title: Novel MOS-Based Biomolecule Detection Techniques

abstract: This thesis advances the state of the art in biomolecule detection by allowing for quantitative detection using radioactive labels whose decay is detected by a pixelated complementary metal-oxide-semiconductor (CMOS), or CMOS-compatible, sensor. Additionally, the usefulness of this technology as a testbed for radioimmunotherapy (RIT) pharmaceuticals is considered. For the first time a CMOS image sensor has been used to detect the presence of radiolabelled target biomolecules captured on a functionalized surface. Using aptamer functionalization the system successfully detected phosphorus-32 labelled adenosine triphosphate (ATP) at a surface concentration of 2.3 x 10^7 molecules/cm^2, well below those typically associated with fluorescence-based sensor architectures. The system has also demonstrated its amenability to multiplexed biomolecule detection. Geant4, a Monte Carlo toolkit for simulating the passage of radiation through matter, was used to model the detection system. This system has applications in quantitative biomolecule detection and in the development of RIT pharmaceuticals employing beta particle emitting isotopes. Also for the first time, a MOS sensor has been designed, fabricated, and tested for use in the characterization of targeted alpha therapy (TAT) pharmaceuticals. The sensor consists of a 16 by 16 array of 100 micrometer square alpha particle sensitive cells fabricated in-house using a simple nMOS process. A subset of the cells are functionalized for the attachment of chelators under investigation for new pharmaceuticals. To demonstrate the utility of this sensor as a characterization platform, cells functionalized with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-DNA conjugates were used to chelate americium-241 from solution, and the alpha particle emissions over the surface of the IC measured. The IC was able to quantitatively determine the amount of alpha emitter present over each cell, allowing the chelator and chelating chemistry to be assessed. Without any optimization of the chelation chemistry, a 21% increase of emissions was detected on cells functionalized with DOTA relative to unfunctionalized cells.


title: Experimental Evaluation of Reordering Buffer Management Algorithms

abstract: In the Reordering Buffer Management (RBM) problem, we are given an input sequence of size N and a buffer B of size k (k < N). Each item in the input sequence is characterized by its "colour''. The defining characteristic of this problem is that a cost is incurred when we switch from one colour to another in the resulting output sequence. Our goal is to permute the input sequence using the buffer B such that the cost of switching between colours is minimized. In the online version, the input sequence is not known in advance. We propose a new algorithm in this thesis, Accelerated Threshold (Acc-T) for the online version of the RBM problem with non-uniform costs. This thesis also presents experimental results for several existing uniform and non-uniform cost algorithms and compares them against different combinations of input sequence types, cost functions, buffer sizes and number of colours.


title: Wideband Up-Converting Mixer for Digital Communications Implemented in 130nm CMOS Technology

abstract: This thesis presents the design methodology and silicon implementation of a 0.13μm CMOS up-conversion mixer for wireless applications. The design approach is simulation based while maintaining the appropriate reference to the theory. The novelty of this work mainly consists in the implementation of the wide band digital phase shifter on the same chip with the analog mixer/multiplier cells. The design methodology allows a cost effective implementation of a fully integrated solution that requires 1.2x1.55mm of silicon and it can be used in any wireless device that transmits digitally modulated data. The following components were designed, simulated then integrated on chip: wideband digital phase shifter, two Gilbert cells for the I and Q paths, wideband active balun and biasing cells.


title: Towards a Political Economy of Military Spending

abstract: Although the direct costs of the military are well known, there is regular reference to the ‘spin-offs’ that supposedly justify military expenditure. Unfortunately, the heterogeneity and complexity of military institutions and political-economic landscapes has consistently eluded an even-keel and scientific analysis of military spinoffs. To pursue this question of military spending’s externalities further requires a stronger analytical foundation which clearly situates the military’s role within the political-economy. This work thus seeks to navigate a rich ontological landscape across a wide historical spectrum in order to colour the relationship between the military, the state, and society at large. Focusing attention on questions of military investment in human capital, military R&D, Keynesianism and other tenants of military spending, I posit that while military spending is tends to be less economically productive than comparable spending projects conducted through other means, military spending performs functions indispensable to the political-economic structure of the state.


title: The Expansion of Conducted Energy Weapon Use in Ontario: Pacification and Policy Development

abstract: This thesis examines the Ontario government’s decision to allow for the expansion of Conducted Energy Weapons (CEWs) to all front-line police officers. I utilize a framework of pacification strategies that illustrate the way in which police services, particularly the Ottawa Police Service, should implement a CEW policy for the deployment of the weapon in order to achieve effective police-community partnerships. The decision to expand CEWs demonstrates an abdication of responsibility on the part of the province to local police agencies and the new policy provides little guidance. It is important that local agencies develop strong and effective CEW policies for the purpose of enhancing public and police safety as well as ensuring meaningful accountability in Ontario. I analyze several provincial and agency CEW guidelines in order to facilitate the development of effective CEW guidelines at the agency level and, importantly, to ensure accountability for when these weapons are deployed.


title: The Production and Perception of Vowel Height and Duration

abstract: High vowels are generally shorter than low vowels: there is a positive correlation between F1 and duration in English and cross-linguistically (Heffner 1937; Elert 1964; Äimä, 1918). This paper argues that the cross-linguistic height/duration correlation might be explained perceptually: high vowels inherently sound shorter than low vowels. Study 1 analyzed Chilean Spanish vowels to determine whether this correlation is physiological in nature or the result of linguistic rules, finding that the correlation is linguistically-specified. To account for the cross-linguistic occurrence of the correlation, Study 2 tested if speakers perceive shorter high vowels in a forced-choice perception task. Results indicate that high vowels indeed sound shorter, and that this vowel categorization ability is partially learned.


title: Shared Syntax in Turkish-English Bilinguals

abstract: A question of interest in bilingualism research is whether each language has a unique mental representation or whether they share a mental representation. Syntactic priming studies with bilinguals suggest that structural knowledge is shared between languages. This interaction between the two languages is called “shared syntax.” However, these studies have not shown the same effect for typologically dissimilar languages. The current study aims to create an extension of syntactic priming studies by using a specific bilingual population: simultaneous interpretation students. Simultaneous interpreters are well-known for their high proficiency. Thus, interpreters are an ideal participant group to be tested in order to test the validity of the shared syntax account for typologically different languages. This study presents different bilingual populations that have not been heavily investigated. In this respect, it will be one of the few studies that have tested the shared syntax account in Turkish with simultaneous interpretation students.


title: Towards a Visual Simultaneous Localization and Mapping System for Computationally Constrained Systems

abstract: Future robotic planetary exploration missions such as sample retrieval and in-situ resource utilization will require more accurate localization techniques such as Simultaneous Localization and Mapping (SLAM) to achieve the science goals. In this thesis, a visual SLAM system aimed towards computationally constrained systems is presented. In this work, Binary Robust Invariant Scalable Keypoints (BRISK) and Oriented FAST and Rotated BRIEF (ORB) feature descriptors are introduced and compared against Speeded Up Robust Features (SURF). BRISK is shown to achieve similar relative pose estimation performance than SURF while being an order of magnitude faster. This work also discusses a simple back-end pose-graph optimization approach using libg2o. The back end system improved the position estimation as well as detected loop closure events. These initial results show that computationally inexpensive feature detectors such as BRISK and ORB can be used as core feature detection algorithms for a visual SLAM system.


title: Steelcity Living: Hamilton, Stelco and the Post-industrial City

abstract: Brownfield sites in Canada play an essential role in the future development of post-industrial cities. Fundamentally unproductive, these spaces are of no benefit to the city’s recovery and therefore must be adapted for a new use. U.S. Steel Canada (Stelco) has defined Hamilton’s economy and cultural identity as a blue collar city for more than a century. Now under bankruptcy protection and seeking potential buyers, concerns of the city’s capacity to exist as an industrial based economy have increased. The growing inventory of brownfields and the demand for affordable housing in Hamilton are influential factors in its season of heightened urban renewal.Steelcity Living seeks to set a precedent for development and affordable housing enriched by the remediation and preservation of Stelco’s industrial ruins and the significance of Hamilton’s cultural past.


title: Why Get Involved in Program Evaluations?: Toward a Model of Stakeholder Involvement Motives

abstract: It is generally recognized that for any evaluation to be successful there needs to be a significant amount of involvement from program staff and other stakeholders who are invested in the program. Ideally, these individuals would be highly engaged in the evaluation process; however, in practice this ideal is rarely met. Two research studies were undertaken to explore different stakeholder motives for involvement in program evaluations and their relative importance in involvement decisions. In Study 1, stakeholder views of their own involvement (or lack thereof) in recent program evaluations were analyzed qualitatively using a thematic analysis approach. The findings revealed diverse stakeholder motives for evaluation involvement that include personal/human factors (e.g., opportunity for personal advancement), evaluation factors (e.g., clarity of evaluation goals) and organ-izational factors (e.g., funding implications). A second study looked more closely at these motives to determine their relative importance to evaluation involvement decision-making. Using the Q-sort method, three involvement profiles were identified which revealed different pathways to involvement based on individual concerns for program funding, learning opportunities, and evaluation quality. A preliminary model of stake-holder involvement motives is proposed in which the value and relevance of the evaluation are determined by expected outcomes of the evaluation.


