Physical Sciences and Mathematics Commons^™

Characterization Of Kelyphite Rims: Relevance To Diamond Exploration, Mallory N.G. Metcalf

Electronic Thesis and Dissertation Repository

A detailed investigation into the mineralogy and chemistry of kelyphitic rims/veins on garnets was conducted using µXRD, EPMA and Raman spectroscopy for a suite of samples from economic and non-economic kimberlites in Canada and South Africa. Mineralogy demonstrates the influence of metasomatic fluids during the reactions which produced kelyphite in all localities and was used to propose P-T regions where kelyphite could have formed. Using chemical analyses of host garnets and the mineralogy obtained for kelyphite, modified chemical reactions representing Types 1 and 2 kelyphite are provided to describe kelyphite reactions in open systems. Elastically-strained secondary garnet is common in …

Impact Craters On Titan: Finalizing Titan's Crater Population, Joshua E. Hedgepeth

Electronic Thesis and Dissertation Repository

Titan is one of the most dynamic moons in the solar system. It is smaller than Earth and much colder, yet Titan is eerily similar to Earth, with rivers, rain, and seas, as well as sand seas that wrap around the equator. However, the rivers are made of hydrocarbons rather than water and the sand made of organics rather rock. We can use Titan’s impact craters to study how these processes modify the surface by comparing the craters depths, diameters and rim heights of Titan’s craters with fresh craters. Therefore, we have used the complete data set from NASA’s Cassini …

Syzygy Order Of Big Polygon Spaces, Jianing Huang

Electronic Thesis and Dissertation Repository

For a compact smooth manifold with a torus action, its equivariant cohomology is a finitely generated module over a polynomial ring encoding information about the space and the action. For such a module, we can associate a purely algebraic notion called syzygy order. Syzygy order of equivariant cohomology is closely related to the exactness of Atiyah-Bredon sequence in equivariant cohomology. In this thesis we study a family of compact orientable manifolds with torus actions called big polygon spaces. We compute the syzygy orders of their equivariant cohomologies. The main tool used is a quotient criterion for syzygies in equivariant cohomology. …

Design, Synthesis, And Oxidation Reactivity Of Palladacyclic Complexes Containing N-Donor Ligands, Ava Behnia

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and reactivity of complexes containing the cycloneophyl-Pd(II) group, PdCH₂CMe₂C₆H₄, in combination with N-donor ligands. These compounds contain both alkyl- and arylpalladium bonds and the selectivity of bond cleavage in reactions with oxidants and protic reagents is studied, often involving oxidative addition and reductive elimination reaction sequences.

The diimine ligand in [Pd(CH₂CMe₂C₆H₄)(MesN=CH-CH=NMes)] does not support formation of stable palladium(IV) complexes, but reactions with Br₂ or I₂ lead to reductive elimination by C-C bond formation of 1,1-dimethylcyclobutabenzene while …

Geomechanical Modelling Of Induced Seismicity, Bodi Zhao

Electronic Thesis and Dissertation Repository

In recent years, there has been a dramatic increase in seismicity (earthquakes) due to anthropogenic activities related to the unconventional oil and gas exploration in the Western Canada Sedimentary Basin (WCSB) and the central U.S. There are compelling evidences that hydraulic fracturing and wastewater injection operations in those areas play a key role in induced seismicity. To better understand the physical mechanisms involved, this thesis aims to explore the mechanisms responsible for occurrence of induced earthquakes: mainshock-aftershock triggering mechanism and poroelastic response. In the first approach, the obtained results indicate the relationship between the Coulomb stress changes after 4 moderate …

Compositional Variations Of Titan's Impact Craters Indicates Active Surface Erosion, Alyssa Werynski

Electronic Thesis and Dissertation Repository

Impact craters on Titan are relatively scarce, but provide ample information about the subsurface properties and modification processes present there. This study utilizes impact craters to examine compositional variations across Titan’s surface and their subsequent modification. Fifteen craters and their ejecta blankets were studied. Subsurface composition was inferred from emissivity data from Cassini’s RADAR instrument, and surficial composition from Cassini’s Visible and Infrared Mapping Spectrometer (VIMS). Results show subsurface composition of these craters is controlled by their degradation state and local environment. Older craters are more infilled with organics than younger, and dunes craters show more organic enrichment than plains …

Effects Of High Pressure On Photochemical Reactivity Of Organic Molecular Materials Probed By Vibrational Spectroscopy, Jiwen Guan

Electronic Thesis and Dissertation Repository

Chemical transformations of molecular materials induced by high pressure and light radiation exhibit novel and intriguing aspects that have attracted much attention in recent years. Particularly, under the two stimuli, entire transformations of molecular species can be realized in condensed phases without employing additional chemical constraints, e.g., the need of solvents, catalysts or radical initiators. This new synthetic approach in chemistry therefore satisfies increasing need for production methods with reduced environmental impacts. Motivated by these promises, my Ph. D thesis focuses on this state-of-the-art branch of high-pressure photochemistry. Specifically, high pressure is employed to create the necessary reaction conditions to …

The Statistical Exploration In The $G$-Expectation Framework: The Pseudo Simulation And Estimation Of Variance Uncertainty, Yifan Li

Electronic Thesis and Dissertation Repository

The $G$-expectation framework, motivated by problems with \emph{uncertainty}, is a new generalization of the classical probability framework. Similar to the Choquet expectation, the $G$-expectation can be represented as the supremum of a class of linear expectations. In the past two decades, it has developed into a complete stochastic structure connected with a large family of nonlinear PDEs. Nonetheless, to apply it to real-world problems with uncertainty, it is fundamentally necessary to build up the associated statistical methodology.

