THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Surveillance Studies and the Surveilled Subject

Surveillance studies has been somewhat inattentive to the perspective of the surveilled subject. It is the functioning of the surveillance apparatus, not the relatively inconsequential subject, which has tended to frame the focus of surveillance inquiries; leaving understandings of surveilled subjects’ experiences relatively limited. This research addresses this gap in the literature, exploring ways in which surveillance studies might understand the surveilled subject with greater consistency. Participants (N=47) shared their encounters with and perceptions of surveillance in a specific (Pearson International Airport) and general (everyday life) context through semi-structured interviews. The findings suggest that surveilled subjects’ encounters can be understood with some consistency – characterized by consistent criteria across subjects and contexts, and through a consistent theoretical framework across subjects in a specific context. However, consistency should not be confused with uniformity; encounters with surveillance must also be recognized for the extent to which they are nuanced and situated. For example, as this study also highlights, participants’ perceptions of encounters with surveillance at Pearson International Airport were differentially distributed in relation to identity characteristics (particularly minority status).

BEYOND WORDS: HOW LEARNING TO READ AND MENTAL HEALTH ARE RELATED FOR STRUGGLING READERS

The overarching purpose of this research program was to describe how intervening for academic deficits may be accompanied by changes in mental health. This multi-dimensional, multi-perspective, and iterative research program was developed to report on two distinct but related studies that addressed the same issue: in what ways does the mental health of students change as they transition from being struggling readers to more able readers? To describe the changes, these studies used a number of qualitative research methodologies—focus groups, individual interviews, and ethnographic case studies. Themes that emerged from the focus group and interview data in the first study were used to create a model that guided observations and interview questions in the second study. The first study described what parents, classroom teachers, and two reading instructors of nine previously struggling readers reported as the outcomes of becoming a more proficient reader. Data from this study indicated three broad domains in which change, as perceived by participants, occurred―cognitive/learning, behavioural/social, and psychological/emotional. Within these three domains, six dimensions were identified as having changed as reading improved: (a) academic achievement, (b) attitude, (c) attention, (d) behaviour, (e) mental health, and (f) empowerment. These domains, dimensions, and 15 constituent elements were used to create the model to guide the subsequent study. The purpose of the second study was to validate and refine this model by using an ethnographic case study approach to explore the ways in which the model accounted for the changes in reading and mental health seen in three boys over the months they participated in the intervention. By investigating the relationship between learning to read and mental health, this research aimed to enhance our understanding of how gains in reading may also improve the mental health of struggling readers. The model was found to be robust and a convenient conceptual framework to further our understanding of this relationship. Importantly, gains made in the cognitive/learning domain through an effective reading intervention, offered in a supportive learning environment, were shown to be accompanied by concomitant gains in both the behavioural/social and psychological/emotional domains—all of which enhance student thriving.

RELIGIOUS SCULPTURE OF THE CHILOÉ ARCHIPELAGO, FROM THE 17TH TO THE 21ST CENTURY

Despite its central role in religious life of the region, the sculptural tradition of the Southern Chilean Chiloé Archipelago, ranging from the 17th century to the present day, has been vastly understudied. Isidoro Vázquez de Acuña’s 1994 volume Santeria de Chiloe: ensayo y catastro remains the only catalogue of Chilote sculpture. Though the author includes photographs of a vast array of works, he does not attempt to place the sculptures within a chronology, or consider their place within the greater Latin American context. My thesis will place this group of works within a chronological and geographical context that reaches from the 16th century to the present day, connected to the artistic traditions of regions as far afield as Paraguay and Lima. I will first consider the works brought to the Archipelago by religious orders – the Jesuits and Franciscans – as well as influences on artistic style and religious culture throughout the 17th, 18th and 19th centuries. I will focus in particular on three works generally considered to be from the 17th and 18th centuries – the Virgin of Loreto at Achao, the Saint Michael at Castro, and the Jesus Nazareno of Caguach – using visual analysis and sifting through generations of primary and secondary sources to determine from where and when these sculptures came. With this investigation as a foundation, I will consider how they inspired vernacular sculptural expression and trace ‘family trees’ of vernacular works based on these precedents. Vernacular artistic traditions are often viewed as derivative and lacking in skill, but Chilote sculptors in fact engaged with a variety of outside influences and experimented with different sculptural styles. I will conclude by considering which aspects of these styles Chilote artists chose to incorporate into their own work, alter or exclude, artistic decisions that shed light on the Archipelago’s religious and cultural fabric.