title: Advanced Framework for Transient Simulation of High-Speed Circuits and Interconnects Using L-Stable High-Order Integration Methods

abstract: The trends toward higher operating frequencies and sharper rise times \hla{coupled} with faster switching signals have made modeling and simulation of high-speed interconnects an increasingly challenging task. Typically, the circuit models arising from characterizing coupled high-speed interconnects are very large linear circuits with many linear components, making the transient analysis a cumbersome task. Recently, waveform relaxation methods based on transverse partitioning (WR-TP) were proposed to address this issue. It was shown that the complexity of WR-TP grows only linearly with the number of lines. However, as the coupling between the lines becomes stronger, the WR-TP algorithm either fails to converge or the number of iterations required for convergence increases. To address the issue of convergence in WR-TP, an overlapping partitioning (OP) method is presented in this thesis proposal. Using the OP approach, the coupled interconnects are partitioned such that each subcircuit contains one or more lines that are tightly coupled, while allowing the lines between adjacent subcircuits to overlap. The weak coupling between the subcircuits are represented using voltage/current sources. Next, each subcircuit is simulated independently using a suitable integration method for the whole time of interest. The voltage/current sources representing the coupling between the subcircuits are then updated. This process is repeated until convergence is obtained. Typically, during the simulation of each subcircuit, an integration method is used to discretize the time points by taking finite time steps to approximate the waveforms at those time points. Recently, it has been shown that using a high-order and $L$-stable integration methods based on Obreshkov formula (ObF) can lead to a large reduction in the transient analysis time of general circuits. In this thesis, we show that by using ObF and taking advantage of the special structure of the mathematical formulation of the interconnect circuits, the simulation time of each subcircuit can be significantly reduced. Thus, reducing the overall simulation time.


title: Geographic Partitioning Techniques for the Anonymization of Health Care Data

abstract: As the demand for the availability of detailed health care data sets continues to increase, organizations are faced with the conflicting interests of releasing this important information while protecting the confidentiality of the individuals to whom the data pertains. A major concern when releasing health care data is the geographic information which has a large influence on the re-identifiability of the data and yet is essential for many research applications. In this work, a novel system for data anonymization is presented. At the core of the system is the aggregation of an initial regionalization guided by the use of a Voronoi diagram. Testing is conducted via an implementation designed to run and analyze the results of the various combinations of approaches. In addition, a comparative test is conducted with another system, GeoLeader. It is shown that our system is capable of producing comparable results with a much faster running time.


title: Simulation of Next Generation Sequencing Short Reads for Mutation Spectrum Analysis

abstract: Next generation sequencing (NGS) of mutant reporter transgenes is increasingly being used for mutation spectrum analysis (MSA) to characterize the genomic effects of mutagens. The ability to simulate NGS-MSA experimental data will permit the tuning of various parameters in the downstream analysis pipeline. However, no simulator currently exists that is capable of producing the read depths (up to 100,000x) required for MSA experiments. In this study, we introduce MutSim, a short read mutation simulator that enables researchers to generate NGS data for simulated samples exposed to a mutagen. MutSim generates data following the Ion Proton™ instrument error model and also a mutational model of a given mutagen. MutSim is shown to be highly scalable both with respect to genome length and read depth coverage. MutSim simulated data is validated against real experimental data in several aspects including genotype content, quality scores, read depth coverage and read length.


title: Architecture of Assimilation: A Vernacular Approach to Housing for China's Rural to Urban Migrants

abstract: China is urbanizing at an unprecedented rate, primarily as a result of rural-to-urban migration. Rapid urbanization, comes with challenges and consequences, both for migrants and municipalities. New arrivals must forge new identities and adjust to the novel and dynamic environments around them. This thesis considers the experience as the move into urban environments and the impact housing form has on their ability to assimilate. Among the questions to consider, is whether, and with what modifications the lilong might present an alternative to China's current predilection for high-rise tower ensembles. The design portion of this thesis draws on the lilong to propose a flexible and adaptable housing model to challenge the existing approach to housing form. The goal is to find a culturally resonant approach of housing that better facilitates the formation of social networks, accommodates informal entrepreneurial activity, and eases the transition from rural to urban life.


title: Sensitivity-Analysis-Based Adjoint Neural Network Techniques for Nonlinear Applications

abstract: Artificial neural networks (ANN) have recently emerged as a powerful computer-aided design (CAD) tool for modeling nonlinear devices and circuits. The overall objective of this thesis is to develop sensitivity analysis based neural network techniques for both frequency domain and transient modeling of nonlinear circuits. The proposed techniques not only add sensitivity data to the obtained model but also make conventional training more efficient. The first contribution of this thesis is the development of sensitivity-analysis-based adjoint neural-network (SAANN) technique for modeling microwave passive components. This method adds sensitivity data to the obtained model. In addition, the SAANN technique reduces the amount of training data required for model development increasing the efficiency of model development. As a further contribution, this thesis presents a novel robust modeling technique, adjoint state-space dynamic neural network (ASSDNN), for transient modeling of nonlinear optical/electrical components and circuits. This technique adds time-domain sensitivity data, which does not exist in current optoelectronic and physics-based simulators, to the output of the obtained model. The proposed technique requires less training data for creating the model and consequently makes training faster and more efficient. Furthermore, this technique was developed such that it can take advantage of parallel computation. This results in the technique being much faster and more efficient than conventional transient modeling techniques. In addition, the evaluation time for models of nonlinear optical-electrical and physics-based devices generated using the proposed technique is reduced compared to current simulation tools.


title: The European Public Sphere: European Commission Initiatives on Creating Transnational Media Networks

abstract: The results of the European Parliament Elections 2014 demonstrated a rise of Euroscepticism in the EU. The reasons of this are a lack of information about the EU in the Member States and insufficient mechanisms for debate and citizens' engagement in decision making. The analysts explain it also by the weakness of providing a forum for the development of common identity and legitimacy of the European public sphere. This thesis looks at media as mechanisms of the European public sphere. The thesis examines institutional models of two transnational audiovisual media on European affairs supported by the European Commission: the Euronews television and the Euranet Plus radio network. The author considers the roles of Euronews and Euranet Plus in the European public sphere and in attempting to reduce Euroscepticism.


title: Russia's Nineties Generation and their Cultural & Collective Memory of the Soviet Union

abstract: This thesis explores the legacy of Russia’s Soviet past in the memory of its youth. It examines the ways of remembering and interpreting the past in light of Russia’s present tenure and global collective, and cultural memory theory. Primary findings support the anti-establishment view that history is manipulated with a propagandistic aim in Russia. Findings also show that the memory of this generation is frequently recalled from two divergent and contradictory perspectives, referred to as memory parallels in this work. An assertion is made that this generation’s memory of its Soviet past is constructed and susceptible to current trends in Russia’s internal and foreign policy. The memory of Russia’s ‘90s generation lacks autonomy and uniformity, when recalling their Soviet past.


title: Data Mining the Play-by-Play: Assessing and Applying NHL Performance Metrics Using Statistical Methods

abstract: Hockey statistics are traditionally simple with limited analytical value, especially for individual assessment. The National Hockey League provides Play-By- Play and Time-On-Ice files for every game, recording game events and players present during them. These are combined to derive Corsi, Fenwick, and shot differentials, now commonly used in the hockey analytics world. Using regression and data visualization we examined their value in explaining win percentage and goal percentage, demonstrating the value of full-strength tied Corsi particularly. We also examined the effects of score on shot attempts, and the effects of special teams and home advantage on win percentage. Finally, we created a binary transaction database of players and Corsi events and applied association rule learning to clearly measure individual performance and player chemistry, demonstrating significant potential for use in management and coaching.


title: Investigating disjunction in American Sign Language:  The importance of nonmanual signals and the influence of English

abstract: This thesis investigates the importance of nonmanual signals (facial expressions, movements of the head and body) in American Sign Language (ASL), and argues that nonmanual signals are the overt realization of logical operators. First, we explore the effect of English influence on nonmanual signals, using Kidd’s (2010) theory of the displacement of elements. Second, we examine native signers’ interpretation of a nonmanual coordinator that is ambiguous between inclusive-disjunction/conjunction, and may be disambiguated with additional nonmanual signals (Davidson, 2013). We find a mismatch between linguistic competence and linguistic performance in delayed first language learners, and a preference for a conjunctive interpretation by native signers when there is a lack of disambiguating cues. We show that this preference is part of a general pattern in populations with the inclusive-disjunction/conjunction ambiguity, such as adult speakers of Warlpiri (Bowler, 2014) and English-speaking children (Singh et al., 2013).


title: The Ethics of Care and the Newfoundland Paid Family Caregiver Program: An Assessment

abstract: The ethics of care has gained traction as a feminist normative lens from which to examine policies and policy issues. This thesis aims to contribute to this growing literature by employing a critical ethics of care lens to assess a new long-term care initiative in the province of Newfoundland and Labrador, Canada. This initiative, called the Newfoundland Paid Family Caregiver Program, allows eligible participants to pay family members for care services. This analysis uncovers numerous tensions, both practical and theoretical, related to the way this program (re)organizes care. Specifically, the ways in which this program downloads caring responsibilities onto the family and monetizes caring relations is discussed. Finally, this analysis explores what care policies starting from the premises of a critical ethics of care might look like, and argues that such policies would have greater reach and positive consequences in terms of (re)producing healthy, flourishing lives for us all.


