Graduate Theses & Dissertations

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Electrochemical versus Chemical Oxidation of Bulky Phenols
Phenolic compounds are used in industry, such as agriculture and biotechnology, and inevitably end up in our environment. These compounds may serve as a phenolic precursor to produce raw materials for a wide range of applications. Chemical oxidation has been the common synthetic pathway to oxidize phenols and related compounds. However, traditional chemical approaches suffer from use of harsh chemicals, waste generation, and lack of reaction selectivity. Electrochemical synthesis has emerged as an alternative method to mitigate common challenges associated with organic synthesis. Herein, electrochemical oxidation of 2,6-diphenylphenol (DPP) and 2,2-dihydroxybiphenol (DHBP) was carried out and compared to traditional chemical oxidation. Contrasted with chemical oxidation, cyclic voltammetry of DPP resulted in a range of products based on the specific potential ranges used, whereas chemical oxidation of DHBP yield a dark-coloured polymeric product. The electrooxidation and chemical oxidation of DPP and DHBP resulted in a solution colour change, indicative of the formation of new, but different products monitored by UV-vis, and characterized by nuclear magnetic spectroscopy (NMR), X-ray single crystal diffraction, IR spectroscopy, transmission electron microscopy (TEM), and gas chromatography-mass spectrometry (GC-MS). The data indicate that the synthetic outcomes are dependent on the synthetic methodology employed, and that electrooxidation and chemical oxidation can form products unique to the pathway utilized. Author Keywords: chemoselectivity, electrochemistry, phenols, radical, synthesis
Genetic Networks to Investigate Structure and Connectivity of Caribou at Multiple Spatial and Temporal Scales
Understanding genetic structure, connectivity, and movement of a species iscritical to management and conservation. Genetic network approaches allow the analysis of genetic information with flexibility and few prior assumptions. In chapter one, I tested the ability of individual-based genetic networks to detect fine-scale structure and connectivity in relation to sampling efforts. My findings revealed individual-based genetic networks can detect fine-scale genetic structure of caribou when using 15 highly variable microsatellite loci. Sampling levels less than 50% of the estimated population size resulted in highly disconnected networks which did not allow for accurate structure analysis; however community detection algorithms were robust in grouping closely related individuals despite low sampling. In chapter two, I used individual-based and population-based genetic networks to investigate structure, connectivity, and movement of caribou across a large study area in Western Canada. A community detection algorithm partitioned the population-based genetic network at multiple spatial scales which uncovered patterns of hierarchical genetic structure and highlighted patterns of gene flow. The hierarchical population structure results aligned with the known distribution of different caribou Designatable Units (DUs) and additional structure was found within each DU. Furthermore, individual-based networks that were constructed with a subset of samples from the Mackenzie Mountains region of the Northwest Territories revealed patterns of long-distance movement and high connectivity across the region. Author Keywords: Biological Conservation, Caribou, Community Detection, Connectivity, Genetic Networks, Structure
Effects of Agricultural Land Use Change on Nitrogen and Phosphorus in North Shore Lake Ontario Tributaries
Row crop agriculture and associated land use practices including tile drainage and conservation tillage have been cited as a probable cause of re-emerging eutrophication in the lower Great Lakes. In this thesis, I sought to quantify and evaluate the effect of agricultural land cover and land use changes on total phosphorus (TP) and nitrate-nitrogen (NO3-N) concentrations and export in north shore Lake Ontario tributaries. This included (a) a long-term data analyses at 12 large watersheds (47 to 278 km²) using historical land cover and water quality data (1971-2010), and (b) a space-for-time study examining 12 small sub-catchments (< 8 km²) with majority (> 50%) row crop, pasture, or forest cover. Concentrations of TP were greatest in urbanized watersheds and declined particularly during the first decades of the study period, while NO3-N concentrations were greatest and steadily increased in agricultural catchments with increasing row crop cover. The space-for-time approach revealed that TP concentrations were similar across agricultural land uses and that export was most dependent on runoff. Meanwhile, NO3-N concentrations and export were greatest in row crop catchments and were positively related to row crop area. These results suggest that increases in row crop cover and associated agricultural practices including increased nutrient amendments and tile drainage may be responsible for increased NO3-N concentrations and export in northern Lake Ontario tributaries. Author Keywords: agriculture, Lake Ontario, nitrogen, phosphorus, streams, Water quality
