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Synthesis and Properties of π- Extended Phenoxyl Radicals.
Phenoxyl radicals are a class of π-radicals synthesized by single-electron oxidation of phenols. The spin density from the unpaired electron of a phenoxyl radical is highest at the oxyl position, as well as at the ortho and para positions relative to the oxyl group. The stability of phenoxyl radicals can be improved by substituents at the ortho and para positions, including aromatic, O, N, S-alkyl, and sterically hindered alkyl groups, which compensate for electronic deficiency through resonance or inductive effects. In 2016, Lemaire group reported a crystal structure of the stable phenoxyl radical 2,6-bis(8-quinolylamino)-4-(tert-butyl)phenoxyl (BAQP), which lacks the commonly utilized tert-butyl groups at the ortho position relative to the oxyl group. Moreover, the BAQP radical also showed reversible π-dimerization in solution.
This thesis describes the synthesis and characterization of two sets of phenoxyl radicals that lack ortho tert-butyl groups, similar to BAQP. The first set of phenoxyl radicals is ortho-substituted with amino derivatives of large aromatic π-systems, namely pyrene, naphthalene, and phenalenone. The second set is the halogenated derivatives of the BAQP radical. This thesis also explores the stability and the reversible π-dimerization of both of the above-described novel sets of phenoxyl radicals.
Notably, one of the radicals synthesized during this work, 5-(tert-butyl)l-2-oxy-1,3,-bis(1- prenylamino)benzene, was proven to be stable as crystal structures were obtained from the pure compound. This particular radical, like BAQP, showed reversible π-dimerization in solution detected by spectroscopic methods such as EPR and 1H-NMR spectroscopy methods. The solid- state properties of this radical were also explored through DC susceptibility measurements and EPR spectroscopy
Edge Communication Efficiency with GNN in the Internet of Vehicles
Vehicular edge plays a central role in ensuring an effective allocation of resources to provide services and applications. Resource allocation and communication in dynamic vehicular environments face numerous challenges in efficiently managing resources and data sharing, specifically managing the intricate balance of connectivity, storage, energy, computing, and cost of resources. These challenges are also affected by mobility, resulting in the demand for precision in communication range, density, and resource availability. Efficient resource allocation is a critical objective within vehicular networks, and to achieve this, intelligence, prediction, optimization, and incentive modelling are often employed. However, challenges persist, such as sporadic connectivity, transmission delays, and the inherent uncertainty of highly dynamic environments. In response to these challenges, this paper introduces the use of graph neural networks (GNNs) to learn hidden spatial and functional patterns in complex vehicular networks. Combining with clustering-based methodologies. This approach enables the intelligent organization of network nodes, reducing transmission delays and enhancing connectivity in dynamic environments. The resulting framework supports predictions and estimates based on evolving communication and mobility patterns. They are further improving the efficiency of connectivity and communications in vehicular edge networks. Using graph neural networks (GNN) and clustering techniques to address connectivity challenges, reduce transmission latency, and manage the inherent unpredictability of rapidly changing vehicular settings, this study is poised to enhance the delivery of services and applications in vehicular networks. It also lays the foundation for prospective research into resource management
Sumner family fonds, 1849-1850, n.d.
