English
Palladium N-Heterocyclic Carbene Complexes in Cross-Coupling Reactions: Ligand and Catalyst Development
The synthesis of biaryls through transition metal catalyzed cross-coupling reactions has been instrumental for synthetic organic chemists. The Hiyama reaction, which features organosilicon derived cross-coupling partners with aryl chlorides, remains relatively underdeveloped compared to other cross-coupling reactions. In this thesis, it is demonstrated that bench stable Palladium N-Heterocyclic Carbene (NHC) precatalysts of the general type [(NHC)Pd(allyl)Cl] are highly active in the Hiyama cross-coupling of activated aryl chlorides with low catalyst loading. Notably, this research demonstrates that catalysts featuring sterically less demanding NHCs display higher activity in this reaction, which contrasts with other cross-coupling reactions. Preliminary mechanistic investigations including in situ reaction monitoring by 19F NMR spectroscopy have uncovered side reactions. These side reactions may explain the low catalytic performance observed with unactivated substrates. These studies could help to further develop this reaction and improve catalytic performance. Additional investigations have also been made into ligand development by altering the electronics of sterically hindered NHC ligands for use in other cross-coupling reactions.
Author Keywords: Catalysis, Cross-coupling, Organic Chemistry, Organometallics, Side Reactions, Synthesis
Lifting up the Voices of Tyendinaga's Healthcare Professionals
For this study, I asked Tyendinaga's healthcare professionals if they had any solutions to make the healthcare system run more smoothly when working with settlers. I wanted answers to four questions: 1. what role does our culture play in implementing or delivering mental/physical/spiritual/emotional midwifery/health/social services? 2. are there any gaps in services, or more precisely, any barriers that midwifery/health/social professionals encounter in implementing or delivering our holistic health services? 3. could they identify any problems they might face in completing paperwork to justify funding for their program? 4. could they offer their opinion regarding alternative approaches where they might create space for an intercultural dialogue regarding holistic health?I trusted that this would advance answers to my major dissertation questions: What are the obstacles or gaps and possible solutions to Indigenizing healthcare implementation, services, and delivery in Tyendinaga Mohawk Territory (TMT), Ontario? Is there a "space" like the Two-Row Wampum where two distinct peoples can negotiate their relationship regarding health in an equally respectful and reciprocal atmosphere?
Author Keywords: holistic health, Indigenous community engagement, Indigenous methodologies, Thanksgiving Address, Two Row Wampum
Guidance for Healthcare Professionals when Caring for People Who Use Drugs: A Perspective from Persons Who Use Drugs: A Scoping Review
Individuals who use drugs face stigma in healthcare, leading to poor health outcomes and limited treatment access. This scoping review aims to provide healthcare professionals with key evidence needed for delivering acceptable care from the perspective of those who use drugs. A Lived Experience Advisory Panel determined what contributions represented the perspective of people who use drugs. Over 22,000 grey and white literature articles were screened, resulting in 14 relevant articles. Participant quotes illustrate five emerging themes: Being someone who matters, I trust that the people taking care of me trust me, I'm happy that you listened… I clearly have knowledge in this area, You don't know unless you've been there… We can tell you and Help me access services and resources—the importance of listening weaves through each theme. The findings have significant implications for healthcare professionals, aiding them and decision-makers provide more acceptable care for people who use drugs.
Author Keywords: patient perspective, patient satisfaction, patient voice, people who use drugs patient perspective patient voice patient preference patient satisfaction, PWUD, substance use
The Influence of Atmospheric Circulation on Snowmelt and Carbon Fluxes in the Canadian Low Arctic
This study examines the atmospheric (synoptic) controls on snowmelt and snow-free season carbon dioxide (CO2) fluxes at Daring Lake, Northwest Territories. Atmospheric circulation patterns were derived from 500 hPa geopotential height and classified using the self-organizing maps artificial neural network. Snowmelt timing was not found to be influenced by atmospheric circulation patterns or large-scale teleconnection indices, but a shift from meridional to zonal atmospheric circulation marked the transition from pre-melt to melt period. Multiple linear regression identified heating degree days and incoming solar radiation as the most important meteorological predictors of melt length; however, the model would have benefitted from additional variables. Analysis of CO2 (net ecosystem exchange, NEE) during the snow-free season highlighted a strong correlation between NEE and temperature anomalies. Like the snowmelt period, no atmospheric circulation patterns were found to significantly influence NEE; however, these findings prompt further questions regarding snowmelt and CO2 fluxes in the Canadian low Arctic.
