VictorJuiz/thesis huggingface dataset:
Design and Investigation of Clean Energy Materials: From Stable Perovskites to Economical Catalysts for Oxygen Evolution Reaction

As we strive to find sustainable and economical materials for green technologies, developing next-generation materials that are efficient, durable, and affordable is crucial. In this thesis, I present my research on improving phase and bandgap stability in lead halide perovskites and explore nanostructuring and non-precious metal alloys as a route to economical catalysts for oxygen evolution reaction (OER) in an acidic medium.In the first section of the thesis, I discuss my work on perovskites. I start with a density functional theory (DFT) study of a dual-dopant strategy to increase the structural stability of the black phase CsPbI3 (chapter 4). The DFT studies revealed the importance of stereoelectronic effects in dopant-induced phase stabilization and found that the combination of Ca and Mn-doped CsPbI3 is the most effective in stabilization. The synthesized dual-doped thin films retained the black phase for up to 16 days at 40-60% relative humidity, while the non-doped controls degraded on the order of seconds. I also used DFT to evaluate additive-based design principles to improve the bandgap stability of lead halide perovskites and aid in elucidating the structure of the smallest CdSe magic-sized cluster. My work reveals the ability of chelating agents to modulate the quantum-well distribution of CsPbBr3 to achieve bandgap stability. My computational work also highlighted the importance of surface coverage in mitigating the phase segregation that plagues mixed-halide perovskites. The results are supported via experimental validation, producing spectrally stable blue and red PeLEDs. In the second part of the thesis, I discuss my work on economical catalysts for OER in an acidic medium. I demonstrate the use of a metal-organic framework (MOF) structure to bolster the performance of Mn, a non-precious metal catalyst, in this application. The Mn MOF outperformed the classical bulk MnO2 under the same conditions. I also demonstrate the OER capability of a commercially available FeAlCr alloy (Kanthal) as an affordable catalyst in an acidic medium. I conclude by offering my perspective on the future directions of the outlined work, thereby delivering the desired efficient, durable, and affordable next-generation materials.

Keywords: Clean Energy
Green Hydrogen
Light Emitting Diodes
Oxygen evolution reaction
Perovskite
Solar Cell
Advisor: Voznyy, Oleksandr
Cello-Piano Duos: Analytical, Practical and Rehearsal Strategies for the Collaborative Pianist

The ability to play collaborative music is one of the most important skills learned by undergraduate students majoring in piano performance. As pianists are required to play with a range of instruments, they must be well informed of the unique features and idiosyncrasies presented by the combination of piano and the instrument, or instruments, with which they arecollaborating. Compared to other instrumentalists, undergraduate pianists often have less experience with collaborative music. Students learning orchestral instruments or voice generally acquire experience in various ensembles from a younger age. These experiences are viewed as a vital component of studying these instruments from a relatively early stage. The comparatively limited experience as collaborative musicians many pianists have before their undergraduate degrees amplifies the importance of teaching pianists various skills needed as collaborative pianists and chamber musicians. This document describes a method of analyzing works from the collaborative pianist’s repertoire, exploring how a pianist can use analysis to develop their interpretation and conception of a chamber music work. Analysis can inform strategies for practice and rehearsal. Since this document focuses on repertoire for the cello-piano duo, it also identifies specific challenges and characteristics of the cello-piano instrumentation—a topic that has received little attention in the current literature. This dissertation is in four chapters. The first chapter provides a literature review, while also highlighting other relevant topics that have not been examined in the current literature. The second chapter presents insights from interviews with professional pianists and cellists regarding their early training and experiences with chamber and collaborative music. The third chapter proposes a step-by-step guide to analysis for the collaborative pianist, discusses how to use analysis when learning duo works for cello and piano, and addresses challenges specific to collaboration with the cello. The final chapter takes Rachmaninov’s Sonata for Cello and Piano in G Minor, Op. 19 as a case study, demonstrating the practical application of the analytical process presented in the third chapter.

