title: Magnetically Interesting Coordination Complexes Based on Macrocyclic Ligands

subject: crown ether, Schiff-base  macrocycles, SMMs

abstract:
The synthesis and study of select 3d and/or 4f coordination complexes prepared from crown ether and Schiff-base dual compartmental macrocycles are described herein, working towards the discovery and study of new families of macrocyclic-based single molecule magnets (SMMs). Chapter 1 introduces the general theory of magnetism, molecular magnetism and SMMs and provides the reader with a brief overview of the relevant coordination chemistry of the two families of macrocycles.
In Chapter 2, two 15-crown-5 complexes [Ln(NO3)3(OH2)2(MeOH)], (where Ln(III) = Tb (I) and Dy (II)) have been prepared and characterized. X-ray diffraction studies reveal the two complexes crystallize as 1-D chains. Variable temperature ac magnetic susceptibility studies reveal that (II) is an SMM with two effective energy barriers, Ueff = 26 K (18 cm−1); τ0 = 4.10 × 10−7 s and Ueff = 41 K (29 cm−1); τ0 = 1.35 × 10−8 s, whereas ab initio studies suggest that the observation of slow relaxation of magnetization in the Tb complex (I) is hindered by the presence of rapid quantum tunneling mechanisms (QTM). Solid state photoluminescence measurements reveal the two complexes have well-resolved f–f transitions, where a Gaussian fit of the fine structure of the highest-energy emission band for the Dy(III) complex allows the Stark splitting of the ground state to be determined.
In Chapter 3, select Ln(III) complexes with benzo and dibenzo 15-crown-5 macrocycles were synthesized and characterized. Reaction of Dy(III)  together with benzo 15-crown-5 afforded  a unique [Dy(OH2)8]3+ complex (III), where the hydrated Dy(III) cation is fully encapsulated within a supramolecular cage formed by three benzo 15-crown-5 macrocycles. Interestingly, the close to perfect square antiprismatic geometry of the 4f ion enhances its axial anisotropy, which suppresses quantum tunnelling mechanisms (QTM) in the ground and first excited states, resulting in the observation of SMM behavior in zero dc field. For this system the magnetic data were further supported by solid-state photoluminescence and ab initio studies, The introduction of a second benzene ring into the organic framework of the macrocycle increases its rigidity, where on coordination to Dy(III), affords the partially encapsulated complex (IV), which displays slow relaxation of magnetisation, consistent with SMM properties.
In Chapter 4, the coordination chemistry of a dual compartmental Schiff-base macrocycle H2L3 containing O3O2 and N3O2 cavities was explored together with select 3d and 4f ions. In the first part of this chapter, the coordination chemistry of H2L3 with 3d metal ions is presented, where in the presence of NaOH, the Na(I) ions reside in the O3O2 cavity and the 3d ions occupy the second N3O2 cavity. Three coordination complexes containing Cu(II), Zn(II), and Mn(II) ions were prepared and characterized. The Cu(II), and Zn(II) complexes are monomeric with molecular formulae [CuNa(L3b)ClCH3OH]‧6H2O (V) and [ZnNa(L3b)(CH3COO)(CH3OH)]‧H2O (VI) respectively, while the Mn(II) complex crystallizes as a trimer with stoichiometry [Mn3Na2(L3)2(CH3COO)4]·5.75CH3OH·0.5H2O (VII). For complexes (V) and (VI), nucleophilic addition of the NH of the N3O2 cavity to the carbon atom of the adjacent imine results in a contraction of the N3O2 cavity and the formation of a five-membered imidazoline ring to afford the modified ligand L3b.The magnetic properties of (V) and (VII) are also reported. In the second part of this chapter, coordination of the macrocycle to select 4f ions in the absence of any base afforded the mononuclear complexes [Dy(H2L3)(H2O)2(CH3OH)2]Cl3·CH3OH, (VIII), and  [Ln(H2L3)(H2O)3(CH3OH)] Cl3, where Ln(III) = Tb (IX), Er (X), and Gd (XI), in which the Ln(III) ion is coordinated in the O3O2 cavity. Magneto-structural studies on these complexes reveal that the Dy complex has a slightly different structure than the other three complexes, however all four 4f ions crystallize with square antiprismatic geometries, where only the Dy(III) complex (VIII) displays SMM properties.


title: Synthesizing Self-Healing and Recyclable Silicones Using the Diels-Alder Reaction as a Cross-Linker: Investigation of Various Dienes and Dienophile Systems

subject: Self-healing, Diels-Alder, Recyclable, Cross-linking

abstract: This thesis focuses on the synthesis of recyclable and self-healing polysiloxane elastomer networks. These features were achieved through the use of thermally reversible Diels-Alder (DA) and retro-Diels-Alder (rDA) reactions. In this work, for the model system, two different dienes (3 and 8) and six dienophile were explored, of which five of the dienophiles are commercially available and one of them was synthesized in the lab (13) to produce a series of model DA adduct. Model systems consisting of diene-functionalized trisiloxanes and bismaleimides as dienophiles were utilized to develop a fundamental understanding of how the electronic differences in the coupling systems would influence the efficiency of the overall reaction. Then for the elastomers, three different methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxane terminated (PDMS) with different molecular weights and Si-H group mole percentages [32 a = 3-4% Si-H and 13000 g/mol; 32 b = 7-9% Si-H and 5500-6500 g/mol; 32 c = 25-30% Si-H and 2000-2600 g/mol] were used and functionalized with two different dienes (3 and 8) to produce six polymeric diene systems (33 a, 33 b, 33 c, 34 a, 34 b and 34 c). After analyzing the model systems, the optimal temperature for adduct formation was determined to be between 60 °C – 70 °C, while the rDA reactions occur were found to occur between 90 °C and 110 °C , depending on the system. The tensile strengths of the elastomer systems correlated well with the cross-link densities of individual elastomers (elastomers were elongated between 0.3 cm and 2.54 cm). Furthermore, the hardness of the elastomers also correlated with the cross-link density of the elastomer (Shore 00 values ranged from 32 to 8 ). However, all of the elastomers displayed a decrease in their Shore 00 values after being damaged and healed. Of particular note in this study are elastomers 35 b and 35 c.  Not only were these the only examples of translucent and colourless materials, the elastomers fully cured at room temperature in only 5 h. After mechanical damage the elastomers were heated to 80 °C to induce mobility in the polymer chains, complete healing of the mechanical damage was observed to occur in approximately 3 min and upon cooling to room temperature it cured and got solid again.


title: Chemoenzymatic Formal Total Syntheses of Tetrodotoxin and an Approach to Daphenylline

subject:
tetrodotoxin
daphenylline
total synthesis

abstract: This thesis describes chemoenzymatic formal total syntheses of tetrodotoxin and a concise synthetic approach to daphenylline. Advanced intermediates for the syntheses of tetrodotoxin reported by the groups of Fukuyama, Alonso, and Sato were prepared. Key steps included toluene dioxygenase-mediated dihydroxylation of either iodobenzene or benzyl acetate and a [4+2] hetero-Diels-Alder cycloaddition/Kornblum–DeLaMare rearrangement sequence to construct a common enone intermediate. The resulting key enone was transformed into Fukuyama's intermediate in four steps, into Alonso's intermediate in six steps, and into Sato's intermediate in seven steps. Fukuyama’s route employed a highly stereoselective allyl cyanate-to-isocyanate rearrangement to install the nitrogen atom at C8a. This protocol was also successfully applied in designing a synthetic avenue to daphenylline. The ABC tricyclic skeleton of daphenylline was successfully constructed in just eight steps starting from readily available (S)-carvone.


title: Negotiating a Gendered Neo-Calvinist Pillar: Immigrant Loss, Transformation, and Lifelong Learning

contributor: Department of Graduate and Undergraduate Studies in Education

subject:
Life history
Dutch neo-Calvinist immigration
critical feminist
lifelong learning
dialectic method

abstract: Employing a critical feminist perspective, I conducted a sociocultural analysis of the lifelong learning of Dutch neo-Calvinist women who immigrated to Canada shortly after World War II. The purpose of the research was a critique of the institutional ruling relations (schooling, religion, family, workplace) that shaped and influenced the trajectory of these women’s lifelong learning. More specifically, the inquiry included an interrogation of their Canadian schooling experience, in the context of an immigrant family life, their pillarized Dutch culture, and Calvinist religiosity. In choosing a life history methodology, the scope of the research broadened where one’s life story was juxtaposed to a theory of context. Applying this methodology, I critically analyzed structures, operations, and contestations of power in lifelong learning institutions through an exploration of the multiple contexts that shaped the lives of immigrant women. It is within that relationship that the critical feminist was possible. The life histories were not a description of the mainstream but rather were positioned to dialectically interrogate the meaning and significance of the past as it influenced the present and future. Applying a dialectic method to the participants’ life histories, 7 tensions were raised that made visible ruling relations relevant to the participants’ everyday experiences and brought awareness to the underlying contextual and ideological assumptions related to their trajectory of lifelong learning. Employing a critical feminist perspective, I examined how 3 neo-Calvinist immigrant women interpreted and negotiated the ambiguity created by cultural contradictions experienced in a Canadian context. As a researcher who herself has been shaped by this specific immigrant experience, a key attribute of life history methodology was its capacity for the researcher self to be visible in the research.