title: A Novel Clock Distribution System with Injection Locked Rotary Traveling Wave Oscillator and Built-In Self-Test

abstract: The thesis implemented a clock distribution system with novel Injection Locked Rotary Traveling Wave Oscillators (IL-RTWOs) and Built-In Self-Test (BIST). Both trans-conductance injection locking and pulse injection locking techniques are explored. The combination of switched Metal-Insulator-Metal capacitors (MIM-caps) and a novel use of Complementary Varactor Pairs (CVPs) target a 1.7 GHz to 2.0 GHz frequency tuning range and 100 kHz frequency resolution. The Complementary Varactor Pairs (CVPs) implemented for RTWO phase tuning achieves 56° phase tuning range and 0.34° worst case phase tuning resolution. The RTWO scheme is implemented in IBM’s 130 nm CMOS technology. The RTWO free running phase noise is -126dBc/Hz at 1MHz offset from 2 GHz operating frequency. With the injection locking techniques, the RTWO inband phase noise is further reduced. This project also describes a Built-In Self-Test (BIST) circuit used to verify and tune the timing integrity of the clock distribution system. The die area is limited by the outer parameter of the RTWOs – leaving internal space for other circuits. The BIST circuit occupies 0.025 mm^2 chip area. The BIST circuit allows testing of the integrity of the clock distribution system at speed by determining if the system clock skew can be tolerated or needs adjustment. The clock distribution network consumes a total of 26.5 mA current from a 1.14 V power supply. The close-in spurs of the IL-RTWO are 79 dB lower than the output spectrum. The IL-RTWO attains an inband phase noise performance of -132 dBc/Hz at 100 kHz offset from 2.039 GHz output and its integrated rms jitter from 1 kHz to 40 MHz offset frequency is 39 fs. The pulse and transconductance injector circuits are analyzed and measured and it is shown that the pulse injector tends to achieve better phase noise performance. To the author’s best knowledge, the implementation of CVPs and injection locked techniques on RTWO, and the implementation of this BIST technique to determine clock integrity of an injection locked clock distribution network have not been explored previously.


title: Developing and Validating a Risk Assessment Scale to Predict Inmate Placements in Administrative Segregation in the Correctional Service of Canada

abstract: Concern over the use of administrative segregation has motivated efforts to reduce segregation placements. The purpose of this study was to develop and validate an actuarial risk assessment scale to predict admissions to administrative segregation (for reasons of jeopardizing security or the inmate’s own safety) for at least six consecutive days within two years of admission to the Correctional Service of Canada (CSC). The sample (N = 16,701) included all male offenders admitted to CSC from fiscal years 2007/2008 through 2009/2010 and all female offenders admitted from 1999/2000 through 2009/2010. Offenders were randomly divided into a development sample (N = 11,110) and a validation sample (N = 5,591). Analyses were separated by reason for administrative segregation, gender, and Aboriginal ancestry. Overall, 413 potential predictor variables were examined, including items from assessment scales, demographic information, current offence information, flags/alerts/needs, and information from previous federal sentences. Approximately 24% of offenders were placed in administrative segregation. Of the 413 variables examined, 86% significantly predicted segregation placements. The item pool was reduced using Principal Components Analysis, tests of unique contributions within the measured components, and considerations of general utility and face validity. Several scales were developed and validated. Considering both accuracy and efficiency, the optimal scale had six static items (age, prior convictions, prior segregation placement, sentence length, criminal versatility, and prior violence) – this scale was called the Risk of Administrative Segregation Tool (RAST). Attempts to develop scales unique for men and women and those of Aboriginal ancestry did not yield meaningfully higher accuracy than the overall RAST. The RAST generalized well to the validation sample (AUC = .80) with high discrimination, suitable calibration (mostly non-significant E/O indexes), and superior performance to other risk scales used by CSC. Normative data (absolute segregation rates, percentiles, and risk ratios) were presented for the RAST. The RAST is an appropriate scale to use in practice for identifying risk of administrative segregation placements among CSC inmates and may serve as a first step in future efforts to divert offenders from segregation. Limitations of the current study and suggestions for future research are discussed.


title: Identifying Latent Cognitive Constructs in a Comprehensive Model of Aviation Outcomes:  The Role of the Dynamic Mental Model for Pilots

abstract: Background: Older private pilots are at greater risk for general aviation accidents when compared with younger pilots. Predicting which older pilots are vulnerable to accidents has proven elusive, despite the inclusion of domain-independent cognitive factors, such as working memory and processing speed, in outcome models. Thus, it has been suggested that domain-dependent cognitive factors should feature in models of pilot performance. The mental model for pilots was highlighted as a domain-dependent variable particularly relevant to explanations of pilot performance (Hardy & Parasuraman, 1997). The present study specified a mental model for pilots and examined its capacity to predict aviation outcomes. Methods: A flight simulation program of research collected performance data for 108 pilots who “flew” a Cessna 172. The findings from the flight simulation research produced a robust set of data structures utilized in the modeling phases of this work. A dynamic mental model for pilots (DMM) was developed with guidance from a framework first proposed by Herdman and LeFevre (2004). Structural equation modeling was used to validate the DMM as a central element in a cognition-oriented model of pilot performance for aviation (COMP-A). The COMP-A, based on work by Hardy and Parasuraman (1997), was used as a platform for quantifying the effects of pilot attributes and cognition on aviation outcomes. Findings: Confirmatory factor analysis demonstrated the DMM convergence as a formative-reflective construct composed of domain-relevant components. The COMP-A included an expansive selection of predictor variables and outcomes of relevance to aviation: critical incidents and runway incursion management. The DMM scores provided the best explanation of critical incidents. The DMM also mediated the majority of effects from upstream variables, such as pilot age, on aviation outcomes and was the only variable to predict risk of a critical incident with reasonable sensitivity and specificity. Implications: Findings challenge current strategies for assessing the aging aviator. First, visual-spatial attention, and not working memory or processing speed, was the domain-independent variable with the largest explanatory power in the COMP-A. Second, domain-dependent, not domain-independent, constructs were the most efficacious predictors of risk.


title: “It’s a game, you've got to play the game”: Motivation and ‘Being Employable’ in Ontario Unemployment Supports

abstract: This thesis research analyses and explores the ways neoliberal conceptualizations of individual responsibility are embedded in practices of becoming employable. This occurs through provision of employment services, which reflect neoliberalization in funding policy documents. An ethnographic case study was conducted in one agency providing job-seeking assistance and services to unemployed Ontarians in a region experiencing high unemployment. Research methods included participant observation of the processes of service provision, as well as interviews with seventeen unemployed job-seekers. During field research, the concept motivation emerged as a mechanism for filtering whether job-seeking clients are suitable for receiving provincially-funded employment resources. Definitions of motivation in funding policy documents embody a neoliberal rhetoric that positions individuals as ‘agents’ responsible for enacting willingness and flexibility to engage in the labour market. Findings suggest that definitions and interpretations of the concept motivation lead to practices that delegitimize disincentives to employment, thus exacerbating demotivation.


title: The Discursive Enactment of Edward Snowden

abstract: Edward Snowden’s whistleblowing on the National Security Agency (NSA) has resulted in widespread discursive battles on popular and social media. The purpose of this study was to theoretically and empirically explore how various participants discursively engaged the debate with digital media. It sought to identify and analyze the discursive forces at play, investigating how ‘storylines’ and ‘antagonisms’ are enacted, reinforced, and contested. Performing a type of ‘online ethnography’, the digital realms were analyzed on a macro-level before 22 articles were selected for in-depth analysis. Additionally, a corpus of nearly 40,000 YouTube comments was built then analyzed, and 5 interviews with Snowden were taken into consideration. Analysis reveals how and why the terms ‘hero’, ‘patriot’, ‘traitor’ and ‘villain’ come to be used for many whistleblowers, including Snowden. Furthermore, the study offers explanations for the roles that these ‘terms’ played when taken up and resisted by diverse participants.


title: Rhetorical Moves in an Occluded Genre: A Qualitative Analysis of Suicide Notes

abstract: The purpose of this study is to investigate suicide notes from the perspective of English for Specific Purposes (ESP) (Bhatia, 1993, 2004; Swales, 1990) genre approach. Specifically, the study examines the communicative purpose(s) and the rhetorical move/step structure (Swales, 1990) in a corpus of suicide notes. Eighty-six suicide notes (Leenaars, 1988; Shneidman & Farberow, 1957) were analyzed using the rhetorical move/step analysis (Swales, 1990). The findings suggest that suicide notes share common communicative purposes and rhetorical move/step structure, and, therefore, constitute a genre from the ESP perspective. By establishing the rhetorical move structure of suicide notes, this study addresses the lack of genre-based studies of suicide notes in the literature and makes a theoretically-based contribution to the fields of genre studies and, potentially, forensic linguistics. Keywords: Suicide notes, ESP, genre, rhetorical move/step analysis


title: A Geochemical Study of Cenozoic Magmatism Along an East-West Transect from Central Great Basin, Nevada to the Ancestral Cascade Arc, California – A Compositional Journey Over Space and Time

abstract: Processes linked to shallow subduction, slab rollback and extension are recorded in the whole-rock major, trace element and Sr, Nd, Pb and O isotopic compositions of magmatic rocks in both time and space. Over 250 Eocene to Mio-Pliocene volcanic rocks were sampled along a transect across Central Great Basin (GB) in Nevada to the Ancestral Cascade Arc (ACA) in northern Sierra Nevada, California (ca. 39 to 40 o latitude), which are interpreted to represent the southwestward migration of magmatism that occurred as a result of the shallow subduction and eventual rollback of the Farallon plate. Volcanic rocks from the study area are chemically and chronologically zoned into four regions: central GB (5 to 35 Ma), western GB (5 to 14 Ma), eastern and western ACA (2.5 to 16 Ma). The volcanic products are dominantly calc-alkalic but transitional to alkalic in the eastern part of the study area. Intermediate lavas are the dominant lava-type, which evolved from the mafic lavas by fractional crystallization and variable degrees of assimilation with lower crustal melts. Central GB lavas have shoshonitic affinities with higher K, P, Ti, La/Sm as well as lower (Sr/P)pmn and Ba/Nb. Western GB lavas are chemically uniform with low K, La/Sm and Rb/K. Compared to GB lavas, ACA lavas were largely modified by subduction processes with higher La/Sm, Ba/Nb, and Th/Rb values. Pb-Pb isotope plots for ACA mafic to intermediate lavas show linear trends to higher Pb-isotopic values, which combined with lower Ce/Ce* and high Th/Nb ratios are interpreted to come from slab sediment. Pb-isotope ratios for GB lavas increase with increasing silica, indicating assimilation of continental crust. Mafic and intermediate lavas from both the GB and ACA have overlapping 87Sr/86Sr and 143Nd/144Nd values that are consistent with primary melts mixing with a subduction-modified lithospheric mantle source. Percent melting of the mantle is enhanced by fluid flux from the dehydrating subducting slab, which is lowest for GB lavas due to low P-T conditions from a shallow slab dip, and highest for western ACA lavas, generated from higher slab dehydration and P-T conditions due to greater slab dip.