Perspectives of Teachers Regarding the Integration of Mathematics and Science at the Secondary School Level

The integration of mathematics and science in secondary schools in the 21st century continues to be an important topic of practice and research. The purpose of my research study, which builds on studies by Frykholm and Glasson (2005) and Berlin and White (2010), is to explore the potential constraints and benefits of integrating mathematics and science in Ontario secondary schools based on the perspectives of in-service and pre-service teachers with various math and/or science backgrounds. A qualitative and quantitative research design with an exploratory approach was used. The qualitative data was collected from a sample of 12 in-service teachers with various math and/or science backgrounds recruited from two school boards in Eastern Ontario. The quantitative and some qualitative data was collected from a sample of 81 pre-service teachers from the Queen’s University Bachelor of Education (B.Ed) program. Semi-structured interviews were conducted with the in-service teachers while a survey and a focus group was conducted with the pre-service teachers. Once the data was collected, the qualitative data were abductively analyzed. For the quantitative data, descriptive and inferential statistics (one-way ANOVAs and Pearson Chi Square analyses) were calculated to examine perspectives of teachers regardless of teaching background and to compare groups of teachers based on teaching background. The findings of this study suggest that in-service and pre-service teachers have a positive attitude towards the integration of math and science and view it as valuable to student learning and success. The pre-service teachers viewed the integration as easy and did not express concerns to this integration. On the other hand, the in-service teachers highlighted concerns and challenges such as resources, scheduling, and time constraints. My results illustrate when teachers perceive it is valuable to integrate math and science and which aspects of the classroom benefit best from the integration. Furthermore, the results highlight barriers and possible solutions to better the integration of math and science. In addition to the benefits and constraints of integration, my results illustrate why some teachers may opt out of integrating math and science and the different strategies teachers have incorporated to integrate math and science in their classroom.

An Investigation of the Features and Effectiveness of the Full-Day Early Learning Kindergarten Program in Ontario

This dissertation includes two studies. Study 1 is a qualitative case study that describes enactment of the main components of a high fidelity Full-Day Early Learning Kindergarten (FDELK) classroom, specifically play-based learning and teacher-ECE collaboration. Study 2 is a quantitative analysis that investigates how effectively the FDELK program promotes school readiness skills, namely self-regulation, literacy, and numeracy, in Kindergarteners. To describe the main components of an FDELK classroom in Study 1, a sub-sample of four high fidelity case study schools were selected from a larger case study sample. Interview data from these schools’ administrators, educators, parents, and community stakeholders were used to describe how the main components of the FDELK program enabled educators to meet the individual needs of students and promote students’ SR development. In Study 2, hierarchical regression analyses of 32,207 students’ self-regulation, literacy, and numeracy outcomes using 2012 Ontario Early Development Instrument (EDI) data revealed essentially no benefit for students participating in the FDELK program when compared to peers in Half-Day or Alternate-Day Kindergarten programs. Being older and female predicted more positive SR and literacy outcomes. Age and gender accounted for limited variance in numeracy outcomes. Results from both studies suggest that the Ontario Ministry of Education should take steps to improve the quality of the FDELK program by incorporating evidence-based guidelines and goals for play, reducing Kindergarten class sizes to more effectively scaffold learning, and revising curriculum expectations to include a greater focus on SR, literacy, and numeracy skills.

Everyday Enchantments and Secular Magic in Montréal

In this thesis I argue that dominant ways of imagining modernity constitute a modern imaginary that carries with it particular expectations concerning modern places, spaces, emotions, and affects as well as expectations concerning the place of religion and enchantment in the modern world. I argue that this modern imaginary and the expectations it entails works to conceal and trivialize supra-rational beliefs and behaviours in scholarship but also in the lives of individuals. I focus on one particular subset of the supra-rational beliefs and behaviours that modern imaginary conceals and trivializes, namely beliefs and behaviours associated with lucky and protective objects. I also focus on the ways the modern imaginary conceals the presence and prevalence of these objects and the beliefs and behaviours they entail in one particular context, namely Montréal, Québec. I argue that these supra-rational beliefs and behaviours constitute a subjunctive mode for understanding and experiencing daily life and describe how the modern imaginary works to discredit this subjunctive register. Finally, I argue that scholars must begin to recognize and examine this subjunctive mode and the playful engagement with half-belief it involves.