title: The Effects of Chronic High Intensity Interval Training on Cardiometabolic Health in Individuals With Spinal Cord Injury

subject:
High Intensity Interval Training
Spinal Cord Injury
Metabolic Syndrome

abstract:
Abstract
	Advancements in medicine and post-injury care has allowed for the extended life expectancy following spinal cord injuries (SCI). However, such advancements have led to a paradigm shift in the prevalence of secondary health complications from renal and pulmonary to cardiovascular and metabolic. In the able-bodied literature, accumulating evidence for high intensity interval training (HIIT) has shown that this time efficient, heart safe style of exercise may have advantages over moderate intensity continuous training (MICT) as a means to reduce cardiometabolic risk. The effectiveness of HIIT in an SCI population has yet to be explored. The current study examined the effectiveness of the “5 by 1” HIIT protocol over a 6-week timeframe, consisting of three supervised sessions per week in an SCI population. Outcome measures included VO2peak, cholesterol, triglycerides, waist circumference, blood pressure, pro an anti-inflammatory cytokine, and adipokines leptin and adiponectin. Results of the current study suggest that this protocol is an effective means to significantly improve aerobic fitness, however the intervention did induce significant metabolic change. Limitations such as small sample size (N=7) and the relatively short intervention duration may have limited these results. Further research focused on the effectiveness of HIIT in an SCI population is warranted to explore whether the metabolic benefit from HIIT may be dependent on a minimum baseline fitness level or power output that some individuals may not possess. In conclusion, the “5 by 1” HIIT protocol proved to be an effective means of improving aerobic capacity and therefore represents an alternative to the currently suggested MICT.


title: Development and Investigation of the Fluorescence of Cyclopropenium Ions

subject:
Proton Sponge
Boronium
Fluorescence
Fluorophores
Cyclopropenium Ion

abstract: The work presented herein employs cyclopropenium ions as a central design element towards the goal of developing fluorescent, superbasic and boronium-substituted compounds. A novel guanidine-cyclopropenimine proton sponge with exceptional basicity is reported that was further utilized to develop a stable tetracoordinate boronium-substituted proton sponge. A large focus of this thesis was also placed on the development of the recently discovered fluorescence of cyclopropenium ions leading to a new class of small molecule organic fluorophores. Among this new platform of fluorescent compounds, a specific fluorophore featured an impressive photophysical profile that bodes well for future applications in fluorescent imaging techniques. Insight into the structure, electronics, bonding and photophysical properties of these derivatives is offered.


title: Assessing environmental controls for candidate microbial ichnofossils in hydrothermally altered basaltic tuffs of Upsal Hogback, NV

subject: astrobiology volcanology hydrothermal carbonate ichnofossil

abstract: Putative biogenic alteration has previously been identified in basaltic glass of the ocean floor, in subglacial hyaloclasts, in meteorite impact glass, and more recently in tuff erupted in a lacustrine environment. Documentation of putative biogenic alteration and characterization of the environments in which they have formed improves understanding of the thermophilic chemotrophic euendoliths to which the ichnofossils are attributed, which may enhance humankind’s understanding of the origins of life on Earth and potential evidence of life elsewhere. Upsal Hogback is a series of monogenetic tuff rings in the topographic low of the Carson Sink in the Lahontan Basin in Western Nevada. These tuff rings erupted into pluvial Lake Lahontan between 19 ka and 33.7 ka. Tufas emplaced on the tuff rings are especially abundant at two elevation intervals, which can be correlated to stillstands of Lake Lahontan, providing the minimum age constraint for the emplacement of Upsal Hogback. Chemical analysis of basalts from each ring indicates a common magmatic source that was likely affected by fractional crystallization of olivine and plagioclase as the rings erupted from north to south. In basaltic tuff of Upsal Hogback, petrographic analysis has revealed the presence of putatively biogenic alteration textures in association with palagonite, calcite, and zeolites. Tuff samples with the most abundant putative biogenic alteration are those from the interior of the tufas. Biogenic origin of the textures is indicated by their size, the log-normal distribution of their sizes, and the complex morphology which cannot readily be explained by known abiogenic processes. Measurement of palagonitization and consideration of zeolite assemblage indicates a hydrothermal fluid of sustained temperature between 40°C and 60°C. Upsal Hogback’s autochthonous carbonates, basaltic tuff, palagonitization, and the emplacement of the tuff rings in an alkaline lake may make it a good analogue for the Mars 2020 landing site in Jezero crater, Mars. The geologic characteristics of Upsal Hogback, including the hydrothermal regime, together with the early stage of putative biogenic alteration identified, provide an instructive example for future work investigating terrestrial and extraterrestrial environments for evidence of life.


title: An in vivo, ex vivo, and in vitro exploration of the use of chronic hypoxia/physioxia and ROS/RNS-mediated alteration of physiological function in mitochondrial disease

subject:
cell culture
reactive oxygen species
SERCA
mitochondrial disease
SOD2

abstract: Reactive oxygen species (ROS) and reactive nitrogen species (RNS) are by-products of cellular O2 metabolism and participate in cell signalling and normal physiological homeostasis. Although ROS/RNS are normal and important molecules in cell physiology, production in excess or in absence of sufficient cellular antioxidant capacity can lead to critical cellular damage which has shown to contribute to a plethora of disease pathologies. Experimental evidence has also supported the use of chronic limitation of ambient O2 gas as a means to reduce the amount of ROS/RNS in both animals and cell culture. The purpose of this thesis was to explore the use of a regulated O2 environment to determine if chronic hypoxia and/or physioxia may influence ROS/RNS production in animal and cell culture models of various known mitochondrial diseases. The absence of superoxide dismutase 2 (SOD2) has been proven to be extremely lethal, so I attempted to breed and house entire mouse dams in hypoxia (11% O2) to investigate if limiting O2 might reduce the amount of ROS/RNS-mediated damage and extend the life span of SOD2 knockout (KO) mouse pups. Many attempts to rescue these KO mice failed due to premature death and/or maternal cannibalism, however, the SOD2 heterozygote (SOD2+/-) – which experience halved SOD2 expression compared to wildtype controls – were viable and body mass data was examined. Although no main effect was found of genotype on body mass over time, male, but not female, mice housed in chronic hypoxia gained significantly less weight than their normoxia (20% O2) counterparts. After examining live animals, I focused on measuring the effects of regulating the O2 environment on ROS production in a variety of cellular models of different mitochondrial disease. Some measure of structural and/or functional integrity is compromised in mitochondrial disease, typically leading to exacerbated proton leak, subsequent superoxide/hydrogen peroxide (H2O2) formation, and, unsurprisingly, a significant potential for cellular damage. These features of mitochondrial disease are further compounded by the fact that a great deal of published cell culture work does not actively regulate O2 levels and thus cells often experience an environment with O2 levels hyperoxic relative to what is typically experienced in vivo. The purpose of this second study was to investigate whether growing and assaying mito-disease cell lines in a regulated, physiologically-relevant O2 environment would reduce H2O2 output to levels similar to wildtype controls. Measuring H2O2 production from various mito-disease cell lines, almost all cell lines produced more H2O2 when grown in normoxia (18% O2) culture conditions compared to physioxia (5% O2), however, only a few of the mitochondrial disease cell lines tested here produced the expected increase in cellular H2O2 efflux than their wildtype counterparts at 18% O2. As expected, almost all mitochondrial disease cell lines produced H2O2 at a similar level to their respective controls when grown in 5% O2. Furthermore, NADPH Oxidases (NOX) were explored as a potentially significant source of elevated ROS production at 18% O2. However, upon NOX inhibition, no significant measurable changes in H2O2 production were reported in any of the cell lines tested here. Finally, the last study in this thesis explored structural and functional consequences which may accompany halved SOD2 expression in adult SOD2+/- female mice over time. Sarco-endoplasmic reticulum ATP-ase (SERCA) is an enzyme responsible for calcium handling in myocytes and its function is critical for proper muscular relaxation and contraction. The soleus and extensor digitorum longus (EDL) were analyzed to determine whether muscle type (ie. slow-oxidative muscle or fast-glycolytic muscle) would influence the effects of heterozygous SOD2 deletion. Interestingly, the soleus muscle showed significant impairments in SERCA function with a reduction in SERCA’s apparent affinity for calcium, whereas there were no differences between genotypes in the EDL muscle. This corresponded well with the fact that SERCA tyrosine nitration was significantly elevated in the soleus, particularly on SERCA2a. Conversely, there were no signs of elevated SERCA tyrosine nitration on SERCA1a, the predominant SERCA isoform in the EDL. In conclusion, the results from these studies provide some insight to the roles that O2 and ROS generation have on physiological function in vivo and in vitro, though it also prompts further investigation due to mixed results in many cases.


title: Positive Body Image and Physical Activity in Pregnant Women

subject: Pregnancy, body appreciation, embodiment, self-objectification, physical activity

abstract:
Generally, research has shown pregnant women have a more negative body image pre-pregnancy
and early pregnancy compared to mid-to-late pregnancy. Negative body image in this population
has been linked to several important pregnancy-related behaviours and poorer mental health that
may put the mother’s and baby’s health at risk. In regards to positive body image, there has been
a lack of research investigating how positive body image constructs such as body appreciation
and embodiment change, and little work has examined how self-objectification changes. In nonpregnant
populations, positive body image has been linked to several health behaviours and
outcome; thus, it is important to determine if pregnant women experience positive body image
during their pregnancy. In addition, participation in physical activity has been linked to
improvements in body image via an increase in embodiment and a decrease in selfobjectification
in young adult women. Whether this is true for the pregnant population is
unknown.