Advisor: McClelland, Ryan
Foreign Relations? A Comparative Study of Foreign Policy and the Media in Britain and America, 1939-1941

How do a people experience their country’s foreign policy statements? This thesis explores the projection of publicly stated foreign policy and how it is constructed by the media. The existing research literature rarely covers in any depth this fundamental aspect of modern foreign policy. That said, analysing the relationships between governments, media, and peoples in a comparative context offers essential insights into the way these connections work. Choosing Britain and America, both liberal democracies facing similar challenges in the international landscape, provides the lens to explore the intricate processes of policy projection.The approach of this thesis falls within the methodological ambit of International History with its emphasis on insights gained from comparative studies and its liking for ‘borderlands’ and suggestive conclusions. The thesis has two parts. Part 1 is thematic and contextual in approach. It explores three determinants - national political structures and belief systems, the importance of the personal assumptions of policy makers, and role of the media - looking at foreign policy between 1929 and 1938 for illustrative material. Part 2, using the years 1939, 1940 and 1941, examines how these three determinants buttressed government and public reactions to the expanding war. The voices in this thesis are the human voices of the players of the time not the voices of later historical judgement. They are found in speeches, diaries, letters, and commentary in the media. These are the broad questions asked of the research: How resistant were underlying beliefs and assumptions - the determinants of Part 1 - to the stresses of wartime events? How deliberate were policy makers in organising statements for the media? Did public reaction influence policy? The analysis shows the strong persistence of established structures and assumptions as the context for the projection of wartime foreign policy in both countries. It shows media commentators consciously adjusting to perceptions of their own country’s national needs and constraints as they reported the war. As far as changing stated foreign policy, the reception in the media seemed only to influence timing and strategies for implementation as events unfolded rather than policy itself.

Keywords: 1930s
Anglo-American comparison
Foreign policy
Media
World War II
Advisor: Pruessen, Ronald W
Sport for Development Side-lined Youth: An Empowering Intervention or Socializing Agent?

Faith in the positive outcomes of sport has led to its mobilization to fulfill several ‘developmental’ goals for youth in under-resourced communities (e.g., improved life skills, improved academics, etc.) under the name sport for development (SFD). The dominant narrative that sport is effective in the development of youth has been challenged by many scholars who illustrate that such a perspective is rooted in colonial practices that socialize participants to maintain power imbalances rather than empower participants and lead to social change. Hartmann and Kwauk (2011) term this the dominant vision approach. Within it, participants are not made aware of the institutions that play a role in their marginalization rendering them powerless in advocating for real change, growth, and development. This doctoral research program aimed to critically explore the dominant narrative that SFD programming is developmental for side-lined youth. Community-based participatory research (CBPR) strategies were used to engage young adults from marginalized communities as co-researchers by way of a young adult advisory board (YAAB). The YAAB co-designed data collection strategies deployed in two studies that captured the voices of side-lined youth and program facilitators. Life history interviews were used to capture the counter stories of side-lined youth which were analyzed to yield five narratives that illustrate a range of developmental gaps SFD programs have the potential to address. Semi-structured interviews were used to capture program facilitators’ intentions for side-lined youth who participated in their programs. The YAAB took part in thematic analysis that revealed alignment between youth narratives and program facilitator intentions, as well as differences in developmental approaches between program facilitators with lived experience in comparison to those without (i.e., learned experience). In addition, the CBPR process was evaluated to produce a systematic method for meaningful engagement of side-lined youth in the research process. Overall, this doctoral research program discusses the role of power in SFD programming and research, while providing theoretical and practical considerations for researchers and practitioners in this field. Furthermore, it explores the socioeconomic challenges that side-lined youth face, and demonstrates how sport can be used to address those gaps in a useful and realistic way.