title: Effects of Agricultural Intensity Vary across Anuran Species

abstract: Documented effects of agricultural intensity on anurans have been inconsistent. One possible explanation for this is that agricultural intensity can be correlated with adult habitat amount. Differences in tadpole life history could also cause different responses to larval habitat quality. We identified 39 ponds in Eastern Ontario, surrounded by a wide variation of row crop cover, where we measured anuran abundances, nitrate concentration, and a suite of local pond variables. We then constructed path analyses for each species to determine the direction and potential causes of effect of agricultural intensity on abundance. We found variable responses to agricultural intensity across anurans. As predicted, much of this variation could be explained by adult habitat amount and larval habitat quality. Overall, our results suggest that agricultural intensity itself is not strongly affecting anurans in our region, but confirm that habitat loss due to agriculture is particularly detrimental for forest species.


title: Three Essays on Social Assistance in Canada:  A Multidisciplinary Focus on Ontario Singles

abstract: A single employable adult relying on social assistance in Ontario receives approximately $7,500 annually on which to live. In spite of this very low amount, singles make up Ontario’s fastest growing household group on social assistance. In 2012, a review of the province’s social assistance system recommended an immediate $100 increase in monthly benefit levels for singles. This raises three key questions: How did Ontario’s social assistance system develop into its current form? What do social assistance recipients do with increased monthly benefits? To what extent might increased benefit levels lead to higher caseloads? The present dissertation comprises three essays—each one looking to answer one of the above questions, and each with a different methodological approach. Each essay also has a different geographical focus: the first looks exclusively at Ontario; the second looks at Ontario’s welfare system while interviewing a sample of Toronto-based recipients; and the third looks at six provinces, including Ontario. The first essay offers a historical consideration of the emergence and development of Ontario’s social assistance system. With the 1965-1975 period being its major focus, the essay finds that the Great Depression prompted senior levels of government in Canada to spend more on income assistance, and that the strength of Canada’s post-World War II economy made it more palatable for both the Canadian and Ontario governments to expand social assistance coverage and increase benefit levels. For the second essay, I interviewed 10 Toronto-based men on social assistance, asking each of them detailed questions about their monthly budgets. Five themes emerged from the research, and each theme forms the basis for a hypothesis that may be examined in future research. For the third essay, I undertook an OLS regression analysis of determinants of social assistance caseloads for single employables across six Canadian provinces over the 1989-2010 period. Results suggest that the determinant of singles caseloads in a given year with the highest amount of statistical significance is the previous year’s caseloads. What is more, of all the independent variables—and aside from the previous year’s caseload level—only British Columbia’s stricter administrative rules attain five percent significance or better.


title: Recording Vanier's Changing Identity Through New Urban Infrastructure

abstract: This thesis examines how an always-evolving urban public realm can continue to honour its past history and peoples while simultaneously creating a more vital and vibrant environment. Whereas increasing the vibrancy of a neighborhood is generally coupled to the erasure of authentic history via gentrification, must that always be the case? This thesis posits that by decanting key programmatic requirements of conventional housing to new urban infrastructure, a neighborhood’s existing character and affordability can be maintained together.


title: The Veil of Modernity: Heritage Preservation in Toronto's Liberty Village

abstract: Through etymological interpretations and a study of architectural roots, this thesis will propose a modern intervention to a historically rich component of Toronto’s urban fabric. The dichotomy presented between the grounding truth of the authentic and the fleeting temporality of the modern in architecture will play a key role in developing a program and contemporary intervention to the Toronto Central Prison Chapel. Located in the highly developed east end in Liberty Village, this thesis will propose a design strategy that will link Toronto’s founding architectural language to the ever changing needs of the modern individual. The proposed design will serve as framework to embrace the collective and cultural past of the city while preserving and adapting the Prison Chapel to suit contemporary needs of the residents of Liberty Village.


title: Orientation Centre for the Wood Industry and Trades in the Chaudière Region

abstract: In a digital world obsessed with the image, how can we convey the importance of the trades to future generations? This project will explore the concept of architecture as a mirror for the trades; a space of observation and reflection for the trades themselves and for the public. Through the design of a small centre for training woodworkers on Amelia island, this thesis will use the site and its history, the building program and the materials and methods of construction to frame literal and phenomenological observation and reflection of the wood trades.


title: Knitting Takes Balls: Masculinity and the Practice of Knitting

abstract: Historically, the craft of knitting has been associated with femininity within the domestic sphere. However, knitting has experienced a revival within the past 15 years. This work examines how some men engage in the practice of knitting and how participation in a feminized activity affects re-negotiations of masculinity. Through an examination of R.W. Connell’s theory of Hegemonic Masculinity and Eric Anderson’s theory of Inclusive Masculinity, this piece explores the manner in which men are formulating new ways of performing their masculinities in environments of diminished homophobia.


title: Grain-size analysis and Arcellinida as tools for inferring paleoclimatological variability: a case study from Holocene Canadian Subarctic Lake Sediments

abstract: The central Northwest Territories of the Canadian Subarctic, and the myriad of lakes found therein, has through previous research been shown to archive records of past Holocene climate variability. Due to the low temporal resolution of previous paleoclimatic reconstructions questions remain as to past rates of natural climate change, a deficiency of concern to policy makers and modelers responsible with addressing human induced climate change. Two paleolimnological proxies of climate variability, end-member mixing analysis (EMMA) of lake grain-size distributions and the Arcellinida were further developed to increase the temporal resolution of paleoclimate reconstructions and provide a more complete picture of environmental response to past climate variability. A mm-interval subsampling strategy made possible through use of a custom-designed sledge microtome combined with EMMA of lake sediment cores significantly increased the temporal resolution of paleoclimate reconstructions. EMMA of lake sediment cores was used to describe changes in lake catchment hydrology and track the rate of climate deterioration and subsequent amelioration associated with known Holocene events such as the Holocene Climate Optimum (HCO) and the onset of the Neoglacial. Arcellinida as demonstrated here, are sensitive to treeline dynamics. Due to their well-preserved dissolution-resistant tests, rapid generation time and trophic position within lacustrine environments they offer unique insight into climate variability and change. Arcellinida are also characterized by ecophenotypes, which respond markedly to changing environmental conditions making them valuable tools for reconstructing environmental change. Three ecological transitions were seen in the observed Arcellinida communities through the past ca. 6600 cal yBP. Zone 1 spanned ca. 6600-2800 cal yBP and characterized the hydroecology of the lake during the HCO. Zone 2 spanned ca. 2800-140 cal yBP, which represents the Neoglacial. Zone 3 spans ca. 140 cal yBP to present and archives the recovery of the region from the Little Ice Age. Further development of these proxies will help to constrain the rate of climate variability and increase our understanding of the many ways in which the environment responds to climate change. This has implications not only for the Canadian Subarctic but for the Taiga biome, the largest terrestrial biome in the world.


title: Efficient Density Estimation using Fejer-Type Kernel Functions

abstract: We consider a class of kernel-type density estimators with Fejér-type kernels and theoretical smoothing parameters. In theory, the estimator under consideration dominates in $\mathbb{L}_p$, $1\le p<\infty$, all other estimators from the literature, in the locally asymptotic minimax sense. We demonstrate via simulations that the kernel-type estimator is good by comparing its performance to other fixed kernel estimators. We also consider two empirical bandwidth selection methods, namely, the common cross-validation and the less-known method based on the Fourier analysis of kernel density estimators. The common $\mathbb{L}_2$-risk is used to assess the quality of estimation. The kernel-type estimator is then tried to real financial data for a risk measure that is widely used in many applications. The simulation results show that the theoretical estimator under study provides very good finite sample performance and the bandwidth obtained by using the Fourier analysis techniques performs better than the one from cross-validation in most settings.


title: Metis Identity in Canada

abstract: The understanding and acknowledgement of Aboriginal rights has grown in importance within Canada as a result of the ever changing legal landscape and as Aboriginal groups more forcefully confront decades of colonial rule to assert their historic rights. While this has predominantly come out of First Nations issues, there has been a gradual increase in the rights cases by Métis communities. Primary among these was the 2003 Supreme Court of Canada Powley decision which introduced how Métis identity and community identification are key in a successful litigation claim by Métis. This research considers questions surrounding the contentious nature of Métis identity including how Métis see themselves and how it is prescribed by others including the state, through tools such as the Census of Canada.


title: An Assessment of the Antidepressant-like Properties of Erythropoietin in an Animal Model of Depression

abstract: Impaired neuroplasticity and altered connectivity between different brain regions may be key features of depression. As the cytokine erythropoietin (EPO) increases brain derived neurotrophic factor (BDNF) levels, EPO may enhance neuron survival and growth, leading to antidepressant effects. Here, EPO was tested for its ability to reverse depressive-like symptoms in rats following three weeks of chronic mild stressors. Neither stressor exposure nor EPO affected sucrose preference, which has been used to model the anhedonia characteristic of depression. Additionally, EPO did not reverse stressor-induced social avoidance. BDNF mRNA expression was reduced by stressor and EPO treatments in the prefrontal cortex, and elevated in the amygdala with EPO treatment. Additionally, FGF-2 expression was reduced in the amygdala with stressor exposure, but normalized following EPO treatment. Many of the results are inconsistent with a priori hypotheses, possibly owing to factors such as the timing of tissue collection and a lack of environmental enrichment.