The overall purpose of this study was to understand the relationship between positive body
image and physical activity in pregnant women. The first purpose was to determine whether
body appreciation, embodiment, and self-objectification levels differ across trimester. The
second purpose was to determine if physical activity was associated with body appreciation, and
if this relationship was mediated by an increase in embodiment and a decrease in selfobjectification.
Thirty-one women in the first trimester, 55 in the second trimester, and 75 in the
third trimester completed measures of body appreciation, embodiment, self-objectification, and
physical activity online. Multivariate analysis of covariance showed all measures differed by
trimester. Post-hoc tests showed body appreciation (M = 3.79; SE = 0.08) and embodiment (M =
2.92; SE = 0.05) were higher and self-objectification (M = 3.86; SE = 0.14) lower in third
trimester compared to first trimester (M = 3.37; SE = 0.12; M = 2.56; SE = 0.09; M = 4.54; SE =
0.22). Embodiment was also higher in the third trimester (M = 2.92; SE = 0.05) compared to the
second trimester (M = 2.67; SE = 0.06). Serial mediation analysis revealed physical activity was
associated with body appreciation through an increase in embodiment and a decrease in self-objectification.
The findings from this study indicate positive body image improves across
pregnancy and physical activity could be one way to improve positive body image in pregnant
women.


title: Health Care Aides' Conversations with Families About End-Of-Life and Dementia

subject:
Dementia
End of life
HCA

abstract: Background: Research has demonstrated that health professionals have a difficult time talking with family members of people with dementia about end-of-life and avoid these conversations. A palliative approach is appropriate for dementia and effective communication between healthcare providers and relatives is imperative in this approach. Research Question: How do health care aides (HCAs) in long-term care (LTC) homes experience discussions about death and dying with relatives of residents who have dementia? The aim of this descriptive qualitative study was to explore the experiences of health care aides’ (HCAs) and understand the conversations they have with family members when a resident in long-term care has dementia and is nearing end-of-life. Methods: This study was a descriptive qualitative study, with thematic analysis of interviews of 14 HCAs from 6 LTC homes in Ontario, Canada. Findings: There were four themes. Findings include conversations occur in-person and families initiate conversations. Conversations can be difficult and emotional and relationships with residents, families, fellow HCAs, and nurses, influence the conversations. Conversations occur in the context of written and unwritten rules and can make conversations difficult. Discussion: Conversations between HCAs and families occur, and HCAs respond to relatives’ questions. It is important to support HCAs and provide them with a clear understanding of responding to relatives’ questions.


title: Evaluation of the PLCOM2012 Risk Prediction Model and National Lung Screening Trial Criteria for Selecting Individuals for Lung Cancer Screening

subject:
Cancer Epidemiology
Bio-statistics
Lung Cancer Screening
Risk Prediction Modelling

abstract:
Background: Lung Cancer (LC) is the leading cause of cancer death in North America. Cancer screening trials, such as the PLCO (Prostate, Lung, Colorectal and Ovarian) and NLST (National Lung screening trial) evaluate LC mortality. There has been a growing interest in risk prediction modelling for selecting high-risk individuals for LC screening. Increased risk for developing LC is however associated with greater risk of dying from non-LC (competing) causes; the presence of coexisting illnesses may negate the net benefit of LC screening.
Purpose: The focus of this study was to compare the two selection criteria methods, the NLST criteria and the PLCOM2012 model (at 1.5% and 2% 6-year risk), for selecting smokers age of 55 to 75 for screening who may develop LC, and to evaluate which risk factors are strongly associated with competing causes of death (CCoD).
Methods: Contingency table and logistic regression analysis, using STATA software, were used to analyze the results of applying both criteria on the PLCO ever-smokers population
(N= 74 207). A CCoD logistic regression model was developed using 5-year follow-up data to assess the association between each PLCOM2012 model predictor and non-LC death. Predictor variables were ranked by their ability to predict 6-year LC incidence and 5-year non-LC death. Predictive performance, discrimination (area under the receiving-operating-characteristic curve [ROC-AUC]) and calibration were assessed.
Results: Significantly higher LC proportions were found using the PLCOM2012 model than the NLST criteria in various individual characteristics. Increasing the model threshold resulted in less false positives, higher positive predictive value and probability of 6-year LC incidence. The PLCOM2012 model was also shown to be significantly associated with 5-year non-LC death (p<0.001). The CCoD model demonstrated fair discrimination (AUC=0.7114) and good calibration. There was an overall agreement in the rank order of variables predicting LC incidence and non-LC death, with the top four variables being age, smoking intensity and duration, and body mass index (BMI), however the effects were opposite in nature for the latter.
Conclusion: Findings show that the PLCOM2012 risk prediction model accurately identifies higher proportions of LC cases compared to the NLST criteria, however it also selects individuals for LC screening who are at risk of dying from competing causes who will not benefit from screening. Decisions on LC screening among individuals at high-risk of developing LC should be based on an appropriate assessment of each person’s health status and life expectancy, in order to maximize the benefit-harm ratio from LC screening.
Keywords: Lung cancer, epidemiology, risk prediction modelling, lung cancer screening, competing causes of death


title: Dance with a B-E-A-T: Recreational Dance with Behaviour Analysis and Therapy for Children and Youth with Exceptionalities

subject:
Exceptionalities
Neurodevelopmental Disorders
Cognitive Behavior Therapy
Applied Behavior Analysis
Recreational Dance

abstract: While there is much research highlighting the positive benefits of recreational dance for typically developing individuals, there is considerably less research pertaining to individuals with unique needs, abilities and diagnoses (Burkhardt & Brennan, 2012). Evidently, there is a need for recreational dance programs that blend the proper interventions, supports and adaptations uniquely in order to support and include participants with varying abilities and challenges. The purpose of this research study was to pilot Dance with a B-E-A-T (Dance with Behavioral Analysis and Therapy), a recreational dance program with behavioral principles and therapeutic components for children and youth (7 to 12 years of age) with various exceptionalities such as neurodevelopmental disorders and/or anxiety disorders. This 8-week dance intervention program resulted in varying yet promising results across three primary domains for its three participants which were: (a) gross motor dance skills, (b) gross motor balance skills, (c) parent and child self-efficacy. Significant results showed improvements in gross motor skills across all three clients; with regards to self-efficacy however, results revealed significant changes in one out of three clients and two out of three of the client’s guardians. Further, consumer satisfaction results concluded a high level of satisfaction and program effectiveness across all three families. These findings are discussed in terms of the lack of previous research conducted within the field and the importance of therefore propelling such research in order to reach more youth with exceptionalities through alternative, enjoyable and empowering forms of therapeutic approaches.


title: How Do Adventure-Based Team Building Programs Produce Change? A Case Study.

subject:
team building
challenge course
change theory
adventure education
group dynamics

abstract: Adventure-based team building programs are commonly used for the purposes of creating positive change in individuals and groups of people. Nevertheless, the body of research on these programs is largely composed of quantitative studies that examine their efficacy and outcomes, but fail to address questions regarding how these programs facilitate positive change. Answering past scholars’ call for theory-based research that explores processes, the present study utilized a qualitative case study design to explore how a challenge course program facilitated interpersonal and intrapersonal change among a group of post-secondary students employed as Residence Life Staff at a mid-sized Canadian university. Data were collected via researcher observations of the program, focus group interviews, individual interviews, and document collection, and analyzed through inductive and comparative analysis. Results revealed that the program facilitated increases in group sociability and participants’ interpersonal relationships, communication and confidence. Program elements that facilitated those changes, such as an informal atmosphere and an element of challenge, were also identified. Kurt Lewin’s (1947a) theory of planned change was utilized as a theoretical framework for understanding the process of change, which illuminated the importance of participants’ pre-program readiness for change (i.e., unfreezing) and the sustainment of those changes post-program (i.e., freezing). Lewin’s conceptualization of field theory and group dynamics offered further relevant theoretical insights. Findings have implications for future participants, practitioners, and researchers, and make a theoretical case for the continued use of Lewin’s theory of planned change as a framework in the field of adventure and experiential education.


title: Sleep and Emotion Processing in Individuals with Insomnia Symptoms and Good Sleepers

subject:
insomnia
emotion processing
hyperarousal
EEG

abstract: Despite complaints of deficits in waking socioemotional functioning by individuals with insomnia, only a few studies have investigated waking emotion processing performance in this group. Additionally, the role of sleep in socioemotional processing has not been investigated using quantitative measures of sleep. The thesis investigated sleep and behavioural processing of emotionally expressive faces in individuals with insomnia symptoms (n=14) compared to healthy, good sleepers (n=15). The primary aim was to investigate the degree to which sleep predicted emotion processing. Participants completed two nights of at-home polysomnography-recorded sleep, and sleep diaries, which was followed by an afternoon of in-lab performance testing on tasks measuring processing of emotional facial expressions with an emotional Stroop task and a face categorization and intensity rating task. The insomnia group reported less total sleep time on their diary but no other differences in subjective or objective sleep were observed. No behavioural differences in emotion processing were observed overall. Post-hoc analysis of the individuals with insomnia symptoms that had a poor night of sleep on the night prior to performance assessment (n=8) revealed that a poor night of sleep in insomnia was associated with reduced time in Stage 2, REM and NREM sleep, and, there was trending support for elevated Sigma and Beta activity throughout the night as well as performance deficits for identifying emotional face expressions. For individuals with insomnia symptoms, greater levels of Beta EEG activity throughout sleep was associated with greater intensity ratings of happy, fearful, and sad faces. In conclusion, the thesis identified that the hyperarousal phenomenon in insomnia was related to altered waking salience assessments and gives promise for a new stream of research that investigates the relationship between hyperarousal in sleep and waking emotion functioning in insomnia.


title: Lessons learned from a critical appraisal of a fall break policy in higher education: A case study

subject: Fall Break, Mental Health, Policy Analysis, Case Study

abstract:
The incidence, severity and persistence of mental health issues is increasing across post- secondary campuses (Zivin et al., 2009; Canada Newswire, 2012) with these students now viewed as a high-risk population (Stallman, 2010). Many Canadian universities are implementing a policy for a fall break in hopes of alleviating students’ stress and anxiety in order to improve mental health, heighten retention, and increase academic productivity. To date, there is limited empirical evidence to guide the development of policy and the delivery of effective practices to alleviate school-related stress and anxiety.
This thesis is presented as a three paper, manuscript approach. The focus of this project was to appraise the development and implementation of a fall break and then evaluate its effectiveness in an effort to address rising concerns related to mental health for post-secondary students.
Three thousand and seventy-one students in years one to four completed a post-break survey during one week in January of 2013, 2014, 2015. Of those, 1019 were male and 2052 female. Thirty-three students varying in years from one to four participated in focus groups in February of 2013, 2014, 2015. Of those 4 were male and 19 were female. Ten faculty from varying faculties and one informant participated in interviews in spring, 2018.
Analyses from the surveys revealed that overall, students are in favour of having a fall break. Even though a small percentage of participants perceived their workload to go up before and after the break, 90% of students agree that the fall break was useful in reducing school related stress levels. However, the focus group, faculty and informant interviews revealed that the timing of the fall break had an impact on how students and faculty experienced the break and thus influenced perceptions on the impact that the break had on student mental health.
Comprehensive evidence about whether a fall break policy supports or undermines the mental health of students needs to be assessed using a range of indicators before its implementation. This will help post-secondary institutions determine whether a break in the fall semester can be an effective approach to addressing students’ stress and anxiety.