Keywords: athletes
critical race theory
marginalized youth
positive youth development
social change
sport for development
Advisor: Arbour-Nicitopoulos, Kelly A
Parent Involvement in the Lives of College Students in Ontario

When working at a community college in Ontario, my colleagues and I frequently interacted with students and their parents. However, limited institutional resources supported such interactions and much of our work with parents was performed off the sides of our desks. As both an administrator and academic researcher, I was conflicted by how scholarly descriptions of parent involvement differed from my professional encounters with parents of students. I was inspired to synergize the support students receive in their college journeys: both the familial and institutional. Thus, the purpose of my doctoral research became to explore the involvement of parents in their students’ education journeys at four public Ontario Colleges. I grounded my research in Bronfenbrenner's (1977) & Bronfenbrenner & Morris' (2006) bioecological model. I used the bioecological model to conceptualize influences (including parents) on human (student) development. Through website content analysis, telephone interviews, and surveys, I sought to elucidate the nature of parent involvement in the context of college in Ontario. I used the parallel-databases variant of convergent design to collect and analyze data on the involvement of parents in the lives of college students, through three distinct research strands: (i) interviews with college employees,(ii) surveys of college employees, students, and parents, and (iii) college website content analysis. My study yielded novel contributions to the literature, including that the involvement of parents impacted both students and college employees. My research documented that parents (& other family members) were involved in a myriad of ways and that their involvement both positively and negatively affected students. My findings also highlighted a range of perspectives in regards to how parents were foreseen as involved in students’ college related experiences. In particular, I found institutional and college employees’ perceptions of the home-school relationship, often conflicted with student expectations and the involvement practices of parents (especially for families from marginalized backgrounds). Overall, I concluded that, in Ontario, parents are involved throughout students’ college journeys, from recruitment through to graduation, and beyond. Ultimately, I hope that my dissertation may inform professional practices seeking to support the involvement of parents in students’ college journeys in Ontario.

Keywords: college students
colleges in Ontario
family involvement
parent engagement
parent involvement
supporter involvement
Advisor: Waterman, Stephanie
Molecular Recognition and Catalysis – Amino Acids, Epoxide and Carbon Dioxide

Molecular recognition and catalysis are fundamental areas of research in chemistry. Stereoselective recognition of amino acids, catalytic asymmetric epoxidation, and CO2 fixation were investigated combining experimental and computational methods. Chapter 1 focuses on the stereoselective recognition of amino acids by imino boronate complexes. The origin of stereoselectivity is explained in terms of covalent, steric, and cation-π interactions. Conflicting reports on the stereoselectivity of this system is addressed. Moreover, proline derivatives were synthesized diastereoselectively from the amino acid boronate complexes. In Chapter 2, stereoselective recognition of (2R,3S)-2-phenyl-3-methylaziridine with diaminocyclohexane (DACH)-based Co-salen complexes was investigated where experimentally observed stereoselectivities and structures were reproduced with DFT calculations. Computation also shows that substituting the metal from Co to Mn and aziridines to corresponding epoxides does not significantly change the position of the coordinated substrates or their stereoselectivity of recognition. In Chapter 3, the origin of stereoselectivity for the Jacobsen-Katsuki epoxidation was examined by computation based on the lowest energy transition state structures. Through computation, we found a new origin of stereoselectivity that has not been previously reported. The enantioselectivity can be explained for the first time in terms of a unified transition state for different catalysts and substrates. In Chapter 4, the electronic effect on enantioselectivity of Jacobsen-Katsuki epoxidation is investigated by computation and analyzed using Hammond postulate, Reactivity-Selectivity principle, and Marcus equation. This study shows that Marcus’ intrinsic barrier is sensitive to the electronic effect, which results in greater stereoselectivity. In Chapter 5, we show that the electrophilicity of CO2 matches that of diaryl carbonates with the leaving group phenol pKa of around 7.6 and 5.4 when the nucleophiles are water and thiomethyl acetate, respectively. Enthalpic activation of CO2 can be achieved towards all nucleophiles by conversion to carbonates or carbamates with good leaving groups. A novel mechanism of biotin-dependent carboxylases is proposed based on computation, which considers N-phosphocarboxybiotin as the carboxylating agent rather than the conventionally proposed carboxybiotin. Each step of the new catalytic cycle was shown to be chemically reasonable and thermodynamically downhill by DFT computation. With the new mechanism, enthalpic activation of CO2 can be achieved unlike with carboxybiotin.