Author Keywords: atmospheric circulation, carbon fluxes, net ecosystem exchange, self-organizing maps, snowmelt, synoptic patterns
Effects of a Topographical Gradient on Food Availability, Nest Site Selection, Nest Initiation, and Nest Success for Two Small, Low Arctic Breeding Bird Species
Climate change affects birds' reproductive ecology by altering breeding timing, distribution, and habitat suitability. Snowmelt patterns complicate these changes affecting habitat availability and suitability for birds and their arthropod prey. Snow varies as a function of both large-scale climate patterns and local-scale topography. I used elevational gradients as a proxy for local- scale snow impacts, investigating how elevation affects arthropod abundance, and nest placement, initiation, fate, and habitat for Lapland Longspur (Calcarius lapponicus) and Semipalmated Sandpiper (Calidris pusilla) north of Baker Lake, Nunavut. I found and monitored nests over multiple breeding seasons and used pitfall traps and conducted vegetation surveys. Results show that elevation significantly affects arthropod biomass and nest placement, but not nest initiation or success. Both species preferentially nested at lower elevations with higher arthropod biomass. Thus, birds in the central Arctic choose nesting sites at lower elevations with better food availability rather than higher elevations with earlier snowmelt.
Author Keywords: Arctic, arthropod biomass, Lapland Longspur, nest site selection, nest success, Semipalmated Sandpiper
The ecology and evolution of animal migration – an integrative approach to the drivers of phenotypic variation
Animal migrations are ubiquitous and one of the most threatened ecological processes globally. Because of the multifaceted nature of migration – seasonal movements between home ranges – it can be difficult to tease apart the underlying mechanisms influencing this behaviour. It is necessary to understand these mechanisms, not only to deepen our fundamental understanding of migration in animals, but also because migrations in many species are vulnerable to environmental change. In Chapter 2, I first systematically identify the broad proximate drivers of migration and offer generalities across vertebrate taxa. I quantitatively reviewed 45 studies and extracted 132 observations of effect sizes for internal and external proximate drivers that influenced migration propensity. Through this meta-analysis, I found that internal and external drivers had a medium and large effect, respectively, on migration propensity. Predator abundance and predation risk had a large effect on migration propensity, as did individual behaviour. Of the studies that examined genetic divergence between migrant and resident populations, 64% found some genetic divergence between groups. In Chapter 3, I explore the genetic basis for migration and identified genes associated with migration direction from pooled genome-wide scans on a population of 233 migrating female mule deer (Odocoileus hemionus) where I identified genomic regions including FITM1, a gene linked to the formation of lipids, and DPPA3, a gene linked to epigenetic modifications of the maternal line. These results are consistent with the underlying genetic basis for a migratory trait which contributes to the additive genetic variance influencing migratory behaviours and can affect the adaptive potential of a species. Finally, in Chapter 4 I used a pedigree-free quantitative genetic approach to estimate heritability and sources of environmental variation in migration distance, timing, and movement rate of the same population of mule deer. I found low heritability for broad patterns of migration timing, and greater variation in heritability for behaviours during migration, with low heritability for distance and duration and high heritability for movement rate along the route. Insights into the genetic and environmental sources of variation for migration are critical both for the eco-evolutionary dynamics of migration behaviour, and for the conservation of species whose migrations may be vulnerable to environmental change. My thesis reveals that broad patterns of migration are driven largely by environmental effects while within these broad patterns, migration behaviour is driven to a measurable degree by genetic variation.