title: The Synthesis of Phosphatidylinositol Bolalipids

subject: Sec14, Pik1, bolalipid, phosphatidylinositol

abstract:
This thesis describes the attempted synthesis of phosphatidylinositol bolalipids to be used in the investigation of the mechanism of the phosphatidyl inositol transfer protein, Sec14, and the PI(4)-kinase, Pik1. The synthesis of two unique bolalipids was the goal of this thesis. The esterification of the sn1 position of a protected glycerol unit to stearic acid as well as esterification at the sn2 position to either the C20 or C36 diacid gave the framework of the desired bolalipid. Further success was seen in the coupling of benzyloxybis(diisopropylamino) phosphine to the sn3 position of the deprotected glycerol unit in the generation of a phosphoramidite. However, efforts in the final step of the synthetic method were unsuccessful and did not lead to the complete synthesis of the bola-PI. Though it was possible to couple the 2,3,4,5,6-benzyl protected myo- inositol to the phosphoramidite, the most significant issues in the synthesis of the bola-PI is the oxidation of the phosphite to the phosphonate. Despite multiple attempts with varying oxidizing agents, no oxidation was observed by TLC, P NMR or mass spectrometry data. Two
phosphoramidites, precursors to the desired bola-PI molecules, have been synthesized to date. The two phosphoramidites were characterized by H NMR, C NMR, P NMR, mass spectrometry, and optical activity. They are both air and water sensitive and have been observed to decompose with storage, even when placed under nitrogen at -4 oC. Spectral and experimental data are provided for all new compounds.


title: A Less Simple View of Reading: The Role of Inhibition and Working Memory in the Decoding-Comprehension Relationship

subject:
reading
decoding
inhibition
working memory
reading comprehension

abstract: The present study examines the influencing effect of executive functions, specifically inhibition and working memory, on the relationship between decoding and reading comprehension. The current research suggests that the decoding-comprehension relationship is likely more complex than past theoretical models have postulated. Recently, the idea that non-linguistic cognitive skills may be responsible for this relationship has gained traction. As a part of the NHLP, a longitudinal cohort study conducted in New Haven, Connecticut, 256 students were asked to complete reading and executive function measures, as the children progressed through grade 1 and 2. These measures included tasks independently designed to assess decoding, working memory, inhibition and vocabulary, as well as two separate measures of reading comprehension. Results showed that inhibition acted as a significant mediator in both the decoding-comprehension and vocabulary-comprehension relationships. The results also showed that working memory acted as a significant moderator of the direct effect in the decoding-comprehension relationship, but did not moderate the vocabulary-comprehension relationship. These findings support the idea that decoding and language alone are not solely responsible for reading comprehension performance, and that other non-linguistic factors must be taken into consideration. Better understanding the decoding-comprehension relationship has important implications for teaching practice, and early identification and intervention required for exceptional learners.


title: Effect of the Side Effect Machines in Edit Metric Decoding

subject: Evolutionary Programming, Side Effect Machine, Error Correcting Code, DNA Sequence

abstract:
The development of general edit metric decoders is a challenging problem, especially with
the inclusion of additional biological restrictions that can occur in DNA error correcting
codes. Side effect machines (SEMs), an extension of finite state machines, can provide
efficient decoding algorithms for such edit metric codes. However, finding a good machine
poses its own set of challenges and is itself considered as an open problem with no general
solution. Previous studies utilizing evolutionary computation techniques, such as genetic
algorithms and evolutionary programming to search for good SEMs have found success in
terms of decoding accuracy. However, they all worked with extremely constricted problem
spaces i.e. a single code or codes of the same length. Therefore a general approach that
works well across codes of different lengths is yet to be formalized.

In this research, several codes of varying lengths are used to study the effectiveness of
evolutionary programming (EP) as a general approach for finding efficient edit metric decoders.
Two classification methods—direct and fuzzy—are compared while also changing
some of the EP settings to observe how the decoding accuracy is affected. The final
SEMs are verified against an additional dataset to test their general effectiveness. Regardless
of the code length, the best results are found using the fuzzy classification methods. For
codes of length 10, a maximum accuracy of up to 99.4% is achieved for distance 1 whereas
distance 2 and 3 achieve up to 97.1% and 85.9%, respectively. Unsurprisingly, the accuracy
suffers for longer codes, as the maximum accuracies achieved by codes of length 14 were
92.4%, 85.7% and 69.2% for distance 1, 2, and 3 respectively. Additionally, the machines
are examined for potential bloat by comparing the number of visited states against the number
of total states. The study has found some machines with at least one unvisited state.
The bloat is seen more in larger machines than it is in smaller machines. Furthermore, the
results are analyzed to find potential trends and relationships among the parameters. The
trend that is most consistently noticed is that — when allowed, the longer codes generally
show a propensity for larger machines.


title: Examining the Roles of Octopamine and Proctolin as Co-Transmitters in Drosophila melanogaster

subject:
Synaptic Modulation
Octopamine
Proctolin

abstract:
The nervous system is a highly complex and intricate system that interacts with and controls nearly all the other body systems. The basic functions of nerve cells are conserved across most species and are very similar between vertebrates and invertebrates. Chemical transmitters (neurotransmitters) facilitate communication between nerve cells and their targets. The effects of these signals can be modified by co-transmitters that are released from neurons in conjunction with neurotransmitters, and by neuromodulators that are released as hormones. This thesis examines the effect of two neuromodulators on neuromuscular junctions of the fruit fly, Drosophila melanogaster. Two modulators, proctolin and octopamine, have been identified in motor nerve terminals and are thought to be released as co-transmitters to modify the effects of glutamate, the neurotransmitter that depolarizes muscle cells and triggers contraction.
The neuropeptide proctolin (Arg-Tyr-Leu-Pro-Thr) was found to increase the amplitude of body wall muscle contractions elicited by glutamate in the absence of nerve stimulation. Thus, proctolin appears to enhance contractions by acting postsynaptically. Previous work reported that increasing neural activity lowers the threshold and EC50 for proctolin’s ability to enhance nerve-evoked contractions by two orders of magnitude. To determine whether such activity-dependence is caused by increased release of glutamate, effects of varying glutamate concentrations on the effectiveness of proctolin are examined here. The threshold for proctolin to increase body wall contractions decreased from 100 nM to 10 nM when glutamate concentration increased from 5 mM to 7 mM, but the threshold increased again to 100 nM for glutamate concentrations of 10-20 nM. Thus, although the effectiveness of proctolin shows some dependence on glutamate concentration, alterations in glutamate levels do not appear to account entirely for the more substantial and more consistent changes in proctolin threshold that occur with increasing neural activity, reported elsewhere.
Since octopamine in known to be present in motor neurons innervating most of the body wall muscles of 3rd instar larvae, it was hypothesized that stimulating the motor neurons should release octopamine together with glutamate, and that increasing motor neuron activity should increase the release of both octopamine and glutamate. This hypothesis led to the prediction that an octopamine antagonist, phentolamine, should reduce the amplitude of nerve-evoked contractions, and that the antagonist should be more effective when the motor neurons are stimulated at higher frequencies. Phentolamine, however, did not alter the amplitude of body wall muscle contractions elicited by stimulating the motor axons using impulse bursts with intraburst stimulus frequencies of 5, 32 and 50 Hz. Surprisingly, exogenously applied octopamine did enhance the amplitude of nerve-evoked contractions, and, this effect was antagonized by phentolamine when contractions were elicited by impulse bursts with frequencies of 5 and 50 Hz. At a concentration of 1x10-6 M, octopamine did not induce contractions or alter the amplitude of glutamate-evoked contractions. These results do not support the hypothesis that endogenous octopamine is released onto muscle fibers as a co- transmitter to augment contraction amplitude.
One possible explanation for these findings is the octopamine may be released at higher concentrations at neuromuscular synapses, and the effects of octopamine on nerve-evoked contractions are mediated presynaptically, by increasing transmitter release. Overall, the results of this thesis indicate that both octopamine and proctolin modulate muscle contractions
in an activity-dependent manner; the level of external nerve-stimulus or exogenous glutamate concentration alter the effectiveness of the contransmitters. However, further work is needed to elucidate the mechanisms of such activity-dependence.


title: Beyond Displacement: Understanding the Intersection of Cultural Variables on Mental Health Service Utilization among Newcomers

subject:
Mental Health
Immigrants
Culture
Service Use
Newcomers

abstract: Existing literature regarding mental health and mental health service access reveals disparities between the experiences of newcomers and their native-born counterparts. Previous studies have mainly focused on how the immigration process and displacement from one’s country of origin influence mental health. Comparatively, few researchers have explored the association between these contributing factors and culture in how immigrants and refugees understand their mental health and approach available services. The goal of this study was to understand newcomers’ perspectives on mental health service access and utilization in order to ultimately meet their mental health needs using a phenomenological approach to inquiry. Interviews and a focus group were conducted with 10 newcomers and 5 support staff at a newcomer community organization in the Greater Toronto Area. A thematic analysis of the narratives was used to identify themes among the data. Findings from interviews with newcomers revealed the following themes: (1) perceptions of mental health challenges are influenced by internal and external pressures, (2) cultural beliefs influence if and when newcomers seek medical intervention, and (3) expectations and experiences of accessing services within the Canadian healthcare system. Additionally, findings from the support staff focus group revealed the following themes: (1) the influence of undocumented status and financial difficulties on newcomers’ mental health challenges, (2) tension between newcomers’ openness with mental health challenges and stigmatization from others in their cultural communities, and (3) barriers and facilitators associated with help-seeking and mental health service utilization. The dissemination of these findings for restructuring current mental health services and providing efficient and effective support for this vulnerable population is discussed.