Keywords: amino acids
biotin-dependent carboxylase
epoxidation
mechanism
molecular recognition
Advisor: Chin, Jik JC
Theoretically Informed Design and Acceptability Evaluation of a Communication Bundle for Adult Intensive Care Unit Patients with an Advanced Airway during Pandemic Conditions

Background. Communication difficulty is associated with adverse physical and psychological sequelae for intensive care unit (ICU) patients managed with an advanced airway for mechanical ventilation. Supportive communication tools exist; however, few are integrated into practice. COVID-19 pandemic (2020-22) infection prevention and control (IPAC) conditions contribute new barriers to communication warranting solutions. Objectives. To use a theoretically informed study design to create and evaluate the acceptability of a co-designed bundled COmmunication intervention for adult patients with an advanced airway during the COVID-19 PandEmic (COPE) from the perspective of diverse health care professionals (HCP), patients, and family in the adult ICU IPAC context. Design. A sequential multiple study design including a scoping review, an interview study, co-design methods, and a convergent mixed-method acceptability evaluation study in a single adult medical-surgical ICU in Toronto, Canada (January 2020 – March 2021). Methods. The Theoretical Framework of Acceptability was used to consecutively analyze reported barriers to and facilitators for: communication tool use in the adult ICU in the scoping review; and stakeholder support of patient communication in the pandemic ICU context in qualitative interviews. The results from these two studies informed the co-design of the COPE intervention. Finally, the acceptability, appropriateness, and feasibility of COPE were evaluated using mixed-methods. Results. The COPE intervention included 1. Stocked IPAC approved physical communication tool cart, and electronic tool cart, 2. Education modules for HCP, and 3. Information for patient-family connection. COPE was rated and described to be acceptable, appropriate, and feasible. Integration of data sets revealed additional recommendations for COPE including enhanced access to tools and training; leadership support of the physical, cognitive, and emotional impact of communication work; and use of a theoretically informed implementation framework. Conclusion. A theoretical understanding of acceptability of communication interventions such as COPE from the perspective of key stakeholders can inform intervention design, improve acceptability, and potentially advance utilization of communication supportive tools in practice. Relevance to practice. Implications include the availability of an acceptable communication intervention for use and further evaluation, a call to action for communication training, and need for leadership support for ICU HCP and communication work.

Keywords: Communication
COVID-19
Critical Care
Advisor: Dale, Craig
Theory and Application of Refracting Metasurfaces for Phased-Array Angular Scan Extension

Most of this thesis discusses metasurface lenses and their application to enhancing the angular scan range of phased antenna arrays -- an application of particular interest for 5G. Theoretical aspects of the problem are first discussed, and we are able to say that most, if not all, lens-based scan enhancers degrade the directivity of the source. This degradation is proportional to the enhancement of the device. To validate some of the theory and test various refracting devices a simulation tool was written to perform quick simulations of 2D scenarios. The simulation tool is discussed in detail as well, and it turns out that the vague metasurface definition (defined via the phase it incurs upon the incident fields) leads to quantifiable "errors." Simulation rigor is improved and the rest of the theory is validated via full-field simulations. In these simulations the lenses are defined according to the theory of ZYK boundary surfaces (a.k.a. omega bi-anisotropic Huygens metasurfaces). This definition performs as an ideal lens in the context of Gaussian beams, and we argue that this definition extends the concept of an ideal lens to electromagnetics. The topic is concluded by experimental verification of some of the theoretical claims. Finally, the theory of cotangent ZY boundary surfaces (a.k.a. Huygen's refracting metasurface, a.k.a.tangent sigma-tau boundary) is revisited. In a somewhat educational manner, we build up the theory of "ideal" refraction and claim that existing treatments of the topic leave the problem somewhat incomplete -- no "general" scattering solution is known. We then proceed to analytically solve for the general scattering of a tangent-like sigma-tau boundary subject to TE illumination. The obtained solution is studied extensively, and new functionalities of cotangent ZY boundaries are discovered -- namely, refraction without specular reflection and oblique absorption.