title: Characterizing the Neurobiological Consequences of Perinatal Exposure to the Obesogenic Endocrine Disruptor Bisphenol-A

abstract: Bisphenol-A (BPA) is a component of polycarbonate and many other types of plastics. BPA has been characterized as an endocrine disruptor, most famously due to observations of its estrogenic activity in various experimental models. Because BPA is a common constituent of food and drink containers, and because it can leach out under certain conditions, human exposure is nearly ubiquitous. In this thesis, we demonstrate that CD-1 mice exposed to low, environmentally relevant doses of BPA during the perinatal period exhibit an adult phenotype characterized by sex-specific metabolic disruptions. Specifically, male mice exhibit impaired glucose tolerance, and females a propensity toward diet-induced obesity. Given the sensitivity of the hypothalamus to the organizational effects of sex steroids, we explored the possibility that early-life BPA exposure adversely affects the development of hypothalamic feeding circuitry to bring about these effects. We found that BPA- and diethylstilbestrol (DES)-exposed pups have respectively delayed and blunted postnatal leptin surges---a state of affairs that points to a role for leptin in the organizational effects of early-life xenoestrogen exposure. qRT-PCR analysis of leptin mRNA expression in white adipose tissue collected at the same time suggests that BPA and DES act at the transcriptional level to bring about these effects. Both male and female BPA-exposed mice showed a reduced density of POMC projections into the PVN. This phenotype was rescued in female BPA-exposed animals given daily injections of supplemental leptin (5 µg/g/day). Adult offspring from this experiment were resistant to leptin-induced suppression of food intake, body weight loss, and hypothalamic POMC upregulation. Taken together, these data suggest that BPA, a known obesogen, may exert its effects through developmental programming of the hypothalamic melanocortin circuitry.


title: Authenticating Adaptation:  Narrating the Incomplete Project

abstract: The purpose of this analysis is to redefine the term “authenticity” in our existing built environment as a narrative process rather than as a completed original. Our surroundings continuously evolve based on our inhabitation. Consequently, the remaining traces resulting from this inherent adaptation narrate the actions that transpired and the values that inspired them. By understanding authenticity within our surrounding as a continuous process rather than as an absolute original, not only will the various remnants that remain from this process be appreciated, new interventions that reflect present values will be also be encouraged. As a result, the act of ‘applied adaptation’, which encompasses all forms of contemporary interventions on existing sites, should be instructed by the process of inherent adaptation to ensure that a continuous narrative linking the traces of past adaptation and relevant contemporary innovation endures.


title: Does Architecture Dream of Upheaval?

abstract: An upheaval , where unsolicited violence has bloomed is a child to the social, political, and economic condition. It is neither a leader nor a follower. Upheaval expresses a different scenario that coexists within the larger cultural context; it re-examines the context it is situated in and generates new conditions. Upheaval demonstrates a collective behavior that is attempting to grab onto an alternative way towards the future. Considering the leading culture of architecture today, instead of preserving the loss, embracing the cycle of degeneration and regeneration as continuous events can result in an alternative strategy for architectural conservation. In the process of introducing such a concept, can architecture take the form of an upheaval, a radical break that resonates enough to generate shared emotions?


title: Local Architecture:  Using Traditional Persian Elements to Design for Climate in Yazd, Iran

abstract: The aim of this thesis is to research and study vernacular architecture in Yazd. Additionally, this study will explore the social and environmental bases of the traditional Yazdi house. In order to develop a cohesive understanding of contemporary issues in Iranian design, a variety of resource materials will be drawn on, including journal articles, reports, books, and field studies. The thesis will culminate in a project to design a large-scale master plan and schematic housing layouts for a residential complex at Yazd University that will house professors and their immediate family members.


title: Personality, performance, and the effects of stress on checkered pufferfish (Sphoeroides testudineus)

abstract: Few studies focus on the mechanisms that regulate consistent individual-level differences in behaviour (i.e., personality) in wild animals, despite their potential evolutionary and ecological implications. I examined whether wild checkered pufferfish (Sphoeroides testudineus) have consistent individual-level differences in locomotor activity, threat-response behaviour, swimming ability, and puffing performance. I also evaluated the relationships between these personality and performance traits. Personality and performance were compared to movements in the field. In addition, I tested whether a treatment of the stress hormone cortisol would alter personality and performance. Pufferfish exhibited personalities but these were not associated with performance or recapture in the field. Performance was consistent between the lab and the natural enclosure but activity was not. The cortisol treatment did not modify personality or performance, which suggests that these traits do not represent a stress-coping syndrome. I conclude by recommending future directions for research on stress and personality in wild animals.


title: Automation of the Cytokinesis-Block Micronucleus Assay Using Imaging Flow Cytometry for High Throughput Radiation Biodosimetry

abstract: The cytokinesis-block micronucleus (CBMN) assay is employed in biodosimetry to determine the dose of radiation to exposed individuals from the frequency of micronuclei (MN) in binucleated lymphocyte cells (BNCs). The assay is traditionally performed using a microscope-based scoring procedure which can be labour-intensive, time consuming and subject to variability of interpretation between scorers. This thesis investigates the feasibility of adapting the CBMN assay to an imaging flow cytometry method using the ImageStreamX (ISX) imaging flow cytometer and hypothesises that dose estimations can be obtained with adequate sensitivity for triage radiation biodosimetry. A protocol to perform the CBMN assay on the ISX along with a data analysis method using the Image Data Exploration and Analysis Software (IDEAS®) were developed. Using irradiated whole blood samples it was shown that the ISX-CBMN method could automatically image and enumerate BNCs and MN. Additionally, between 0-4 Gy the rate of MN per BNC follows a linear quadratic dependence with dose, similar to what is observed when performing the assay using traditional protocols. The ISX-CBMN method was then expanded into a multi-parameter radiation biodosimetry tool. Irradiated whole blood samples were analyzed using an optimized version of the IDEAS® analysis template which incorporated automated scoring of mononuclear cells (MNCs). Dose response calibration curves for the rate of MN per BNC, percentage of MNCs and the replication index (RI) were generated. Results indicated that this multi-parameter method may be able to provide dose estimations for individuals who have received a radiation dose of higher than 4 Gy. The traditional CBMN assay is limited by the large blood culture volume (500 µL - 2 mL) and the 72 h culture time. It was posited that the ISX-CBMN method could overcome both of these requirements and results showed that dose estimations could be generated to within 0.5 Gy of the delivered dose after only 48 h of culture time with an initial blood volume of 200 µL. The adaptation of the CBMN assay to an imaging flow cytometry method greatly increases its applicability in high throughput triage radiation biodosimetry.


title: Pop Up: A Deployable Brand in the Urban Fabric

abstract: This thesis responds to the constant change in the retail industry through the exploration of Pop-up structures. Although there are various ways a brand could connect to the public, Pop-up stores are found effective through its physical presence in cities. Temporary architecture has the flexibility to be assembled, interacted with, and relocated. The adaptability of temporal structure could apply to various forms of retailing, however this study will focus on specialty brands and leisure types. Traditional retail shops are not innovative, but the ability for a Popup to transform shape and change spatially according to program provides a new experience. This allows architecture as the main form of engagement. Through marketing strategies, retail branding, and the evolution of consumer culture, the thesis will apply written research into three architectural explorations. Each project will be placed in different scenarios, using the same deployable tactics to connect people, brand and the urban fabric.


title: Digital Regionalism: Identity, Place and the Ottawa Train Station

abstract: The Critical Regionalist ethos was born of a staunch distrust to the utopian visions of Internationalism, succeeding in a retreat back to an architecture of local identity. With the onset of the globalized 21st-century architecture practice, digital design tools have subsequently come to homogenize a transnational working methodology where the importance of regional peripheries is receding over time. This thesis questions the role of digital design and regionalism in contemporary architecture. How can architecture reconcile regional identity drivers with the increasing use of digital design tools for complex projects? This thesis uses a digital tool set to interpret natural wood phenomena that constitutes a novel design system. It expands the analysis to interpolate multidirectional patterns that otherwise go unseen. In doing so it reinterprets the genius loci of place for a contemporary digital regionalism. This thesis proposes an amalgamated transit terminal at the Ottawa Train Station.


title: Towards Deciphering Metamorphic Reaction Kinetics through Porphyroblastic Textural Analysis in the Bugaboo Contact Aureole (South Eastern British Columbia, Canada)

abstract: The relative rate of intergranular diffusion and interfacial attachment of chemical species during low-pressure metamorphic reactions is determined through analyzing the texture of porphyroblastic phases in the Bugaboo contact aureole. The observed mineral assemblages are predicted to be in equilibrium from 500-590°C at 1.60 kbar with graphite and a COH-bearing fluid. Porphyroblasts of Bt+And+Crd±Pl within the outer aureole display syn-kinematic growth textures while the inner aureole consists of pre-kinematic Bt+And+Crd+Kfs. Chemical homogeneity of Bt+Crd+prograde and retrograde Chl indicate retrograde chemical equilibration. Mineral chemistries therefore do not provide reliable P-T estimates for prograde metamorphism and the relative rate between reaction processes. The 3D spatial distribution of Bt+Crd from the outer aureole is obtained using XR-μCT to study the effects of metamorphic reaction processes on resultant porphyroblastic texture. Mineral texture is shown to be more reliable over mineral chemistry when deciphering the kinetics of metamorphic processes.