title: “We Had More Eyes on Us Than the Boys”: Recollections of Girlhood at Residential Schools for the Blind

contributor: Social Justice and Equity Studies Program

subject:
disability
gender
sexuality
qualitative research
schooling

abstract: This thesis explores experiences of girlhood within residential schools for the blind in North America. The analysis draws upon and contributes to theorizing in feminist disability studies and gendered embodiment in schooling and residential schools as social systems. It also offers insight into methodological approaches to conducting research with the blind and partially sighted community. Qualitative interviews with former female students illuminate how girls in these residential school settings experienced and navigated curriculum, space, informal/formal school rules and peer culture. The analysis focuses on gendered and sexualized inequalities as well as the agency of girls within in this particular educational context. Documenting the experiences of former female students of residential schools for the blind makes an important contribution to understanding the intersecting realities of girlhood and disability in an under - researched educational context, and points to the need for greater initiatives focused at addressing the inequalities that they encounter.


title: That Power: Performing Power, Trauma, and Queer Religious Futurity

subject:
queer trauma
queer futurity
queer theatre performance
queer religious agency
queer relationality

abstract: Conservative religious ideology is a key contributor to the ongoing violence of LGBTIQ2S+ exclusion and discrimination in Canada. This qualitative arts-based research project foregrounds the life experiences of 2 queer individuals from conservative Hindu (Manchari (Ari) Paranthahan) and conservative Christian (Jonathan Brower) upbringings to activate a conversation about the possibilities and limitations of queer religious agency and futurity. Using critical narrative inquiry and theatre creation, Paranthahan and Brower collaged their narratives about gendered, sexual, racial, and religious attachment and exclusion into a script and then publicly performed it as a live full-length play. The script and performance, titled That Power, are included within the thesis as findings. Key theoretical influences framing the discussion are the responsibility of witnessing testimony (Oliver, 2001), depathologizing trauma (Cvetkovich, 2003; Rothberg, 2014), the potentialities of queer performance utopias (Muñoz, 2009; Pryor, 2017), and feminist anti-racist solidarity (Mohanty, 2003). The analysis is guided by questions regarding how performance mobilizes queer trauma through relationality; the ways stories can galvanize an intersecting analysis about race, gender, and faith; and how a theatre creation model enriches the possibilities for queer futurity. The discussion positions That Power as a cultural product that helps reconstitute subjectivity for its creators while also becoming a mode of embodied collective resistance by performatively working through trauma and reframing queer relationality and feminist solidarity.


title: 'How I Teach and Coach': The Epistemological Beliefs of Teacher-Coaches

subject:
epistemological beliefs
physical education
teacher-coaches
teacher beliefs
coaching

abstract: Epistemological beliefs (EB), or beliefs about knowledge and learning, help to inform teaching and coaching practices, and may have significant learning and developmental outcomes for students. Therefore, the purpose of this grounded theory study was to better understand the EB of high school physical education (PE) teacher-coaches as it relates to the sources and simplicity of games knowledge and how those beliefs inform their instructional practices when teaching games or coaching extracurricular sports in schools. In-depth semi-structured interviews were conducted with 6 secondary school PE teacher-coaches from south-central Canada. Teacher-coaches believed that games knowledge in both PE and extracurricular sports originate from a variety of internal and external sources, portray games knowledge as both simple and complex, associate PE and extracurricular sports with different knowledge or learning processes, and differentiate their instructional strategies more in PE compared to their coaching practices. This research study has theoretical and practical implications for enhanced teaching and coaching practices, as well as teacher education and coach-training programs, with the ultimate aim of enriching students’ learning experiences in physical education and interscholastic sport.


title: Scheduling Elective Surgeries in Multiple Operating Rooms

subject:
parallel surgery scheduling
operating room scheduling
simulation optimization

abstract:
This thesis focuses on the problem of designing appointment schedules in a surgery center with multiple operating rooms. The conditions under which overlapping surgeries in the surgeons’ schedule (i.e. parallel surgery processing) at the lowest cost are investigated with respect to three components of the total cost: waiting time, idle time, and overtime. A simulation optimization method is developed to find the near-optimal appointment schedules for elective surgical procedures in the presence of uncertain surgery durations.

The analysis is performed in three steps. First, three near-optimal operating room schedules are found for different cost configurations based on the secondary data of surgery durations obtained from the Canadian Institute for Health Information. Second, these near-optimal appointment schedules are used to test a parallel scheduling policy where each surgeon has overlapping surgeries scheduled in two operating rooms for the entire session (480 minutes) and only attends the critical portions of surgeries in the two operating rooms. Lastly, another parallel scheduling policy is tested where each surgeon has overlapping surgeries scheduled for half of the session duration (240 minutes) and only has surgeries scheduled in one operating room for the remaining time. These two policies are tested using simulation with scenarios for parallelizable portions of surgeries varying from 0.1 to 0.9 at 0.1 increments and three cost configurations.

In the simulated scenarios, the total cost is calculated as the weighted sum of patient waiting time, surgeon idle time, surgeon overtime, operating room idle time, and operating room overtime. Out of the nine scenarios for each policy and each cost configuration, the parallelizable portion of surgeries that result in the lowest total cost is identified.

The results from both policies indicate that implementing parallel scheduling policies for surgery types with higher parallelizable portions results in surgeons remaining idle for longer periods during the session. This idle time cost is justified by a decrease in other cost components for surgeries with parallelizable portions 50% or less; however, the total cost is higher for surgeries with parallelizable portions over 50%. In addition, it has been observed that overlapping surgeries with lower parallelizable portions is more expensive than overlapping those over with 50%.  Therefore, it is concluded that the surgery types that allow parallel surgery scheduling policies to be implemented at the lowest cost have 50% of their duration parallelizable.


title: Characterizing the role of tafazzin in allergically activated mast cells

subject:
Immunology
Allergy
Mast cells
Tafazzin

abstract:
Introduction & Aim: Allergic inflammatory diseases are a constantly growing health concern in
westernized societies. Mast cells, the driving force behind many allergic diseases, modulate
various metabolic pathways to carry out their various functions following IgE-FceRI-mediated
activation. Tafazzin is a cardiolipin transacylase that works to remodel cardiolipin into its mature
form of tetralinoleoyl-cardiolipin. Mature cardiolipin is important for efficient energy production
through oxidative phosphorylation. The aim of this project is to study the effects of a reduction
in tafazzin protein content on IgE-mediated mast cell activation. Methods: Fetal liver-derived
mast cells (FLMCs) were treated with 1 μg/mL doxycycline for 5 days to initiate the tafazzin
knockdown. Western blotting was used to confirm a reduction in tafazzin protein content. Flow
cytometry was used to ensure that the FLMCs expressed both c-kit and FceRI receptors, and that
receptor expression was not impacted by the doxycycline treatment. Oxygen consumption rate
was measured using a Clark-type electrode. b-hexosaminidase release assays were utilized to
assess degranulation during the early phase of the allergic reaction. ELISA assays were used to
examine secretion of de novo synthesized inflammatory mediators, while qPCR assays were used
to examine gene transcription of these mediators. Results: The doxycycline inducible tafazzin
knockdown resulted in a 99.5% reduction in tafazzin protein content. This reduction was
accompanied by a 25% reduction in oxygen consumption and a 31.4% reduction in
degranulation. Secretion of CCL1, CCL2, and TNF was significantly reduced, CCL9 secretion
levels showed a decrease that approached significance. Secretion of CCL3 and IL-6 was not
impacted. Gene expression was not impacted for any of the inflammatory mediators measured.
Conclusion & Significance: These results suggest that tafazzin may play a role in mast cell
oxidative phosphorylation. Functionally, the results suggest that tafazzin plays a role in
degranulation and mediator secretion. However, since gene expression was not impacted it is
thought that the tafazzin reduction causes these decreases due to an impairment of the exocytosis
mechanism. This work adds to the growing field of immunometabolism and improves our
understanding of how mast cells modulate metabolic pathways during an allergic inflammatory
event.


title: Co-activation in the bilingual lexicon: Evidence from Chinese-English bilinguals

subject:
bilingualism
morphology
psycholinguistics
linguistics
online experimentation

abstract: Investigation of the bilingual mental lexicon suggests that one of its defining characteristics is integration. Words across both languages are subject to parallel co-activation during language processing. An auditory stimulus typing task was used to assess connectivity on the basis of both morphology and phonology. English loanwords in Chinese and transparent English noun-noun compounds with Chinese translation equivalents with corresponding compound structure (corresponding compounds) were used as the critical stimuli. Accent was also manipulated to determine whether or not phonological cues may influence the degree of cross-linguistic co-activation. Results suggest cross-linguistic co-activation on the basis of phonological overlap in different script bilinguals but only weakly supported morphological integration in Chinese-English bilinguals. Accent led to greater co-activation of phonologically similar loanword pairs. Results are discussed in terms of inhibitory control, language acquisition, and the structure of the bilingual lexicon.


title: The Larger Stages: The 'Becoming Minor' of South African Theatres.

subject:
Deleuze
minoritarian
immanent
postapartheid
South African theatre

abstract:
ABSTRACT
The Larger Stages: The Becoming ‘Minor’ of South African Theatres.
By Jill Planche
South Africa is layered with entangled histories that have created a fragile
landscape of ambiguities where fractured memories are revealed yet remain concealed.
The social architecture of apartheid still persists in a legacy of hostile urban geographies
and land inequity, while global capitalism and economic disparity are seen in the
dramatic contrast between the developing middle class and the poverty of millions. This
research project interrogates the way in which contemporary theatre in South Africa is
implicated in the country's complex cultural, economic and social realities. Pursuing
rigorous qualitative research in the history, practice and criticism of South African
theatre; contemporary studies in theatre spatiality; and philosophy, cultural theory and
human geography, I explore precisely whose voices are being heard and which audiences
are being reached. What role does – and might – theatre play in addressing South Africa’s
socio-economic and artistic challenges, both as a barrier and a bridge to audiences?
Drawing on the work of such thinkers as Gilles Deleuze, Félix Guattari, Rosi Braidotti
and Achille Mbembe, can we anticipate what we might describe as a ‘minor’ theatre that
will tell the stories that resonate twenty years after the end of apartheid? The term
‘minor’ refers to the Deleuzian concept of affirmative and dynamic processes to create
new political subjects; processes of “becoming” that break from the fixed, proscribed
“being,” which in the South African context has been created by centuries of colonialism
and decades of state-imposed racial construction. Given the insights afforded by such
theorization, I argue that the spaces of performance are potentially dynamic spaces of
intersection within this landscape of layered socio-economic and artistic challenges
created by a milieu of rooted physical and mental boundaries that have informed the
country’s inherited theatrical practices.