Keywords: 5G Antennas
Antenna Arrays
Huygens
Lenses
Scattering
Advisor: Eleftheriades, George V
Navigating Administrative Leadership: An Examination of Brown Women Educators’ Leadership Experiences in K-12 Public Schools in Ontario

This qualitative research grounded in notions of Seva Service Leadership examines the experiences of Brown women in formal (administrative) leadership roles in K-12 Public Schools in Ontario. Through semi-structured interviews, 15 self-identifying Brown women educators (BWEs) shared how they navigate their leadership journeys, factors that influence their decisions to enter formal leadership roles, and what sustains them in their administrative leadership roles. The term ‘Brown’ is used in this study to refer to women who self-identify as Indian, Pakistani, Bangladeshi or Sri Lankan descent/heritage and/or belonging to the South Asian diaspora. BWEs navigating leadership roles in K-12 Ontario public school boards face individual and systemic barriers, while engaging in strategies that sustain their leadership journeys. The findings from the participants’ experiences revealed: a) the Need for and Importance of Mentoring, b) the Need to Prove Oneself, c) Importance of Representation, d) Experiencing and Navigating Microaggressions and Whiteness, e) Navigating Internal Tensions f) Survival Strategies, and g) Pay it Forward. Findings also revealed that BWEs interpret their experiences by using Seva Service Leadership actions and subsequently their agency. Finally, this research can inform hiring and recruitment practices of not only Brown women in formal leadership roles in K-12 schools in Ontario, but all diverse populations. The study concludes with implications for practice and future research.

Keywords: Administrators
Brown Women
Educational Leadership
Leadership Journey
Seva Service Leadership
Advisor: Lopez, Ann E
Type I Interferon Responses in Monocytes Regulate GITRL Expression and Anti-tumor Immunity

Human mononuclear phagocytes comprise specialized subsets of dendritic cells (DCs) and monocytes, but how these subsets individually regulate the expression of the molecular signals involved in T cell costimulation is incompletely understood. In a first study presented in chapter 2, I demonstrate that type-I interferons (IFN-Is) regulate the expression of the T cell co-stimulatory molecule GITRL on human peripheral blood DC3, and to a lower extent on cDC2 and monocytes. Using single-cell transcriptomics to predict regulatory networks and pharmacological inhibitors to validate predictions, I also show that human GITRL expression is regulated by NF-B downstream of IFN-I signaling. Collectively, this study provides insight into the regulation of human GITRL expression and the cell type-specific response of human DC and monocyte subsets to IFN-I. In a second study, I investigated how IFN-I signaling in monocytes affects anti-tumor immunity in the context of STING agonist therapy of cancer. The cyclic GMP-AMP synthase stimulator of interferon genes (cGAS-STING) pathway allows cells to produce IFN-Is upon detection of cytosolic DNA and intratumoral injection of STING agonists drives durable and systemic control of pre-established tumors in mice. In chapters 3 and 4, I show that intratumoral injection of STING agonists drives the accumulation of inflammatory monocytes in B16F10 tumors and tumor-draining lymph nodes. I demonstrate that these monocytes have responded to IFN-Is and express GITRL and IL-18. I further show that GITRL expression on CCR2+ cells and IL-18 are important for the response to STING agonist therapy. Collectively, this study provides novel insights into the role of IFN-Is, monocytes, GITRL, and IL-18 during STING agonist therapy.

Advisor: Watts, Tania H