Larval lake whitefish (Coregonus clupeaformis) recruitment dynamics in Lake Huron
Lake whitefish (Coregonus clupeaformis) recruitment has declined substantially in several regions of the Laurentian Great Lakes since the establishment of non-native dreissenid mussels in the early 1990’s. In Lake Huron, the reasons for the observed recruitment declines are currently unknown and there is limited knowledge about larval life stage. In our study, we determined whether larval hatching and growth rates have changed before and after dreissenid mussel invasion, and the role of several key environmental variables in influencing annual variation in larval densities. Larval fish were collected in the Fishing Islands spawning shoal during two time periods: a historical period (1976-1986) and a contemporary period (2017-2019). Larval densities and growth were lower in recent years, suggesting that recruitment is being limited at the larval life stage and that reduced food availability may be further limiting the growth during the larval stage. Annual variation of larval densities were influenced by spawning stock biomass, water levels, and dreissenid mussel presence, with higher water levels and the presence of dreissenid mussels being associated with higher larval densities. The direction of the effect of spawning stock biomass was either negative or positive depending on the model. We also found that larval density was a significant predictor of age 4 recruitment, indicating that year-class strength may be partly established at the larval life stage. Author Keywords: Coregonus clupeaformis, Great Lakes, Lake Huron, Lake whitefish, Larval, Recruitment
Assessing factors associated with wealth and health of Ontario workers after permanent work injury
I drew on Bourdieu’s theory of capital and theorized that different forms of economic, cultural and social capital which injured workers possessed and/or acquire over their disability trajectory may affect certain outcomes of permanent impairments. Using data from a cross-sectional survey of 494 Ontario workers with permanent impairments, I measured workers’ different indicators of capital in temporal order. Hierarchical regression analyses were used to test the unique association of workers’ individual characteristics, pre-injury capital, post-injury capital, and the outcomes of permanent impairments. The results show that factors related to individual characteristics, pre-injury and post-injury capital were associated with workers’ perceived health change, whereas pre-injury and post-injury capital were most relevant factors in explaining workers’ post-injury employment status and income recovery. When looking at the significance of individual predictors, post-injury variables were most relevant in understanding the outcomes of permanent impairment. The findings suggest that many workers faced economic and health disadvantages after permanent work injury. Author Keywords: Bourdieu, hierarchical regression, theory of capital, work-related disability, workers with permanent impairments
Using Fluorescent Carbon Dots for Biosensing Applications of Amino Acids
Amino acids make up proteins, which are the building blocks of life. A balance of amino acids is needed to maintain a healthy state. Tyrosine (Tyr) is synthesized from the metabolism of phenylalanine, which is an essential amino acid, meaning it can only be obtained from the diet. It is related to many metabolic and neurodegenerative diseases. Tyr can undergo post-translational modifications such as phosphorylation and nitration, which are implicated in cancer and nitrative stress, respectively. Although there are many methods to detect Tyr and its analogues, phosphotyrosine (pTyr) and nitrotyrosine (nTyr), these methods are time-consuming, involve expensive instruments and involve tedious process. This research proposes a new type of nanomaterials, carbon dots (CDs), to detect these amnio acids. Data indicate that CDs can be used to detect nTyr with a limit of detection of 34 μM in the linear range of 20 - 105 μM. The amenability of CD-nTyr assay was also tested in various biological matrices and biological molecules and was shown to be sensitive to nTyr. Nitration of Tyr was carried out in the presence of sodium nitrite and hydrogen peroxide catalyzed by either Cu(II) or Fe(III) to mimic biological reactions and CDs were tested as both inhibitors and indicators of Tyr nitration. Although CDs did not inhibit the nitration reaction of Tyr, they did not serve as indicators of Tyr nitration due to the quenching of CDs by the nitrating agents. This shows the importance of using CDs to detect nTyr and further use it for biological applications to detect diseased states. Author Keywords: amino acids, carbon dots, nanomaterials, sensor, spectroscopy, tyrosine