title: Stress and the Development of Social behaviour in Adolescent Female Rats

subject: Adolescence, Social Instability Stress, Social Interaction, Corticosterone, Female Rats,

abstract: Adolescence is a critical time of brain development for regions governing social behaviour and social learning. In adolescence, social experiences may influence the ongoing maturation of the neural structures involved in social behaviour and ultimately modify the social behaviours of adults in response to social cues. Social instability stress in adolescence (SS; daily 1 hour isolation + change of cage partner in postnatal days [PND] 30-45) leads to deficits in social behaviour in SS rats compared with non-stressed (CTL) rats in males; less is known in females. The main goal of my thesis is to investigate the effects of adolescent SS procedure on the development of social behaviour and brain regions underlying social behaviour in female rats when tested soon after and long after the end of the SS procedure. In the second chapter, I found that SS in male and female rats reduced time spent in social interaction when tested soon (PND 46) or long (PND 70) after the SS procedure in comparison to CTL rats. Irrespective of time post-stress and sex, SS rats spent less time in social interaction than did CTL rats, and female rats spent less time in social interaction than did male rats. The results from the third chapter demonstrated that SS females had higher corticosterone concentrations and lower Zif268 immunoreactive cell counts in the cingulate gyrus after the SI test than did CTLs when tested at PND 46. Furthermore, in the fourth chapter, brains were collected at PND 46 and PND 70 for RT-qPCR in female rats. Effects of SS on mRNA expression were observed for oxytocin receptor, vasopressin 1a receptor, corticotropin-releasing hormone receptor1, glucocorticoid receptor, and mineralocorticoid receptor that depended on age (time since the SS) and brain region (medial prefrontal cortex [mPFC], hippocampus). Some of the differences between SS and CTL rats were evident irrespective of age at which tested at PND 46 (such as GR in mPFC and MR in the hippocampus), whereas others emerged in adulthood at PND 70 (such as OTR and GR in the hippocampus).


title: Tax Evasion by E-commerce Businesses in Bangladesh

subject:
Tax Evasion
Custom Tax
Social Media

abstract:
The unnerving momentum at which digital technology is progressing affects many aspects of business operations. For instance, businesses can now promote and sell their products on social media platforms with ease. Importantly, third world countries such as Bangladesh have been able to share in such technological strides along with more affluent nations. In Bangladesh, a myriad of small businesses have emerged with business models that depend on e-commerce platforms. These businesses are thriving in a fiercely competitive market with many of them importing their goods from the United States. One interesting feature in this marketplace is that the prices are much lower than those offered by brick and mortar stores.
To investigate the reasons for this price differential, interviews were conducted with five respondents who operate businesses online and seem to be charging prices much lower than would be expected based on reasonable assumptions about input costs. In addition, to understand the perspective of potential customers, two surveys were conducted related to purchase intentions for two unrelated goods: the iPhone XS and Colourpop Lipstick. The primary objective of the research was to comprehend the price setting procedures adopted by the firms and customers’ willingness to buy products at different prices.
My findings revealed that custom tax rates were the major cause for the price differential between brick and mortar stores and social media stores. This became clear from descriptions by the business owners of their procedures to import products in ways that avoid payment of customs tax and in pricing models that clearly do not include customs taxes. The results of the customer study suggest that price is the primary determinant of purchase intentions. Apparently, customers do not mind purchasing from a business that is evading taxes as long as it is cheaper. Importantly, the results indicate that the high tax rates charged by the government discourage citizens from complying with laws.


title: A Hybrid Approach to Network Robustness Optimization using Edge Rewiring and Edge Addition

subject:
complex networks
network robustness
optimization
metaheuristics
genetic algorithm

abstract: Networks are ubiquitous in the modern world. From computer and telecommunication networks to road networks and power grids, networks make up many crucial pieces of infrastructure that we interact with on a daily basis. These networks can be subjected to damage from many different sources, both random and targeted. If one of these networks receives too much damage, it may be rendered inoperable, which can have disastrous consequences. For this reason, it is in the best interests of those responsible for these networks to ensure that they are highly robust to failure. Since it is not usually feasible to rebuild most existing networks from scratch to make them more resilient, it is necessary to have an approach that can modify an existing network to make it more robust to failure. Previous work has established several methods of accomplishing this task, including edge rewiring and edge addition. Both of these methods can be very useful for optimizing network robustness, but each comes with its own set of limitations. This thesis proposes a new hybrid approach to network robustness optimization that combines both of these approaches. Four edge rewiring based metaheuristic approaches were modified to incorporate one of three different edge addition strategies. A comparative study was performed on these new hybrid optimizers, comparing them to each other and to the vanilla edge rewiring only approach on both synthetic and real world networks. Experiments showed that this new hybrid approach to network robustness optimization leads to much more highly robust networks than an edge rewiring only approach.


title: The role of mobile elements in recent primate genomes

subject:
Mobile elements
Comparative genomics
Primates
Evolution
Retro-DNA

abstract:
Mobile elements (MEs), which constitute ~50% of the primate genomes, have contributed to both genome evolution and gene function as demonstrated by ample evidence discovered over the last few decades. The three studies in this thesis aims to provide a better understanding of the evolutionary profile and function of MEs in the primate genomes by taking a computational comparative genomics approach.
The first study represents a comprehensive analysis of the differential ME transposition among primates via identification of species-specific MEs (SS-MEs) in eight primate genomes from the families of Hominidae and Cercopithecidae using a comparative genomics approach. In total, 230,855 SS-MEs are identified, which reveal striking differences in retrotransposition level in the eight primate genomes. The second study represents a more focused analysis for the identification of a new type of MEs, which we term “retro-DNA” for non-LTR retrotransposons derived from DNA transposons, in the recent primate genomes. By investigating biallelic DNA transposons that have both the insertion and pre-integration alleles in ten primate genomes, a total of 1,750 retro-DNA elements representing 750 unique insertion events are reported for the first time. The third study provides an analysis of the mechanism underlying the differential SINE transposition in the primate genomes. In this study, Alu profiles are compared and the Alu master copies are identified in six primate genomes in the Hominidae and Cercopithecidae groups. The results show that each lineage of the primates and each species owns a unique Alu profile exclusively defined by the AluY transposition activity, which is determined by the number of Alu master copies and their relative activity.
Overall, work in this thesis provides new insights about MEs and their impact on the recent primate genomes by revealing differential ME transposition as an important mechanism in generating genome diversity among primate lineages and species through discovering a new type of MEs and preliminary analysis of the mechanism underlying the differential ME transposition among primates. Furthermore, taking advantage of the recently available primate genomes and transcriptomes data, the work in this thesis demonstrates the great potential of the comparative genomic approach in studying MEs in primate genomes.


title: Epimeric L-Proline Derived Imidazolone Chiral Auxiliaries for the Stereoselective Alkylative Birch Reduction of Aromatic Esters and Benzonitriles

subject:
Stereoselective
Reductive alkylation
Birch reduction

abstract: Described in this thesis are several advancements of imidazolidinone chiral auxiliaries. Initially, attempts were made to develop a N-heterocyclic carbene ligand derived from the N-benzyl analog of the auxiliary. Attempts to design a monodentate ligand as well as a bidentate ligand bearing an alcohol side chain were both shown to be unsuccessful. Work on the N-phenyl variant of the auxiliary included expanding upon our recently discovered methodology; a Birch reduction alkylation sequence of an aromatic ester yielding chiral quaternary carbon centres in a stereoselective matter. In substrates that demonstrate poor stereoselectivity, modification of the auxiliary to include a larger neopentoxy directing group gives way to increased selectivity. This work also includes the same Birch reduction alkylation sequence on a series of benzonitrile substrates with up to 64:36 diastereomeric ratio from either epimer of the auxiliary. The low selectivity of the benzonitrile substrates is offset by the resulting diastereomers of the dihydrobenzonitrile products being chromatographically separable. This results in the first preparation of optically pure quaternary carbons alpha to nitrile by Birch-type reductive alkylation. Progress was also made in the manipulation of chiral auxiliaries bearing the chiral alkoxy moiety. These functional groups were transformed into hemiaminals by citric acid hydrolysis in a 3:2 ratio with imidazolone by-products formed by acid mediated elimination of alcohol.


title: Relationships Between Sleep Quality, Sleep Hygiene, and Psychological Distress In University Student-Athletes

creator:
Gladney, Chris
Gladney, Chris

subject:
Psychological Distress
Sleep Quality
Sleep Hygiene
Student-Athlete

abstract: Post-secondary student-athletes are one of the most vulnerable populations that experience poor sleep quality, which has detrimental effects on psychological distress due to the strong relationship between sleep quality and psychological distress. Research suggests that by improving sleep hygiene behaviours an individual can improve sleep quality, which will improve psychological distress. Few studies have examined sleep quality, sleep hygiene and psychological distress together among a post-secondary population and none have investigated a student-athlete population. The present study examined if sleep hygiene mediates the relationship between sleep quality and psychological distress among post-secondary student-athletes. A sample of 94 student-athletes completed the Kessler Psychological Distress Scale, Pittsburgh Sleep Quality Index, and Sleep Hygiene Practice Scale (Buyess et al., 1989; Kessler et al., 2002; Lin, Cheng, Yang, & Hsu, 2007). A mediation model was used to examine the relationships between the variables using the global scores. Bootstrapping was conducted to increase power of the model, which resulted in confidence interval levels that did not include zero indicating the indirect effect is significant and sleep hygiene mediates the relationship between sleep quality and psychological distress. This study can implicate future studies regarding sleep hygiene interventions changing the lifestyle habits and behaviours affecting their sleep hygiene, which is shown to impact sleep quality and psychological distress. In conclusion, Sleep hygiene mediated the relationship between sleep quality and psychological distress.