Cyrus Sumner (1808-1850) was the son of Dr. Cyrus Sumner (1772-1834) and Mary Bell. Dr. Cyrus Sumner began a medical practice in Grimsby Township in 1806 and built a home on King Street in Beamsville. During the War of 1812 he accompanied Isaac Brock to Detroit as a surgeon and continued to serve in that capacity until the end of the war. Cyrus Sumner and Mary Bell had 10 children, including Cyrus Sumner Jr. In 1849, Cyrus Jr. traveled to California in 1849 seeking gold. He contracted a fever and died in Sacramento City, California, in November 1850.The fonds consists of a journal of Cyrus Sumner’s trip to California during the gold rush with a transcription of the diary; a silhouette portrait of Mary Bell Sumner; and a photocopy of a manuscript titled A Brave Pioneer by Helen Sumner Manson. Many of the journal entries are written as letters to family
Regulation of social behaviour via oxytocin receptor signaling in the caudodorsal lateral septum in Long-Evans male and female rats
The oxytocin receptor (OTR), a class A G-protein coupled receptor, is highly expressed in the lateral septum (LS), a brain region that regulates social behaviors in rodents. This thesis investigates whether OTRs within the LS modulate social approach-avoidance behavior, acquisition of long-term social recognition memory, and anxiety-like behavior in adult male and female rats. In the first experiment, L-368, 899, a selective OTR antagonist, was infused locally into the caudodorsal lateral septum (LSc.d), resulting in the attenuation of social approach, enhancement of social vigilance, and reduction in social novelty preference in male and female rats, with no effect on locomotion. In the second experiment, carbetocin, a biased OTR/Gq agonist, was locally delivered into the LSc.d, leading to reduced social approach and social novelty preference (a measure of social memory), with no effect on social vigilance or locomotion. Intriguingly, carbetocin increased latency to consumption of a highly palatable food only in male rats in the novelty-induced hypophagia test, indicating the sex-specific anxiogenic effects of the OTR/Gq signaling pathway in the region. In the third experiment, a selective full agonist of the OTR, (Thr4,Gly7)-Oxytocin, was infused into the LSc.d of male rats, resulting in a slight, but non-significant increase in social approach. Unlike the antagonist and the biased agonist, (Thr4,Gly7)-Oxytocin-treated rats showed social novelty preference 24 h after familiarization. Moreover, (Thr4,Gly7)-Oxytocin decreased latency to consumption of a highly palatable food compared to vehicle-treated rats, suggesting anxiolytic effects of the OTR full agonism. In conclusion, the findings suggest that OTR signaling in the LSc.d regulates social approach-avoidance, acquisition of social recognition memory and anxiety-like behavior depending on the activation of a specific upstream signaling arm of the receptor. I demonstrated that the OTR/Gq signaling pathway within the LSc.d promotes social avoidance in both sexes and triggers anxiogenic effects only in males, contrasting with the effects induced by the full agonism of the receptor
Empowering New Beginnings: A Holistic Evaluation of a Community-Developed Multi-Sports Program for New-to-Canada Refugee Youths and Its Impact on Physical Literacy, Mental Wellbeing, and Social Health
Resettlement for refugee youth in Canada presents multifaceted challenges, notably in integrating into existing social structures, including sports and physical activity (PA) programs. Sports and PA programs can play a crucial role in promoting physical and mental well-being, yet refugee youth often face lower participation rates compared to their Canadian-born counterparts. To address this gap, this study investigated the impact of a community-developed multi-sport program, the Calgary Catholic Immigration Society (CCIS) multi-sport program, on the physical literacy (PL) development and psychosocial well-being of young refugees in Calgary, Canada. The program aimed to equip refugee youth with the tools to embrace sports and PA opportunities in their new environment, fostering physical well-being and a sense of belonging. A total of 16 refugee youth participants between the ages of 13-19 years old (Mage = 16.00±1.75, n =14 males) were recruited for this study and were living in temporary housing (M = 1.19 months on arrival) while being assisted by CCIS during their resettlement period. The study employed mixed methods, including the PLAYbasic tool and a modified PLAYself questionnaire, to assess program effects on various PL domains. Qualitative data from focus group interviews and an ethnographic approach provided further insights into the program's broader impact on well-being and social health. The findings revealed positive changes, particularly for those who participated frequently. The program improved their fundamental movement skills, boosted their confidence, and influenced their motivation to participate in sports and PA. More importantly, the program fostered social connections and a sense of belonging, contributing positively to their mental well-being. Participants also benefitted from access to well-equipped facilities, structured programs with qualified coaches, and valuable resources within the community. However, challenges remain. Logistical difficulties like competing schedules and lack of awareness about the program hindered consistent participation. Additionally, gender disparities emerged, with female participants highlighting the need for privacy and female-specific programming. This study highlights the value of community-developed, culturally sensitive sports programs. Such programs can effectively promote PL development, social integration, and overall well-being among refugee youth. Future research should explore the program's long-term effects and address specific barriers that prevent female participation
Time Series Prediction: HMMs with TAN and Bayesian Network Observation Structures
This thesis addresses key challenges in time series classification, focusing on enhancing predictive ac curacy through innovative modeling techniques. First, we introduce TAN-HMM, an extension of the
traditional Hidden Markov Model (HMM) that incorporates Tree-Augmented Naive Bayes (TAN) to ac count for correlated features, significantly improving classification performance on complex datasets like
MSRC-12. Next, we propose the Bayesian Network Hidden Markov Model (BN-HMM), which com bines the temporal dynamics of HMMs with the structural flexibility of Bayesian Networks, achieving
superior accuracy and feature relationship discovery. Finally, we tackle the problem of robust early warn ing signals for disease outbreaks, utilizing cutting-edge deep learning models to predict emerging disease
behavior from simulated and real-world noisy datasets. Together, these contributions push the boundaries
of time series classification and offer practical solutions for real-world applications, from human activity
recognition to disease outbreak prediction
Niagara Grape and Wine Industry Collection, 1929-2005, n.d.