Determinants of Deviance
Background: Researchers have provided evidence that attachment may be independently linked to early adversity and criminal behaviour. In this study, I examined the combined associations among these variables in a student and community sample. Method: The first study consisted of undergraduate students (n = 590) who completed surveys to assess early adversity (Felitti, et al., 1988), attachment (Scharfe, 2016), and criminal behaviours. Participants were grouped based on their reports of adverse experiences and engagement in criminal behaviour. The second study was a replication of the first using a community sample (n = 294). Results: My hypotheses were partially supported, and my findings were consistent across Study 1 and Study 2. As I expected, there was a significant main effect for adversity when examining the mean scores of the attachment representations for attachment to mothers (Study 1 F (16, 1763.402) = 3.61, p < .001; Study 2 (F (16, 849.942) = 2.377, p = .002) and attachment to fathers (Study 1 F (16, 1763.402) = 4. 349, p < .001; Study 2 (F (16, 840.776) = 3.067 p < .001)). From examining the means, I concluded that participants who reported greater adversity reported higher insecure-avoidant and lower secure attachment to mothers and fathers. There were no significant main effects for criminal behaviour or significant interaction effects. Impact: To date, no study has explored all three variables explicitly. My findings are able to highlight the critical importance of secure attachment relationships and add further comprehension to exploring factors associated to criminal behaviour. Author Keywords: Attachment, Criminal Behaviour, Early Adversity
Retrograde Amnesia of Fear Memories Following Pentylenetetrazol Kindling
Memories pertaining to fearful events are some of the most salient and long-lasting memories, as they are critical to the survival of an organism. Seizures induce aberrant changes within temporal lobe and limbic brain structures that are critical for supporting fear memories. Seizures can occur at any time; therefore, it is imperative that research address how seizures impact previously learned information. The present series of experiments demonstrate that pentylenetetrazol-kindling induces retention deficits of previously acquired context fear memories in male rats. Kindling induced subsequent fear learning deficits but did not impact spatial learning. Additionally, following kindling, volumetric increase was observed within the hippocampal subfield CA3, as well as increased neural activation within the hippocampal subfield CA1. The results of this work suggests that chronic seizures can alter the function of neural networks important for supporting and retrieving previously acquired memories. Author Keywords: amygdala, anterograde amnesia, context fear conditioning, hippocampus, retrograde amnesia, seizures
Interactome study of the Giardia intestinalis nuclear localized cytochrome b5
Giardia intestinalis is a waterborne enteric parasite that lacks mitochondria and the capacity for heme biosynthesis. Despite this, Giardia encodes several heme proteins, including four cytochrome b5 isotypes (gCYTB5-I – IV) of unknown function. The aim of this thesis is to gain insight into the function of the Giardia cytochrome b5 isotype III (gCYTB5-III) that is found in the nucleus, as first reported by our laboratory using immunofluorescence microscopy experiments with an isotype-III specific antibody. Nuclear localization of isotype-III is supported by two of my experiments: i) immunoblot analysis of crude cytoplasmic and nuclear enriched fractions of Giardia trophozoites; ii) association of gCYTB5-III with the insoluble fraction of Giardia lysates crosslinked with formaldehyde is reversed by DNase I treatment. To gain an understanding of the possible roles of gCYTB5-III, I performed immunoprecipitation (IP) experiments on lysates from Giardia trophozoites to identify its protein partners. Mass spectroscopy analysis of the immunoprecipitate identified proteins localized to the nucleus (RNA polymerase, DNA topoisomerase, histones, and histone modifying enzymes). Intriguingly, over 40% of the known mitosomal proteome, which functions in iron-sulfur (Fe-S) cluster assembly was also associated with gCYTB5-III. One of these proteins, the flavoenzyme GiOR-1, has been shown to mediate electron transfer from NADPH to recombinant gCYTB5-III. These IP results provide evidence that GiOR-1 and gCYTB5-III interact in vivo, and furthermore, suggest that some proteins in the mitosome could interact with those in the nucleus. I also found that DNA stress, caused by low concentrations of formaldehyde (0.1 – 0.2%) resulted in the increased expression of gCYTB5-III. Collectively these findings suggest a role of gCYTB5-III in Giardia's response to DNA stress and perhaps the formation of Fe/S clusters. Author Keywords: cluster, cytochrome, heme, iron, mitosome, nuclear
