has had a BMT were conducted with each participant. Demographic data and field notes were recorded. All interviews and field notes were transcribed. The transcripts were reviewed repeatedly for significant statements in an attempt to find meaning and understanding through themes. The data analysis revealed the essence of siblings’ lived experience of transitioning through the BMT trajectory as an interruption in family life. Four themes communicated the essence of siblings’ lived experience: (1) life goes on, (2) feeling more or less a part of a family, (3) faith in God that things will be okay, and (4) feelings around families. Differences between donor and non-donor siblings are highlighted. Siblings’ recommendations for health care professionals are also provided. Results from this study will help health professionals better anticipate the diverse and shifting needs and demands of siblings of pediatric BMT patients. Recommendations for future research and innovations in nursing interventions are provided. / October 2005

Les zones de transition sont les espaces intermédiaires où tout se joue, car elles sont au seuil de l'action, l'ultime hésitation avant que tout arrive. Elles posent donc encore question, et se faisant, ouvrent l'espace du commentaire. Prendre en considération cet écart transitoire, c'est envisager la frontière non plus comme une limite, mais comme un passage, le lieu temporaire et suspendu d'une interaction. À travers l'étude de scènes filmiques qui permettent d'en discerner plus clairement le mécanisme (Mar Adentro d'Alejandro Amenábar, 2004, Der Himmel über Berlin de Wim Wenders, 1987), la transition apparaît alors comme le lieu propice pour interroger le procès communicationnel, en tant qu'elle manifeste l'espace du tiers: si la transition pose en général la question du passage d'un état à un autre, dans le contexte communicationnel, son trajet s'altère et devient passage par un autre. Cependant la structure horizontale de la communication, en s'ouvrant ainsi par le milieu, découvre sa verticalité, et le passage devient médiation. Le paradoxe de la transition tient au fait qu'elle révèle un tiers qui est à la fois le garant extérieur de la communication, et son corps interne, l'agent de sa transitivité. Pour le faire surgir, elle le met en scène, et c'est du reste son seul pouvoir, car elle est un tour du discours. Ainsi la pratiquer au niveau social, c'est la changer en rituel de passage, mouvement dialectique où la communauté s'engendre. La transition constitue en fait l'interstice dans lequel se pense une société, l'endroit propre de sa fabulation: pour « concilier des puissances qui nous échappent », il faut, curieusement, commencer par disposer d'un espace et d'un moment liminaires, qui échappent justement à la structure sociale. Au terme de l'analyse, les vides de l'entre-deux apparaissent comme des plages vacantes, repères libres prêts à accueillir les constructions symboliques. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Transition, Médiation, Rituel, Passage, Processus, Dialectique.

The reactions and photochemistry of atomic and diatomic transition metals with methanol, water, hydrogen, and carbon monoxide in noble gas matrices at cryogenic temperatures have been studied with the use of Fourier Transform infrared inert matrix spectroscopy. Atoms and dimers of iron and cobalt reacted with methanol to form the adducts, M(CH30H) and M2(CH30H), respectively. M(CH30H) underwent metal insertion into the 0-H bond of methanol to yield methoxymetal hydride, CH3OMH, with irradiation of the matrix in the violet (400 nm < λ < 500 nm) region. Ultraviolet (280 nm < λ < 360 nm) photolysis of the matrix rearranged CH30MH to yield the methylmetal hydroxide species, CH3MOH. CH30MH dissociated into carbon monoxide and hydrogen after prolonged irradiation in the ultraviolet region. Surprisingly, nickel atoms reacted spontaneously to insert into the 0-H bonds of methanol and water to form CH30NiH and HONiH, respectively. Violet photolysis caused CH30NiH to rearrange to form methylnickel hydroxide, CH3NiOH. This is effectively a two step process of the C-0 activation of methanol by a nickel atom. In addition to rearrangement, CH30NiH dissociates into carbon monoxide and hydrogen with violet photolysis. Nickel dimers also reacted spontaneously with water to form both an adduct and insertion products. Atomic nickel spontaneously inserts into the H-H bond of molecular hydrogen to yield a bent nickel dihydride, NiH2, in krypton and xenon matrices. Nickel dimers and trimers insert into the H-H bond of hydrogen to form Nix(H)2. In addition to the insertion products, nickel atoms, dimers, and trimers form adducts molecularly with hydrogen to yield complexes of the form Nix(H2)y, where x or y = 1-3. Reactions of iron with carbon monoxide in an argon matrix yielded the iron-carbonyl complexes, Fex(CO)y, where x = 1-3 and y = 1-2.

Background: Quality of care and patient safety have been demonstrated to be at increased risk during care transitions; making older adults with complex medical issues especially vulnerable due to the multifaceted care they require (Coleman, 2003; Cook et al., 2000; Forster et al., 2003; Murtaugh & Litke, 2002; Picker Institute, 1999; van Walraven et al., 2004). While a strong focus on patient issues during care transitions exists in current literature, there is a dearth of knowledge surrounding the role of informal caregivers in this process. As the senior population continues to grow in Canada, it is inevitable that the health system will be increasingly reliant upon informal caregivers to meet the demanding and complex care needs of older adults. This research explored informal caregiver experiences following an older patient’s medical crisis in order to foster a deeper understanding of caregiver needs during transitional care. This work will support efforts to develop viable interventions within formal care settings to better support and prepare individuals for informal care responsibilities (Canadian Caregiver Coalition, 2008; National Centre for Social and Economic Modelling, 2004). Methods: A qualitative, post-positivist grounded theory study was employed to acquire an understanding of the role and needs of informal caregivers during transitional care. Semi-structured interviews were conducted with six community and resource case managers, and informal caregivers of eight hip fracture and two stroke caregivers. Two additional interviews were conducted with hip replacement caregivers. Questions explored individual experiences interacting with and/or providing informal care, and honed in on observed and experienced challenges, support received, and recommendations for future efforts to support care. NVivo8 software facilitated qualitative data analysis through hierarchical coding (Glaser & Strauss, 1967). Results: Six properties of caregiver needs arose from the data, each consisting of several important ideas fostering its understanding. The core concept threading across all properties was building capacity to care. Combined, thematic interpretations were integrated into a comprehensive theory of caregiver needs to support a successful care transition from hospital to home, consisting of three layers: 1) Timeline of caregiver needs; 2) Instrumental needs; and 3) Emotional needs. A member-checking process of the theory consisting of both a focus group and individual interviews indicated high face and content validity, and highlighted priority areas for future interventions. Discussion: The developed substantive theory is a valuable tool for which to understand the instrumental and emotional needs of hip fracture and stroke caregivers along a timeline of transitional care between hospital and home. Focus group and individual feedback indicate strong endorsement for theory adoption as a guiding framework for an intervention strategy to support informal caregivers within formal care settings and throughout the transition home. Results suggest the potential to broaden the conceptualization of the substantive theory to a formal explanation of transitional care needs for other medical crises across numerous types of transitions between formal hospital settings and the community.