title: Self-Care as a Pedagogical Ontology in the Professional Care Practice of Others and with Others: A Hermeneutic Phenomenology of Self-Care in Nursing Education

subject:
self-care education
nursing self-care
pedagogical ontology
professional care practice
hermeneutic phenomenology

abstract: Healthcare practitioners work in reciprocally dynamic roles in which their health and well-being directly impact their professional competence.  This interplay is often understated in ways that regulatory colleges influence training and education programs. In Ontario, for example, we see this in nursing.  Although the College of Nurses of Ontario stipulates nursing professional competencies, it does not provide explicit performance expectations related to nursing self-care (i.e., the intentional way one takes care of one’s self).  Accordingly, not all Ontario nursing education programs teach self-care.  Different from research that deliberates nursing as a discipline or body of knowledge, this research examined how self-care is articulated, prioritized, taught, and assessed in nursing education.  As such, the scholarly contribution it offers in the context of education is a pedagogy supporting self-care as a professional competency.  Eight nursing faculty shared their lived experiences (through one-on-one interviews) surrounding the notion and phenomenon of self-care in nursing.  Through a reiterative hermeneutic interchange that focused on whose voice is missing, an art-informed method that paralleled knowledge creation metaphorically according to the depth and breadth of “delving beneath the surface,” transformed participants spoken words into interpretive texts.  Study conclusions suggest that self-care in nursing may be understood and taught through emotionally engaged self-reflection, not as a prescribed set of behaviours or individual task-based activities, but instead, as a pedagogical ontology in the professional care practice of others and with others.  To foster successful self-care practice in nursing, educators should consider using arts-based methods to help learners enter and navigate spaces for emotionally engaged self-reflection.  Given the urgent need for innovative and rigorous curriculum to support successful self-care practices as part of a healthcare practitioner’s professional role, this research is both timely and relevant.


title: Resistivity of Single Crystal Molybdenum Dioxide

subject: Molybdenum

subject: MoO2

subject: mo4O11

subject: Resistivity

subject: Crystal

abstract:
The chemical vapour transport method was used to grow molybdenum oxide single crystals
so that their electrical properties could be analyzed. Satisfactory single crystal samples of
MoO2 and Mo4O11 were grown successfully using I2 as a transport agent. Crystal growths
using TeCl4 as a transport agent were also performed, though with mixed results. This
approach yielded MoO2, MoO3, and Mo9O26, but this produced samples of a quality not
suitable for single crystal analysis. Measurements performed on these samples yielded
unique results, due to their mixed oxide nature, but as the composition of each sample
was inconsistent, even between crystals from the same growth, little can be said about
them definitively. Rubidium doped single crystal growths were also attempted, to build
on previous polycrystalline Rb doped sample research, however no growths successfully
included measurable amounts of Rb. While resistivity and heat capacity measurements
performed on MoO2 did identify a phase transition in the area of 267K reported by other
researchers, there was however no evidence found to support a reported 220K electronic
transition [1]. In Mo4O11 two previously identified 109K and 30K charge density wave
transitions were observed in the DC resistivity. When AC resistivity measurements were
performed the 30K transition was not apparent. Instead, a divergence of the cooling and
warming curves not seen in the DC experiments occurred above 200K, with previously
unseen peaks appearing at 285K and 250K when cooling from 400K.


title: Testing a Hypothesis of Non-REM Sleep Reinforcement and REM Sleep Refinement for the Benefits of Post-Learning Sleep on Memory Retrieval

subject:
sleep
memory
NREM sleep
REM sleep

abstract:
It is well established that post-learning sleep benefits later memory retrieval, but there is still much to learn about the processes involved and the nature of these benefits. Sleep is composed of stages of non-REM (NREM) and REM sleep: NREM sleep,
especially slow wave activity of NREM sleep, and REM sleep have been implicated in memory performance benefits, but the specific contributions of each state remain unclear. This thesis presents a hypothesis proposing that post-learning NREM sleep supports memory accessibility, benefitting the likelihood of successful memory retrieval, and that post-learning REM sleep supports memory fidelity, allowing for more accurate retrieval when retrieval is successful. This hypothesis was tested over studies examining the effects of an afternoon nap (Chapter 2), targeted memory reactivation during NREM slow wave sleep (Chapter 3), and both targeted memory reactivation during NREM slow wave sleep and selective deprivation of REM sleep (Chapter 4) on measures of memory accessibility and memory fidelity in visuospatial memory tasks. In each study, measures of sleep architecture and electroencephalographic power in sleep were examined as predictors of memory performance. Several identified associations and interactions further inform an understanding of how NREM sleep and REM sleep may benefit memory performance. Most notably, these studies consistently found greater slow wave activity of NREM sleep to be specifically associated with better maintenance of memory accessibility. These studies did not identify a clear effect of REM sleep. It is hoped that the hypothesis and findings presented stimulate additional inquires that will further our understanding of the individual and combined contributions of NREM and REM sleep.


title: Examining the adherence to clinical guidelines for the assessment of pain, agitation and delirium in a Canadian community intensive care unit

subject:
Pain, agitation and delirium
Intensive Care Unit
PAD Guidelines

abstract: The purpose of this study was to evaluate the impact of a multifaceted and multidisciplinary intervention on the adherence of assessments for the management of pain, agitation and delirium (PAD) in a community intensive care unit (ICU) setting. All patients admitted to the community ICU for over 24 hours were included. Data were collected on a total of 430 patient-days during the pre-intervention period and 406 patient-days during the post-intervention period. A 6-week baseline data collection was performed, followed by a 4-week intervention, and a 6-week post-intervention data collection. The multifaceted intervention targeted nurses, physicians and family members and included online nurse education sessions, cue cards, posters, physician round scripts, patient family interviews, patient education pamphlets, and patient education videos. In addition, a PAD Advisory Committee was formed to engage, motivate and support frontline healthcare staff during the design and the implementation of the intervention. There were improvements in the number of patient-days with pain assessment at least 4 times per shift using NPRS or CPOT (68.0% vs 87.5%, p=0.0001), agitation assessment at least 4 times per shift using CAM-ICU. There was no significant improvement in the number of patient-days with at least once delirium assessment per shift using CAM-ICU (74.4% vs 76.3%, p=0.514). The mean number of patient-days with significant pain assessed as NPRS ≥ 4 or CPOT ≥3 was 0.026 lower in the post- intervention period compared to the pre-intervention period (95 % CI: 0.043, 0.008). Further, the mean number of patient-days with over sedation defined by RASS of < -2 at least 50% of the time was 0.063 higher in the post-intervention period compared to the pre-intervention period (95 % CI: 0.016, 0.109). This study demonstrates that involving frontline healthcare professionals in the design and implementation of multidisciplinary and multifaceted interventions improved the adherence to PAD care processes in a Canadian community ICU.


title: Supplier Selection and Relationship Management: An Application of Machine Learning Techniques

subject:
Supplier relationship management
Machine learning
Supplier relationship strategy

abstract: Managing supply chains is an extremely challenging task due to globalization, short product life cycle, and recent advancements in information technology. These changes result in the increasing importance of managing the relationship with suppliers. However, the supplier selection literature mainly focuses on selecting suppliers based on previous performance, environmental and social criteria and ignores supplier relationship management. Moreover, although the explosion of data and the capabilities of machine learning techniques in handling dynamic and fast changing environment show promising results in customer relationship management, especially in customer lifetime value, this area has been untouched in the upstream side of supply chains. This research is an attempt to address this gap by proposing a framework to predict supplier future value, by incorporating the contract history data, relationship value, and supply network properties. The proposed model is empirically tested for suppliers of public works and government services Canada. Methodology wise, this thesis demonstrates the application of machine learning techniques for supplier selection and developing effective strategies for managing relationships. Practically, the proposed framework equips supply chain managers with a proactive and forward-looking approach for managing supplier relationship.


title: A Case Study to Explore Women's Body Image Experiences Practicing Hot Yoga

subject: Hot yoga, fitness, embodiment, positive body image, body functionality.

abstract: Yoga is an embodying activity associated with positive body image; however, hot yoga may have differing impacts on body image and embodiment than traditional yoga, as several features of hot yoga differ from traditional yoga (e.g., heat, clothing worn, emphasis on fitness) and may influence women’s body image and practice of hot yoga.  Using an exploratory case study approach, one hot yoga studio (Modo Yoga St. Catharines) was chosen for this study. The research questions pertaining to this case were: 1) In what ways is body image related to women’s practice of hot yoga? 2) What are women’s experiences practicing hot yoga at Modo Yoga studio St. Catharines? Ten women were recruited from the yoga studio and interviewed about their body image and experience practicing yoga at Modo Yoga. Four women, with differing experiences and body image, completed a follow-up interview to further clarify their experiences. Overall, it was found that women tended to emphasize the fitness aspects of hot yoga, which impacted their body image and undermined some benefits of yoga. However, there were also positive effects on body image and mental health as a result of the practice. Case-specific features, specifically related to the physical characteristics of the studio (e.g., large mirrors in the studio) and the social environment within the studio (i.e., instructor cues and other members) impacted women’s body image both positively and negatively. Further, some differences based on age and experience at the studio were also identified, with long-term members (6 months+) experiencing more psychological benefits (e.g., mindfulness, feeling less anxious, body acceptance, body responsiveness), with the physical challenges of hot yoga being an additional benefit.  Overall, hot yoga had a complex impact on women’s body image and experience practicing hot yoga through a larger focus on the fitness elements of the practice.