Fall Migratory Behaviour and Cross-seasonal Interactions in Semipalmated Plovers (Charadrius semipalmatus) Breeding in the Hudson Bay Lowlands, Canada
I used the Motus Wildlife Tracking System to monitor the fall migration behaviour and assess the underlying drivers of migration strategy in a small shorebird, the Semipalmated Plover (Charadrius semipalmatus), breeding at two subarctic sites: Churchill, Manitoba and Burntpoint Creek, Ontario, Canada. Semipalmated Plovers from both sites departed breeding areas between mid-July and early August, with females preceding males and failed breeders preceding successful breeders. Migrants showed between and within-population variation in migration behaviour, though birds from both sites tended to follow interior or coastal routes and congregated in three major stopover regions along the mid-Atlantic coast of North America. I found that later-departing birds had initial flight tracks oriented more toward the south, faster overall ground speeds, were less likely to stopover in North America, and stopped at lower latitudes, suggesting that later-departing individuals use aspects of a time-minimizing strategy on fall migration. My findings emphasize the importance of the mid-Atlantic coast for Semipalmated Plovers and establish connectivity between sites used during breeding and migration. Author Keywords: Breeding, Migration, Motus, Semipalmated Plover, Shorebird, Stopover
Expression of Giardia intestinalis flavoenzyme GiOR-1 and characterization of its electron transfer properties
Giardia intestinalis possesses four isotypes of cytochrome b5 (gCYTB-I-IV) that differ from their mammalian counterparts, suggesting different functions in this protozoan parasite. Although the recently discovered Giardia flavoenzyme, GiOR-1, reduces these cytochromes, its properties have not been thoroughly studied, owing to the difficulty in its expression. Here I describe successful conditions for expression of GiOR-1 using autoinduction. GiOR-1 is obtained with flavins bound as indicated by its UV-visible spectrum. Its ability to catalyze electron transfer from donors (NADH, NADPH) to acceptors (oxygen, ferricyanide, cytochrome c, gCYTB5-III) were studied in spectrophotometric rate assays. NADPH is the preferred electron donor, while cytochromes are the preferred electron acceptors. Interestingly, the His-tag used to purify gCYTB5-III decreases its reaction rate with GiOR-1, as an untagged version has slightly faster rates. These findings establish the appropriate conditions for further studies on GiOR-1, including the identification of endogenous electron acceptors. Author Keywords: Autoinduction, Cytochrome b5, Cytochrome P450 oxidoreductase, Giardia intestinalis, GiOR-1, Polyhistidine tag
Prescription Drugs
Medication used to treat human illness is one of the greatest developments in human history. In Canada, prescription drugs have been developed and made available to treat a wide variety of illnesses, from infections to heart disease and so on. Records of prescription drug fulfillment at coarse Canadian geographic scales were obtained from Health Canada in order to track the use of these drugs by the Canadian population. The obtained prescription drug fulfillment records were in a variety of inconsistent formats, including a large selection of years for which only paper tabular records were available (hard copies). In this work, we organize, digitize, proof and synthesize the full available data set of prescription drug records, from paper to final database. Extensive quality control was performed on the data before use. This data was then analyzed for temporal and spatial changes in prescription drug use across Canada from 1990-2013. In addition, one of major research areas in environmental epidemiological studies is the study of population health risk associated with exposure to ambient air pollution. Prescription drugs can moderate public health risk, by reducing the drug user's physiological symptoms and preventing acute health effects (e.g., strokes, heart attacks, etc.). The cleaned prescription drug data was considered in the context of a common model to examine its influence on the association between air pollution exposure and various health outcomes. Since, prescription drug data were available only at the provincial level, a Bayesian hierarchical model was employed to include the prescription drugs as a covariate at regional level, which were then combined to estimate the association at national level. Although further investigations are required, the study results suggest that the prescription drugs influenced the air pollution related public health risk. Author Keywords: Data, Error checking, Population health, Prescriptions

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Format: 2023/02/04