title: Verbs and Participants: Nonlinguists' Intuitions

abstract: Arguments and adjuncts play a crucial role in linguistic theories. Despite the vast body of research that assumes a distinction between arguments and adjuncts, not only in linguistics, but also in philosophy of language, psycholinguistics and neurolinguistics, there are no universally agreed-upon definitions distinguishing the two. The modest aim of this thesis is to investigate English speakers’ intuitions with respect to verbs and their arguments. To do so, the study makes use of the Core Participants Test, disguised in four different tasks, with each task eliciting, arguably, the same kind of intuitions. The results indicate that different tasks tap into either semantic or syntactic intuitions, or sometimes both. Overall, speakers' intuitions often matched linguists' views.


title: A Nation + Store Worth Saving: The Silenced Narrative of the Hudson's Bay Company

abstract: The Hudson Bay Company's (HBC) rich, abundant, and refined history has generally been narrated from none other but their own perspective, often failing to recognize the important and vital roles of their trading partners: the Aboriginal people. The Aboriginal people have a narrative of their ABSTRACT own, a bleak and silenced narrative highlighting their struggles, tensions, and setbacks. By understanding this silenced narrative of the HBC, it will consequently offer and inform new sets of values and beliefs. The focus of these investigations will be the adaptive re-use of The HBC department store in Winnipeg, MB, and how these new values and beliefs could inform a new architecture, giving way to an authentic Canadian identity making it - A Nation + Store Worth Saving.


title: I'm Still a Kid!: A Proposal for Improving Orphanages through the Integration of Nature, Nurture & The Senses

abstract: My thesis is concerned with how nurturing can be provided through integrating the senses into the architecture of an orphanage, by inviting the natural outdoor setting indoors, to inform the design. The design of a space that allows sensory stimulation and encounters with the environment is important to the well-being and healthy upbringing of children. An environment that encourages physical activity, playful sensory exploration, and a seamless relationship with the natural environment will be carefully integrated towards the design of a children's home in Santiniketan, India.


title: A Positive Prognosis for the Future of the Learning Environment: Designing Schools for Children in Shinabad, Iran

abstract: From 2004 to 2012, Iran experienced six large school fires that led to 51 injuries and five deaths. The tragedy of these injured kids inspired me to improve the conditions of learning for children living in rural conditions in Iran. Although what I offer here is a prototype, it can be hoped that it might serve as a model for improving safety standards in communities that have faced similar tragedies. I am addressing the problems to this community due to the typical school setting for Iran’s rural condition. Some of the ways in which architecture and design can help to ensure a positive prognosis for the future of learning environments in Iran is to create buildings that are good for both body and mind. Thus, this project aims to foster student learning and well being through architecture.


title: Living Heritage:  Re-imagining Wooden Crib Grain Elevators in Saskatchewan

abstract: This thesis explores the tangible and intangible cultural heritage of the wooden grain elevators in Saskatchewan. As wooden elevators become obsolete in the face of progressive agricultural technology, they are facing abandonment, and demolition. While these elevators were once purely functional structures, their unintentional monumentality has contributed to their relationship with Prairie people fostering identities. Wooden grain elevators are explored in the context of the past, present, and future using archival research, site visits, and interviews. A case study demonstrating the adaptive reuse of a wooden elevator is developed for Indian Head, SK. The concept of "living heritage" is employed to investigate the tangible and intangible cultural heritage associated with grain elevators as both theory and action—a way of thinking and a way of acting towards the past. This thesis substantiates the importance of wooden grain elevators to Prairie people and prescribes an architectural response for adaptive reuse.


title: Downtown: Re-imagining the Public Realm in the Toronto Financial District

abstract: Many of the public spaces of the Toronto Central Business District remain empty and dormant after office hours. While during the Monday to Friday workday, the streets are overcrowded and difficult to navigate, after office hours, they are depopulated and severely underused. In Toronto, about two hundred thousand people filter into the spaces of the Financial District every day. At the end of the business day the vast majority of them leave. With a unique blend of open spaces tucked in between super high towers, the CBD has the potential to offer a collection of public spaces that might not be found elsewhere in the city. Part One will focus on identifying this impoverishment, this lack of consistent social density in the CBD. Part Two will offer possible site-specific solutions to address these issues. By this we can hopefully re-imagine that part of the city with the public realm uppermost.


title: Model Based Penalized Smoothing for Panel Data Under a Markov Assumption

abstract: A flexible model for analyzing multi-state panel count data is presented. Panel data here refers to observing the state of individuals or objects under observation at a discrete set of time points. Panel data is found in many disciplines such as the sciences and medicine. It is assumed that the data is being generated by a continuous time, discrete state space Markov process. The transition intensities are represented with model-based penalty smoothing. This provides a class of models ranging between a fully nonparametric and parametric assumption for the transition intensities. Estimation and inference of the proposed approach is outlined and the finite sample properties of the methodology investigated via simulation.


title: Joint Cloud and Wireless Networks Operations in Mobile Cloud Computing Environments

abstract: Unlike most existing studies on wireless networks, where only the spectrum efficiency is considered, we consider not only the spectrum efficiency in wireless networks but also the pricing information in the cloud, based on which power allocation and interference management in the wireless networks are performed. We formulate the problems encountered in the operations of mobile cloud computing environments, including determining the price to charge for media services, resource allocation, and interference management, as a Stackelberg game model. Moreover, we extend this game model with multiple players through network virtualization technology, and adopt the replicator dynamics method to solve the evolutionary game between the different groups of small cells. Furthermore, a backward induction method is used to analyze the proposed Stackelberg game. Simulation results are presented to show the effectiveness of the proposed techniques.


title: On the Correction for Misclassification Bias in Electronic Health Data Using Validation Sample Approaches

abstract: Patient electronic health records (EHRs) are used to assess potential adverse drug reaction risk. These records are assumed to have perfect classification of the outcomes of interest, however, this assumption is not necessarily realistic. There are many reasons for outcome misclassification to be present in EHR data. Coding issues, diagnostic uncertainty (particularly relative to time), and misdiagnoses are causes this type of error. Unbiased estimation with outcome misclassification relies on the availability of additional information. We considered the use of internally validated data and demonstrated misclassification bias adjustment in binary and right censored continuous time survival data with and without the presence of competing risks. These data structures are investigated as they pertain to the underlying nature of EHR data. In misclassified binary data we considered the use of different sampling schemes for acquisition of the validation data. We first considered the estimated asymptotic relative efficiencies between the maximum likelihood estimators derived from these sampling approaches. Monte Carlo simulation demonstrated that the possibility of a minimal variance MLE relative to differing sampling schemes exists, however, the ability to assess this prior to sampling is not possible. We propose a numerical method that results in a validation sample size determination algorithm that can be used to approximate the relationship between sample size, variance of the estimator of the parameter of interest and chosen sampling approach. Finally, we considered methods of estimation used to assess association in a two-by-two contingency table such as the odds-ratio and logistic regression. For right censored continuous time survival data with and without competing risks, we proposed the use of internal validation to adjust for misclassification bias of two different types. First, we considered the problem of failing to observe the occurrence of an event of interest and incorrectly concluding that the individual under study is a censored observation. Second, we considered the situation in which we correctly observe an event occurrence, however erroneously observe the cause-specific event type. Under assumptions based on EHR data, using a multi-sample likelihood based approach we produced unbiased estimators for data with either form of error or both simultaneously being present.


title: Sedimentary and ecosystem response to Late Cretaceous (Cenomanian - Turonian) paleoenvironmental events along the eastern margin of the Western Interior Seaway, Canada.

abstract: During the Cretaceous Period, the Western Interior Seaway (WIS) was influenced by long-term and short-term environmental changes. Vertebrate bonebeds are particularly abundant within the Cenomanian-aged strata of the Western Interior Sedimentary Basin’s eastern margin. The major control for their accumulation is interpreted to be related to the timing and magnitude of sea-level fluctuations. Bioclasts are interpreted to be concentrated as lags along erosion surfaces during transgressions, while their taphonomic character is interpreted to be linked to the frequency of episodic events. In addition to these deposits, the uppermost Cenomanian to Turonian record along the eastern margin is characterized by rich planktic foraminiferal assemblages. Proximal and distal assemblages record a changing environment with frequent catastrophic perturbations including ashfalls and expansion of the oxygen minimum zone. Looking at both depositional and faunal responses to long- and short-term processes improves our understanding of the dynamics of the WIS during this enigmatic time.


title: Application of Adjoint Sensitivity Analysis for Performance Enhancement of Power Plants’ Nitrogen Oxides Control Policies

abstract: Significant investments in nitrogen oxide (NOx) emission controls in the U.S. have led to a substantial reduction in emissions. However, it is unclear whether these programs have optimally reduced ozone concentrations and their corresponding health damages. Current cap-and-trade program allocates emission quotas to participants and allows the trade of quotas on a one-to-one basis. However, it does not account for spatial and temporal differences in health damage of NOx emissions. This shortcoming in the current U.S. NOx control policy is explored in this research. Spatial and temporal differences in NOx emissions can be included in policy design if emission quotas are valued differently (exchange rate policy) or if polluters pay time- or location-specific emission fees (taxation policy). The main objective of this work is to develop a decision support system model for evaluating different policies. The proposed model includes an optimization platform to predict the polluters’ behavior, and an air quality model and its adjoint (or backward) sensitivity model to calculate the derivatives of the environmental or health damage function with respect to NOx emissions used for emission differentiations. The results from a case study of U.S. power plants show that exchange rate trading outperforms current indiscriminate trading policies. These findings imply that by implementing exchange rate trading or taxation policies, current improvements in air quality could have been achieved at lower costs, or alternatively, more substantial improvements could have been reached at little to no additional costs. Furthermore, the results indicate that setting the emission fees on an hourly basis leads to a outcome comparable to setting fees based on location. Moreover, the per ton health benefit of NOx emission reductions is found to increase as emissions are reduced. This finding is particularly important from an environmental policy perspective as it impacts the optimal NOx emission reduction target. Our results also indicate that power plants in the restructured electricity market are willing to pay more for emission quotas. Uncertainties involved in the proposed model, challenges for implementation of the proposed policies, and inclusion of health impacts caused by exposure to particulate matter are main directions for future research.