Author Keywords: heritability, migration, Odocoileus hemionus, reduced representation sequencing, whole genome sequencing
Stand at Attention! Examining Postural Effects on Attention
Office workers consistently report greater productivity in the workplace when standing compared to sitting (Chambers et al., 2019; MacEwan et al., 2015; Mantzari et al., 2018). In contrast, laboratory studies report inconsistent evidence that posture (sitting vs. standing) affects cognitive performance, usually operationalized as selective attention (Caron et al., 2020; 2022; Rosenbaum et al., 2017; Smith et al., 2019). The present work assessed whether the discrepancy between workplace and laboratory findings is because workplace tasks are more difficult than the tasks used in laboratory research. Three visual search experiments are reported. Search difficulty was increased in Experiments 1 and 2 and posture difficulty was increased in Experiment 3. There was no evidence that posture affected attention in any of the experiments suggesting that the failure to find an effect of posture on attention in previous work was not due to the task difficulty.
Author Keywords: Cognition, Cognitive Resources, Dual Task, Embodied Cognition, Posture, Selective Attention
Rethinking Assessment: Students' Experiences, Learning Approaches, and Motivations in University Exams
This thesis aimed to explore students' perspectives on university exams in two studies. Using a phenomenological approach, Study 1 recruited 10 senior undergraduate students to participate in semi-structured interviews. A thematic analysis revealed key themes related to exam purpose, effectiveness, fairness, and emotional responses. These insights informed the development of a sequence model explaining how students form exam perceptions. Study 2 was a concurrent, embedded, correlational mixed-methods case study of sophomore Psychology students' (N = 35) experiences with a case-based take-home exam designed according to motivational design principles. Findings from this study highlight the associations between students' motivation orientation and motivational assessment features and students' positive experiences and perceptions of the exam. This thesis offers an informative framework for instructors aiming to promote student buy-in, while also meeting course learning outcomes and facilitating deeper engagement with assessments.
Author Keywords: alternative assessment, assessment design, learning outcomes, student motivation, university exams
Young children's spatial conceptions of two-dimensional grid structures
Spatial reasoning and spatial structures are relatively new areas of research in mathematics education. In this study of children exploring spatial conceptions of grid structures, twenty-one children (ages 4-9) were given a series of tasks involving square grids during virtual interviews. As a result of an ideal-type analysis of the qualitative data, a typology of conceptions of grids emerged showing five distinct categories sequenced from very early conceptions of square grids (as a series of isolated cells) to more coordinated structuring (as related and intersecting rows and columns). The five categories - Single Cell Structuring, Partial Unit Building, Whole Figure and Parts-of-Figure Noticing, Composite Unit Structuring and Coordinated Structuring - are described through illustrative examples. Students' gestures, language and diagrams were considered together when constructing the types. Interestingly, the spatial structure of grids was not readily apparent to many students and in fact was found to be complex for students to conceptualize. With minimal research on grids as a spatial structure in the mathematics education research field, there is strong potential for further investigation in this area.
Author Keywords: Grids, Mathematics, Spatial reasoning, Young Children
Sustainability and Adaptive Reuse: A Case Study of Historical and Heritage Industrial Sites in Peterborough, Ontario
The study examines the adaptive reuse of historical and heritage industrial sites in Peterborough, Ontario. Industrial-heritage sites face several challenges when being subjected to adaptive reuse. These challenges are largely concerned with the contamination of sites and how industrial buildings and sites can be transformed into reusable sites. The study adopted a qualitative research design and analysis. The study addressed the research gap about nature of adaptive reuse of historic and heritage sites in Peterborough. The study primarily focused on the challenges, best practices, stakeholder initiatives, and the nature of structures in contexts of adaptive reuse in Peterborough. Based on the findings of the study, COVID-19, political will, contamination and the design of heritage and industrial buildings or sites pose a challenge to implementing adaptive reuse practices. These findings provide evidence for policymakers and decision makers on how to apply best practices to adaptive reuse and cultural heritage.
Author Keywords: Adaptive reuse, Cultural, Heritage, Historical, Industrial, Structures