title: The effect of acute low-load resistance exercise with the addition of blood flow occlusion on muscle function in children and adults

subject:
Occlusion
Children
Electromyography
Low-load exercise

abstract:
Background: Resistance training recommendations to increase muscular strength suggest
using high loads. However, some individuals cannot withstand high mechanical stress.
Thus, in adults, low-load training is used with blood flow occlusion (BFO), to mimic
strength increases from high-load training. Due to differing physiological responses to
exercise, children may respond differently to BFO than adults. This study compares the
effect of low-load exercise with BFO on maximal voluntary contraction (MVC) and
electromyographical (EMG) activity in children and adults.
Methods: 16 men (24.4±2.5y) and 14 boys (10.7±2.0y) performed two experimental
conditions: (1) occlusion and (2) control. During the occlusion condition, a blood
pressure cuff on the upper arm was inflated above systolic pressure during 25 wrist
flexions at 35% MVC. Participants then performed an MVC and rated their perceived
exertion (RPE). The control condition was the same as the occlusion condition but
without the use of BFO. EMG signal was recorded from the flexor carpi radialis (FCR).
Results: Men displayed a 16.9±7.1% increase in FCR EMG amplitude across the
occlusion (p=0.005) but not the control condition (p=0.919). The boys did not show a
change in EMG amplitude between time points (p=0.576) or conditions (p=0.549).
Across both age groups, EMG mean power frequency was influenced by a condition-x-time
interaction, with a larger decrease across the occlusion (-20.1±9.6%; p<0.001) than
the control condition (-5.6±9.7%; p=0.002). Furthermore, across both age groups, MVC
torque decreased more following the occlusion (-18.7±12.8%; p<0.001) than the control
condition (-6.7±12.5%; p<0.001).
Discussion: Based on our findings, a partial explanation for increases in EMG amplitude
in the men but not the boys may be that the men recruited more of their higher-threshold
motor units than the boys. However, not all measures were consistent in showing child-adult
differences, as BFO caused similar decreases in MPF for both groups. Thus, while
adults use low-loads with BFO to simulate high-load training, it remains unclear whether
this form of training would be as effective for children.


title: Mindfulness therapy as a means to improve sexual satisfaction in couples with neuromuscular disabilities

subject: Mindfulness Phenomenology Sexuality disability

abstract:
Research regarding sexuality after neuromuscular disabilities has focused on either men or women separately, without considering the couple and how acquiring a disability may influence relationships.
The objective of this study was to investigate the effects of an 8-week modified mindfulness intervention on sexual satisfaction in couples where one or both partners are living with neuromuscular disability.
One couple (male age 42, female age 44) with the female living with neuromuscular disability (relapsing remitting MS, 11 years since diagnosis) participated in the study.
The mindfulness intervention was administered to participants via a booklet and the exercises were explained verbally after the baseline interview. The booklet contained a total of eight mindfulness-based exercises for each week of the intervention. The exercises were explained in a step-by-step manner in the booklet. The booklet also included reflection questions at the end of each exercise in order to prompt the couple to journal about their experiences and record how much time they dedicated to that exercise per week. The exercises were carried out at home.
The intervention also included a psycho-education session that was offered at week five of the intervention. The psycho-education session aimed to challenge thought patterns and negative beliefs about sex and physical abilities. It also involved a discussion about body-image as it relates to mindfulness.
Testing involved a sexual satisfaction questionnaire that was completed by each member of the couple individually at baseline and at the end of the 8-week intervention.
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Also, an in-depth semi-structured phenomenological interview of the couple together was conducted at baseline and at the end of the 8-week intervention.
The results of this study showed that sexual satisfaction and sexual-self view have improved for the couple as a result of participating in the 8-week mindfulness intervention. In addition, the couple reported an improvement in communication, understanding, and awareness. Sensate focus exercises enhanced intimacy between the couple. Themes such as acceptance and feeling present in the moment were discerned from phenomenological analysis.
These findings show promise for mindfulness-based therapies to enhance sexual satisfaction and relationship satisfaction in couples living with neuromuscular disabilities.


title: Synthesis of Heteroleptic Redox-active and Spin-crossover Complexes

subject:
spin-crossover
redox-active ligands
conductivity
mixed-ligands

abstract:
The following research regarding heteroleptic redox-active complexes with the potential for spin-crossover is synthetic in nature.  The intent behind incorporating the Schiff base ligand N-(8-quinolyl)salicylaldimine with some redox-active species into a mixed ligand complex featuring a d4-d7 metal ion center was to prime the material for spin-crossover based on strong intermolecular interactions that would enhance cooperativity of the system.  Single component systems that display spin-crossover behaviour paired with other physical properties like electrical conductivity hold significance in the field of multifunctional materials, of which there are few examples that feature mixed ligand systems.  Information describing this type of chemistry and the magnetic interactions that govern these characteristics is introduced in the first chapter of this work.
The synthetic strategies toward mixed ligand complexes in the form of [(Qsal)Fe(RAL)]+X- and [(Qsal)Co(RAL)]+X- have been realized from the use of mononuclear [(Qsal)FeCl2(CH3OH)] and [(Qsal)Co(OAc)]+OAc- species, respectively.  The redox-active ligand (RAL) component is an arylazo ligand like 10-(8-quinolylazo)-9-phenanthrol (Qapl) or 1-(2-Pyridylazo)-2-phenanthrol (Papl), which possess a low-lying π* MO that makes them susceptible to multi-step reductions that give rise to radical intermediates.  Heteroleptic complexes that were synthesized and isolated like [(Qsal)Fe(Qapl)]+BPh4-, [(Cl-Qsal)Fe(Qapl)]+BPh4-- and homoleptic [Fe(Qapl)2]+BPh4- were diffracted and measured several intermolecular π-π contacts of distances typically between 3.5-3.7 Å, often between the phenanthrene rings of adjacent Qapl ligands.  Complexes In the form of [(Qsal)Fe(Qapl)]+X (X= BPh4- or SCN-) showed early onset of spin transition in solution usually beyond 298 K.  These complexes were overly reduced in the glovebox which resulted in their deterioration, presumably from the cleavage of the RAL azo bond.  The framework developed for the heteroleptic Fe3+ coordination chemistry was applied to cobalt, with some amendments, and afforded several heterleoptic Co3+ complexes using Qsal with the arylazo ligands Qapl and Papl.  The heteroleptic cobalt complexes presented here were found to be LS Co3+ which is diamagnetic.  However, there is potential under inert atmosphere to produce Co2+ and possibly a phenoxyl radical species with redox-active valence tautomers.


title: Investigating the Cluster Chemistry of α-Methyl-2-pyridine methanol (mpmH) with Select 3d Ions

subject:
Single-Molecule Magnet
Metal Cluster Chemistry
Ligand Synthesis
Chiral Magnets
Inorganic Chemistry

abstract: This thesis describes an investigation of the coordination chemistry of the potentially chiral bridging, chelating ligand, α-methyl-2-pyridinemethanol (mpmH) with select 3d ions for the discovery of polynuclear clusters with single molecule magnet (SMM) properties. Chapter 1 introduces the theory of molecular magnetism, SMMs and the concepts of chiral SMMs, magnetochiral dichroism and multiferroics. In Chapter 2, two NiII clusters, {Ni8} and {Ni18} prepared from rac-mpmH are reported. The {Ni8} cluster crystallizes in a trapezoidal prismatic topology and contains tetrazolate ligands that are formed via a metal-assisted click reaction. The molecular structure of the second {Ni18} cluster is highly disordered comprising of eight edge-sharing cubane subunits. Dc magnetic susceptibility measurements reveal dominant ferromagnetic interactions down to  ~18 K, stabilizing spin states with large values, whereas at T < 18 K the antiferromagnetic contribution results in the population of smaller, but appreciable non-zero spin states. Ac magnetic susceptibility measurements confirm the presence of two relaxation processes at two temperature regimes that is extremely rare for a 3d-metal based SMM. The first at low temperature (5 K) is attributed to conventional SMM behavior with τ0 = 3.26 × 10-10 s and Ueff = 11 K. The origin of high temperature (15 K) relaxation process with a large Ueff = 381 K and τ0 = 2.7 × 10-15 s is less clear, but tentatively assigned to spin-glass properties. In Chapter 3, the synthesis and structure of a large mixed-valence [MnII2MnIII28MnIV] polynuclear cluster with a closed cage-like conformation is presented. Ac magnetic susceptibility measurements show the compound is an SMM with Ueff of 58 K, that is large for a 3d cluster, and a τ0 = 3 × 10−8 s.  Chapter 4 describes the coordination chemistry of racemic and chiral-mpmH with CuII and FeIII, where the synthesis and magnetostructural properties of a chiral {Cu4} tetramer, a non-chiral 1-D chain, as well as a chiral {Fe6} and a non-chiral{Fe8} cluster are reported. Dc magnetic susceptibility measurements on all four complexes reveal the presence of dominant antiferromagnetic exchange interactions affording S = 0 spin ground states at low temperature that precludes the observation of any SMM behavior.


title: The Influence of Demographics on Perceived Sport Event Impacts: 2017 Canadian Women’s Curling Championship

subject: Impacts Events NMSE Sport

abstract:
This study examines the perceived event impacts of attendees at the 2017 Scotties Tournament of Hearts (a national women’s curling event), that was held in St. Catharines, Ontario. Drawing on the recommendations of previous literature, the study investigates the perceived event impacts on attendees of a national sport event – the 2017 Canadian Women’s Curling Championships – by multiple socio-demographic characteristics. Multiple theoretical lenses are applied to understand the perceptions of the respondents. Utilizing a previously developed social impact scale model (Kim, Mun Jun, Walker, & Drane, 2015), a survey was completed by event attendees. In total, a sample size of 239 was used to conduct the study. Following reliability and validity tests on the model, MANOVA tests were completed to explore statistically significant impact factors and the influence that age, income levels, education levels, sport affinity, and residency (local and non-local) had on perceived event impacts. Results indicate that age and sport affinity (demographic variables) have a statistically significant influence on the overall perceived event impact.

The study examines the influence of socio-demographic characteristics on perceived impacts at a non-mega sport event. Further, the research provides insight into an approach for conducting sport event impact research in that researchers need to further explore how event characteristics themselves (e.g., total participants, scale or geographic location) can influence perceived impact. Thus, the study suggests that a ‘one-size-fits-all’ approach to event impact research is not realistic. As a result, future research will need to explore the influence of socio-demographic factors and the way in which event characteristics can impact the exchange process that occurs, informing their perceived impact.