International Capital Flows and Monetary Policy Spillovers

This dissertation examines the drivers and implications of international capital flows. The overarching motivation is the observation that countries not at the centre of global financial markets are subject to considerable spillovers from centre countries, notably from their monetary policy. I present new empirical evidence on the determinants of the observed patterns of international capital flows and monetary policy spillovers, and study their effect on both financial markets and the real economy. In Chapter 2 I provide evidence on the determinants of a puzzling negative correlation observed between productivity growth and net capital inflows to developing and emerging market economies (EMEs) since 1980. By disaggregating net capital inflows into their gross components, I show that this negative correlation is explained by capital outflows related to purchases of very liquid assets from the fastest growing countries. My results suggest a desire for international portfolio diversification in liquid assets by fast growing countries is driving much of the original puzzle. In the reminder of my dissertation I pivot to study the foreign characteristics that drive international capital flows and monetary policy spillovers, with a particular focus on the role of unconventional monetary policy in the United States (U.S.). In Chapter 3 I show that a significant portion of the heterogeneity in EMEs' asset price adjustment following the quantitative easing operations by the Federal Reserve (the Fed) during 2008-2014 can be explained by the degree of bilateral capital market frictions between these countries and the U.S. This is true even after accounting for capital controls, exchange rate regimes, and domestic monetary policies. Chapter 4, co-authored with Michal Ksawery Popiel, studies unconventional monetary policy in a small open economy, looking specifically at the case of Canada since the global financial crisis. We quantify the effect Canadian unconventional monetary policy shocks had on the real economy, while carefully controlling for and quantifying spillovers from U.S. unconventional monetary policy. Our results indicate that the Bank of Canada's unconventional monetary policy increased Canadian output significantly from 2009-2010, but that spillovers from the Fed's policy were even more important for increasing Canadian output after 2008.

Fleshing Out and Losing Flesh: The Decomposing Corpse as Narrative Object in American Hardboiled Detective Fiction

This dissertation examines the corpse as an object in and of American hardboiled detective fiction written between 1920 and 1950. I deploy several theoretical frames, including narratology, body-as-text theory, object relations theory, and genre theory, in order to demonstrate the significance of objects, symbols, and things primarily in the clever and crafty work of Dashiell Hammett (1894-1961) and Raymond Chandler (1888-1959), but also touching on the writings of their lesser known accomplices. I construct a literary genealogy of American hardboiled detective fiction originating in the writings of Edgar Allan Poe, compare the contributions of classic or Golden Age detective fiction in England, and describe the socio-economic contexts, particularly the predominance of the “pulps,” that gave birth to the realism of the Hardboiled School. Taking seriously Chandler’s obsession with the art of murder, I engage with how authors pre-empt their readers’ knowledge of the tricks of the trade and manipulate their expectations, as well as discuss the characteristics and effect of the inimitable hardboiled style, its sharpshooting language and deadpan humour. Critical scholarship has rarely addressed the body and figure of the corpse, preferring to focus instead on the machinations of the femme fatale, the performance of masculinity, or the prevalence of violence. I cast new light on the world of hardboiled detective fiction by dissecting the corpse as the object that both motivates and de-composes (or rots away from) the narrative that makes it signify. I treat the corpse as an inanimate object, indifferent to representation, that destabilizes the integrity and self-possession, as well as the ratiocination, of the detective who authors the narrative of how the corpse came to be. The corpse is all deceptive and dangerous surface rather than the container of hidden depths of life and meaning that the detective hopes to uncover and reconstruct. I conclude with a chapter that is both critical denouement and creative writing experiment to reveal the self-reflexive (and at times metafictional) dimensions of hardboiled fiction. My dissertation, too, in the manner of hardboiled fiction, hopes to incriminate my readers as much as enlighten them.

Landfill Leachate Toxicity to Oncorhynchus mykiss (Rainbow Trout) at the Merrick Landfill

At the Merrick Landfill, located outside of North Bay (Ontario, CA), an investigation into the potential for an environmental impact to the Little Sturgeon River as a result of landfill leachate discharge was undertaken using toxicity testing using 96 hour acute lethality on Oncorhynchus mykiss (Rainbow Trout). Landfill leachate may present a risk to receiving environments as it is comprised of an array of chemicals including organics, ammonia, and metals. Testing was conducted in three phases, firstly testing was completed on site throughout an existing natural attenuation zone where the presence of several groundwater seeps down gradient of the site had been identified to determine the effectiveness of the existing leachate control features at reducing the environmental risks. These tests indicated that the existing capture strategies were largely effective at reducing toxicity risks to the receiving environment. Testing was also completed on two pilot-scale hybrid-passive treatment systems to determine their effectiveness for leachate treatment. Summer performance of a constructed gravel wetland system was also shown to be effective at reducing the toxicity of the landfill leachate at the site. Lastly in order to support evaluation of leachate treatment requirements, a toxicity identification evaluation (TIE) was performed to determine the principle cause of toxicity within the leachate. Based on water chemistry analyses of samples collected at various locations at the site, the TIE identified ammonia toxicity as the primary source of toxicity in the leachate, with a secondary focus on metal toxicity.