title: Masters of Uncertainty: Social Scares and the Politics of Change in Energy Policy

abstract: Social scares are periods triggered by a spectacular, deadly, traumatizing, or otherwise disruptive event. The event produces a sudden, broadly shared perception of insecurity that brings an area of activity to the forefront of public and political attention. In these instances, leading political figures must strike a balance between two objectives: appearing as good leaders to temper the insecurity felt by large segments of their population; and obtaining a policy outcome they are comfortable with. This balancing act is no easy task, as the context forces government actors to “do something”, which may lead to policy changes unattractive to them. Nevertheless, leaders who perform well regarding the first objective win a prize consisting of a bulk of symbolic capital, by being perceived as reducing the perception of insecurity. This is how social scares differ from the policy process during other periods: actors who capture a large such prize in the first days and weeks of a scare possess a formidable resource in the battle over potential policy changes, as this bulk of symbolic capital can tilt the balance to their favor, even if other coalitions and actors have substantial resources. Hence the form that the policy process takes in the aftermath of a scare results from the combination of the obligation for actors in power to act convincingly, of the constraints that this obligation imposes on them, and of the clashing sets of interests that the different groups have regarding the policy options. Focusing on scares related to the energy sector, this dissertation shows how this two-dimensional battle is shaped by four aspects: the triggering event and the first prize that emerges from it; the strategies and actions of the actors regarding the two objectives; the framing of uncertainty and risk, and the role played by experts; and the impact of contextual factors, in particular the election timing and the regime type. By using these as broad investigative questions within the method of structured, focused comparison, the model allows for a better understanding of the political battles that occur while societies progressively return to a more normal state of affairs.


Money in economic development:  The Ecuadorian case


Optical properties of a five-layer slab with long-period gratings


The legacy of scientific motherhood : doctors and child-rearing advice in the 1960s and 1970s in English Canada


An inquiry concerning the world-picture: Kojève, Schmitt and Strauss


title: 3D Laser Imaging and Modeling of Iron Meteorites and  Tektites

abstract: 3D laser imaging is a non-destructive method devised to calculate bulk density by creating volumetrically accurate computer models of hand samples. The focus of this research was to streamline the imaging process and to mitigate any potential errors. 3D laser imaging captured with great detail (30 voxel/mm2) surficial features of the samples, such as regmaglypts, pits and cut faces. Densities from 41 iron meteorites and 9 splash-form Australasian tektites are reported here. The laser-derived densities of iron meteorites range from 6.98 to 7.93 g/cm3. Several suites of meteorites were studied and are somewhat heterogeneous based on an average 2.7% variation in inter-fragment density. Density decreases with terrestrial age due to weathering. The tektites have an average laser-derived density of 2.41+0.11g/cm3. For comparison purposes, the Archimedean bead method was also used to determine density. This method was more effective for tektites than for iron meteorites.


The Young Women's Christian Association in Canada, 1870--1920: "A movement to meet a spiritual, civic and national need"


Asphalt concrete characterization using the complex modulus technique


An approach for building and evaluating performance models for component based systems


title: Search for Electroweak SUSY Signatures with Two Leptons and Missing Energy with the ATLAS Detector

abstract: The ATLAS experiment at the Large Hadron Collider (LHC) has collected significant amounts of proton-proton (pp) collision data from 2010 until 2012. These data have allowed the discovery of a new boson consistent with the one postulated by the Higgs' theory, and also enabled to look for hints of new physics beyond the Standard Model (SM). Supersymmetry (SUSY) is an extension of the SM that introduces a symmetry between fermions and bosons. Its signatures are expected to be detectable at the LHC, should it be the true extension to the SM, and the ATLAS experiment offers a dedicated programme to search for such signatures. This thesis presents the analysis and results for the search for SUSY produced from electroweak interactions resulting in two final-state leptons and some missing energy. The full 2012 dataset is used for the analysis, corresponding to 20.3 fb^{-1} of pp collisions at the centre-of-mass energy of \sqrt{s} = 8 TeV. The overall methodology to identify these SUSY signatures is given, with emphasis on the optimization of the SUSY discovery signal region definitions and statistical interpretation of the results. No significant excess of events above the SM prediction is observed in the signal regions. Therefore, the final result is interpreted by means of statistical tests designed to exclude regions of parameter space of specific SUSY models. For this thesis, the phenomenological Minimally Supersymmetric Standard Model (pMSSM) is tested, and exclusion limits are set on gaugino mass parameters (M_2 and mu). The exclusion regions are expanded since the previously published results based on the LHC 7 TeV collision data. By combining these results with those from searches with trilepton final states, the exclusion regions are further expanded, giving the strongest limits on the gaugino mass parameters to date.


Estimation of 3-D reactivities of volatile organic compounds using adjoint sensitivity analysis


Development of GPS-based procedure for tracking vehicle path


Information processing speed in adults with ADHD


Ernest Buckler's The Mountain and the valley; an examination of the development of the character of David Canaan.


title: Modelling and Synthesis of High Speed Craft Acceleration Profiles

abstract:
High Speed Craft (HSC) occupants are subjected to a harsh environment characterized by vibration and repeated shock. Significant research has therefore been invested into HSC shock mitigation. The objective of this work was to determine standard shock acceleration profiles for HSC based on sea trial data. The knowledge of real-life sea inputs is important for in-lab testing of HSC shock mitigation seats. Sea trial vertical acceleration data of a Rigid-Hull Inflatable Boat was analyzed with the aim of characterizing shock acceleration pulses experienced by the boat. Five common types of shock
acceleration profiles were identified. These profiles were represented by a combination of modified Gaussian curves. The statistical characteristics of the observed pulses were obtained by curve fitting the data. An algorithm employing copulas and non-parametric density estimation was developed for generating synthetic time histories which have the same statistical characteristics as the observed data.


The role of women in the survival of Catholicism in post-reformation Lancashire and Yorkshire, 1559-1603


Legalizing the imagination : an examination of how the geographic imagination of the new world led to its construction as free space within international law for the purpose of the English appropriation of North America


Military culture and conflict resolution: a case study of the Rwandan defence forces


Making meaning of racial cosmetic surgery : its implications and effects on the lives of women in America


Intruder capture by mobile agents in mesh topologies


Creations and destroyings: the self-genesis of John Keats.


The effect of driving conditions and ambient temperature on particulate matter emission rates and size distributions from light duty gasoline-electric hybrid vehicles


title: Experimental and Numerical Simulation of Stress Distribution in Landfills

abstract:
This thesis conceptually illustrates stress distribution within landfills by hypothesising the concept of a “hard inclusion”. It was demonstrated, via laboratory experiments and numerical modelling, that the concept of a “hard inclusion” may be partially responsible for elevated stresses measured by Total Earth Pressure Cells (TEPCs) installed within waste in landfills during previous studies as well as horizontal pipe collection/recirculation systems. The high failure rate in horizontal collection systems in engineered landfills and horizontal gas and leachate collection and leachate
recirculation systems in bioreactor landfills may be partially attributed to high contrasts in moduli between the bedding material surrounding the pipe collection/recirculation systems and the waste. Similar contrasts in moduli can explain elevated stress measurements obtained by TEPCs to date. It is important to understand the stress distribution in landfills to help landfill designers in the design of collection/recirculation systems.


title: Exploring Source Routing as an Alternative Routing Approach in Wide Area Software-Defined Networks

abstract:
Software-Defined Networking has been gaining increasing attention in both research and industry communities. Separating the control and data planes has brought many advantages such as greater control plane programmability, more vendor independence, possibility of network virtualization, and lower operational expenses. SDN deployments are possible in a variety of contexts: Enterprise networks, Datacenter networks, and WANs. However, SDN raises several concerns for WANs including performance limitations due to the larger propagation delays, the increased controller work load due to a larger
number of network elements, and concerns about performance impacts of the controller placement.
This study attempts to address some of these issues by examining the effects of using source routing as an alternative to traditional distributed routing in SDN-based WANs. Our simulations and analysis show that source routing can bring significant gains in SDN performance in WANs, improve network scalability, and reduce network performance sensitivity to controller placement.


The cost efficiency of intercity rail and bus transportation in the Quebec City - Windsor corridor.


"A la turca" ways in neo-liberal times: a political economy of Turkey's new state spaces


An investigation of the extent of the fresnel region of aperture antennas with attention to superdirectivity.


title: Small-signal Stability Analysis and Power System Stabilizer Design for Grid-connected Photovoltaic Generation System

abstract:
Solar energy is one of the emerging forms of renewable energy, and has been proved to be a potential source for generation of electricity. However, the rise in number of photovoltaic (PV) generators presents issues for electric power utilities. The objective of this thesis is to achieve stability for a grid-connected PV system with the proposed new power system stabilizer (PSS). Stability is attained by conducting small signal analysis and time domain analysis on the investigated PV system. First, time domain analysis on detailed and average PV system models without PSS is performed. Second,
small signal stability analysis on average PV system model with and without PSS is performed. It is observed that the damping effect and the dynamic stability of the investigated PV system are achieved, with the help of the proposed new PSS.


title: Investigation of the Effects of an Upstream Cavity on the Secondary Flow in Transonic Turbine Blade Passages with Endwall Contouring

abstract:
The investigation documented here aims to contribute to the understanding of secondary flows in modern high-pressure (HP) turbine blade passages. More specifically, it aims to improve the understanding of vortical structures near the endwall with respect to the presence of an upstream cavity that approximates the gap present in actual engines between the rotor and stator of an HP turbine. Further, it aims to assess the viability of using non-axisymmetric endwall contouring to reduce endwall losses, including those generated by the presence of an upstream cavity, using a modern airfoil, at HP
turbine representative speeds and at off-design Mach numbers.
To attempt to achieve this, a combination of flow measurement, flow visualization, and computational fluid dynamics (CFD) with linear turbine cascades was used. The test matrix consisted of three cases all with one common blade cascade geometry (SL2P). SL2P was combined with one of three endwalls: a baseline flat endwall, a flat endwall with a cavity incorporated upstream of the blade row, and a contoured endwall with the same upstream cavity geometry. A combination of pressure probes, pressure taps, and flow visualization were
used to collect quantitative and qualitative data in a blow-down type wind tunnel. Complementary CFD studies were also carried out using the commercial CFD code ANSYS CFX.