The collection consists mostly of promotional material related to the Niagara Grape and Wine industry, including wineries and other industry groups such as the Canadian Wine Institute, Brock University’s Cool Climate Oenology and Viticulture Institute (CCOVI), LCBO, Ontario Grape Growers’ Marketing Board, Vintners Quality Alliance (VQA), and Wine Council of Ontario. There are also programs and promotional material for the Niagara Grape and Wine Festival
Railroad Transportation of Dangerous Goods in Canada: Data-Driven Risk Analysis and Implications for Emergency Management
The purpose of this study is to examine key risk factors associated with the railroad
transportation of hazardous materials (hazmat) and to develop a data-driven risk analysis
methodology using rail incident records from 1999 to 2023 across Canada from multiple
resources and creating a risk management framework in case of hazmat release.
In the first stage, we will identify the primary factors affecting hazmat release during
rail transportation, such as time, location, activity, track type, train characteristics, load specifics,
and weather-related attributes. At this stage, utilizing machine learning techniques, including
Logistic Regression, Decision Trees, and a two-hidden-layer Neural Network, we aim to
facilitate the second stage of the study. This subsequent stage intends to provide insights and
recommendations for effective risk management strategies such as risk mitigation and disaster
prevention, preparedness, and response strategies within the context of hazmat rail
transportation, particularly in Canada
Market Reactions to Dual-class Share Creation and Unification: Evidence from Canada
This study examines the short-term market reactions to the creation of dual-class shares and the unification
of dual-class shares in Canada from 1980 to2022. Specifically, we analyze abnormal returns, trading
volume, liquidity, and institutional ownership changes surrounding these two events. We use the event
study methodology to conduct abnormal return analysis on three event days: The Announcement Day (AD),
the Approval Day (ApD), and the Effective Day (ED). For our creation sample, we observe the market
reaction on all three days and abnormal returns of more than 5% associated with the Announcement Day.
For our unification sample, we find a significant abnormal gain of nearly 4% on the Announcement Day.
We also observe that trading volume activity increases significantly around both the creation and unification
of dual-class shares. Consistent with previous literature, we find that stocks that adopt the dual-class share
structure experience a significant decline in liquidity. Cross-sectional regression analysis suggests that
positive abnormal returns of dual-class share creation can be explained by the firm’s arrangement of
financing or prospect of financing, whereas positive abnormal returns of unification are associated with
changes in institutional ownership. Overall, our analyses suggest strong market reactions and changes in
important aspects, such as liquidity of firms, to both events
A Review of Life Insurance’s Secondary Market
The secondary market for life insurance policies emerged to provide financial relief for terminally ill patients through viatical settlements. Over time, it expanded to include life settlements for seniors and individuals with chronic conditions. This growth was driven by demographic shifts and increased life expectancies.
This paper discusses the historical evolution of the secondary market, the types of transactions involved, and the market dynamics. It explores the benefits and challenges faced by policyholders, insurance companies, and investors. For policyholders, the market offers enhanced liquidity and fair compensation. However, it also requires insurers to adjust premium structures and manage adverse selection. Investors benefit from high returns and risk diversification, but they are also exposed to longevity risk, liquidity risk, return volatility, and regulatory changes. The study highlights the complexities of asymmetric information and emphasizes the need for sophisticated actuarial models and robust regulatory frameworks to ensure market stability and sustainability