Steppe-ing forward? Mongolia, mining, and the resource curse


title: Obstacle Detection Using Monocular Camera for Low Flying Unmanned Aerial Vehicle

abstract:
This thesis describes the research of an obstacle detection system for
a low flying autonomous unmanned aerial vehicle(UAV). The system
utilized an extended Kalman filter based simultaneous localization and
mapping algorithm which fuses navigation measurements with monocular
image sequence to estimate the poses of the UAV and the positions of
landmarks.
To test the algorithm with real aerial data, a test flight was
conducted to collect data by using a sensors loaded simulated unmanned
aerial system(SUAS) towed by a helicopter. The results showed that the
algorithm is capable of
mapping landmarks ranging more than 1000
meters. Accuracy analysis also showed that SUAS localization and
landmark mapping results generally agreed with the ground truth.
To better understand the strength and weakness of the system, and to
improve future designs, the algorithm was further analyzed through a
series of simulations which simulates oscillatory motion of the UAV,
error embedded in camera calibration result, and quantization error
from image digitization.


The emergence and establishment of psychoanalysis in Argentina : an examination of the pre-Freudian and early Freudian periods


Mapping disasters; the application of a disaster-sociological 'Theoretical superstructure' and methodology in a Prima Facie case for investigating the role of hepatitis B vaccines in the contamination of the Canadian blood supply with human immunodef


title: Between Dominance and Demise: The Revitalization of the Former St. Mary's Paper Mill

abstract: Between Dominance and Demise speaks of the industrial ruin as an entity that is in the state of the in-between, which will be elaborated in this thesis. Due to the inevitability of immense changes in technological advancements, the industrial complex is suspended from regular activity. Such an uncertain position is considered to be in a state of transformation for both the physical construct and the community to which it pertains. For many communities, the struggles of adapting to the uncertainty of the post-industrial landscape can often inhibit their regeneration. Consequently, these landscapes are often replaced by contemporary modes of construction that do not consider the past or remain vacant. How do we maintain connections to our industrial heritage, to the memory of place, if it no longer appears to be embedded in the social and physical networks of the surrounding communities?


title: The Design of an Optical Switch Based on Dinuclear Ruthenium Pentaammine Dicyanamide Complexes

abstract:
A novel photochromic polymer (SP-PS) with a polystyrene (PS) backbone linked to spiropyran (SP) by alkyl chain was synthesized (4% yield). Ultraviolet irradiation of SP-PS induces photoisomerization from SP to merocyanin (MC); back-reaction occurs thermally or by visible irradiation. SP-PS was characterized by 1H-NMR spectroscopy, differential scanning calorimetry and gel permeation chromatography. The Tg and Mn were determined to be 118.41 °C and 63,980 g/mol ± 1.731% (Đ=1.24), respectively. Φ365 nm for SP-MC photoisomerization was 0.80 after 5 s (toluene). When SP-PS is combined with
[{Ru(NH3)5}2(μ-dicyd)][BPh4]4, (dicyd2- = dicyanamido benzene dianion), a near-infrared photoswitchable material results.
Interaction between MC and [{Ru(NH3)5}2(μ-dicyd)][BPh4]4 was observed through comparison of MC-SP photoisomerization rates. Thin films of [{Ru(NH3)5}2(μ-dicyd)][BPh4]4 in polystyrene displayed unique photochemistry; 30 s of 523 nm irradiation by light-emitting diode reduced ligand-to-metal charge transfer band absorbance by 70% with 82% recovery after 46h. The mechanism of this effect remains to be determined.


Environmental racism discourse and indigenous peoples


A DNS study on the effects of streamwise convex surface curvature on coherent structures in turbulent boundary layers


The stigma of mental illness: an inquiry into the Toronto Mental Health Court and wheather it reduces the stigma of mental illness for those accused of crimes


title: Behaviour of sensitive Leda clay under simple shear loading

abstract: An experimental investigation was conducted on sensitive Leda clay from Ottawa area using simple shear device. Both small strain and large strain tests were conducted. Carleton University simple shear device was improved to measure shear properties at small strain amplitudes. Strength tests at large strain levels indicate that Leda clay might reach a steady state during monotonic loading. Under cyclic loading, the clay deformed with progressively increasing cyclic strain. Liquefaction becomes a concern when cyclic stress exceeds at least 60% of their monotonic undrained strength. Few small amplitude cycles do not produce significant strength loss. Successful application of small strain quasi cyclic tests proved to be an optimum means of obtaining modulus and damping data in laboratory. Material specific modulus reduction and damping ratio curves are presented for Ottawa area Leda clay. Results show that behaviour of sensitive clays is not similar to that of typical non sensitive clays.


Working memory and solution procedures for single-digit subtraction and multiplication


Central Asian bolsheviks: mediating revolution, 1917-24


Soft decision decoding for binary linear codes.


title: Permafrost and Thermokarst Lake Dynamics in the Old Crow Flats, Northern Yukon, Canada

abstract: Aspects of the thaw lake cycle were investigated in Old Crow Flats (OCF), a 5600 km2 peatland with thousands of thermokarst lakes in the continuous permafrost of northern Yukon. It is located in the traditional territory of the Vuntut Gwitch'n, who expressed concern that climatic change may be affecting the permafrost and lakes of OCF. Field data collected in 2008-2011 provided the first assessment of spatial variability in permafrost temperatures across the treeline ecotone in OCF. Lake-bottom temperatures were recorded near the shores of four thermokarst lakes and talik configuration was defined beneath the lakes by jet-drilling to determine conditions controlling permafrost degradation in the area. Analytical and thermal models were used to relate field observations to current theory. Surface and subsurface conditions were examined in three drained lake basins and four expanding lakes to investigate how shore recession, talik development, and sediment deposition during lake expansion control the topography in lake basins after drainage. Permafrost temperature at the depth of zero annual amplitude varied between -5.1ºC and -2.6ºC on the Flats. Within the forest-tundra transition, spatial variability in permafrost temperatures appeared to be controlled by the snow-holding capacity of vegetation and the configuration of land covers in the surrounding landscape, which controlled snow supply. Annual mean lake-bottom temperatures close to shorelines were unaffected by spatial variations in on-ice snow depth, but accumulation of freezing degree-days at the lake bottom varied sufficiently to affect rates of permafrost degradation beneath the lake. Where ice reached the lake bottom, talik development rates were controlled by the ratio of freezing degree days to thawing degree days and the thermal offset in the lake sediment. After lake drainage and permafrost aggradation, thermokarst lake basins in OCF commonly develop depressed margins and raised centres. An elevation difference of up to 2 m was recorded between the margins and centres of drained basins, but this elevation difference was not associated with increased ice-wedge density or increased segregated ice content. A conceptual model based on sediment deposition patterns during lake expansion was proposed to explain the topography of drained lake basins in OCF.


Governing women's sexuality in Sex and the City: pleasure, relationships and reproduction


title: Mixed Valency in Dinuclear Ruthenium Complexes Bridged by Tetrazine- and Azo-Cyanamide Ligands

abstract: The novel [Ru(II),Ru(II)] dinuclear complex [{Ru(bpy)(ttpy)}2(µ-tdpc)][PF6]2, where ttpy: 4-(tert-butylphenyl)-2,2′:6′,2″-terpyridine, bpy: 2,2′-bipyridine and tdpc2- is 3,6-bis(phenylcyanamido)-1,2,4,5-tetrazine, was synthesized and characterized by elemental analysis, 1H-NMR, IR and UV-Vis spectroscopies. Analysis of the cyclic voltammetry data combined with spectroelectrochemistry results indicates the [Ru(II),Ru(III)] complex is a weakly coupled Class II system. These results were compared against the properties of the strongly coupled Class II complex, [{Ru(bpy)(trpy)}2(µ-adpc)]3+, where trpy: 2,2′:6′,6″-terpyridine and adpc2-: 4,4′-azodi(phenylcyanamide). DFT calculations of the free ligands and mixed-valence complexes suggest that metal-metal coupling primarily occurs via the hole-transfer mechanism. Two dinuclear complexes, [{Ru(bpy)2}2(µ-adpc)2] and [{Ru(bpy)2(dmso)}2(µ-adpc)][PF6]2 where dmso: dimethylsulfoxide, were synthesized and characterized by elemental analysis, 1H-NMR and UV-Vis spectroscopies. Spectroelectrochemistry studies showed delocalized metal-ligand mixed-valence Class II description for [{Ru(bpy)2}2(µ-adpc)2]+. The [{Ru(bpy)2(dmso)}2(µ-adpc)][PF6]2 complex exhibits photo-induced Ru-S to Ru-O and thermal Ru-O to Ru-S linkage isomerism in DMSO solution. DFT calculations suggested the non-innocent behavior of phenylcyanamide ligand in both complexes.