This thesis explores the \emph{computation, simulation, and estimation} of the $G$-normal distribution (a typical distribution with variance uncertainty) by constructing a new substructure …

Computational And Spectroscopic Studies In The Design Of Tetrapyrrole Dyes For Dye-Sensitized Solar Cells, Angel (Qi Wen) Zhang

Electronic Thesis and Dissertation Repository

Cyclic tetrapyrroles, like porphyrins, phthalocyanines, and chlorins, are of great interest for dye-sensitized solar cell (DSSC) applications due to their highly versatile structure, tunable π based spectroscopic and electrochemical properties, and excellent stabilities. As well, they have a structural analogy with chlorophyll, a natural photosensitizer. Chlorophylls exhibit a red and intense lowest energy absorption band that is one of the ideal properties of a dye for application in DSSCs. However, because chlorophylls are unstable, it is necessary to design similar but more stable tetrapyrroles with these ideal properties. The relationship between chlorophyll’s geometric structure and spectral properties were first explored …

Synthesis Of 2-Thiouracil And 2-Thiothymine Peptide Nucleic Acid Monomers Compatible With Fmoc-Based Oligomerization, Timothy Martin-Chan

Electronic Thesis and Dissertation Repository

Pseudo-complementary nucleobases are modified nucleobases which exhibit normal base pairing with unmodified complementary nucleobases; however, will not undergo stable base pairing with other pseudo-complementary nucleobases. The pseudo-complementary nature of these bases is of interest for the synthesis of pseudo-complementary peptide nucleic acid (pcPNA) oligomers, which are capable of binding targets in double-stranded DNA through a double duplex strand invasion. Until recently, pcPNAs were synthesized via Boc-based oligomerization chemistry which is currently less popular than the Fmoc-based strategy.

This research describes the development of a Fmoc protected thiouracil PNA monomer with an acid labile protecting group for use in standard SPPS. …

Impact Melt Emplacement On Mercury, Jeffrey Daniels

Electronic Thesis and Dissertation Repository

Impact cratering is an abrupt, spectacular process that occurs on any world with a solid surface. On Earth, these craters are easily eroded or destroyed through endogenic processes. The Moon and Mercury, however, lack a significant atmosphere, meaning craters on these worlds remain intact longer, geologically. In this thesis, remote-sensing techniques were used to investigate impact melt emplacement about Mercury’s fresh, complex craters. For complex lunar craters, impact melt is preferentially ejected from the lowest rim elevation, implying topographic control. On Venus, impact melt is preferentially ejected downrange from the impact site, implying impactor-direction control. Mercury, despite its heavily-cratered surface, …

The Development Of Platforms For Inhibiting Rhamm-Ha Interactions & The Development Of An Optical Probe For Measuring Glomerular Filtration Rate, Alexandra Hauser-Kawaguchi

Electronic Thesis and Dissertation Repository

Carbohydrates are a class of molecule occurring widely in the body. Their presence has varied biological implications, generating clinical interest regarding their impact on disease prognosis. This thesis will investigate the development of chemical entities surrounding two carbohydrates, hyaluronan and inulin.

The Receptor for hyaluronan mediated motility (RHAMM) is one of several receptors for hyaluronan (HA), a polysaccharide that, when fragmented, has pro-angiogenic and inflammatory properties. RHAMM expression is tightly regulated during homeostasis but increases in response to cellular stress, including during injury or disease states. HA-RHAMM interactions stimulate the Ras-ERK-Mek pathway to promote cell motility, differentiation, and proliferation. Specific …

Coinage Metal Chalcogenide Clusters With N-Heterocyclic Carbene Ancillary Ligands, Alex Polgar

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. …

Stochastic Modelling Of Implied Correlation Index And Herd Behavior Index. Evidence, Properties And Pricing., Lin Fang

Electronic Thesis and Dissertation Repository

In this work, we provide the definition, study properties, and craft new stochastic models for two dependence indices: the implied correlation index and the herd behavior index (HIX). In particular, we model and price financial derivatives on the basic implied correlation index (CIX) as reported by CBOE. Our analysis is the first revealing the presence of heteroscedasticity in the time series of CIX leading to two Correlation Stochastic Volatility (CSV) models. We describe properties of CSV models and use discretization methods for their simulation. A partial estimation methodology is implemented on CBOE S& P 500 CIX historical data treating the …

From Large-Scale Molecular Clouds To Filaments And Cores : Unveiling The Role Of The Magnetic Fields In Star Formation, Sayantan Auddy

Electronic Thesis and Dissertation Repository

I present a comprehensive study of the role of strong magnetic fields in characterizing the structure of molecular clouds. We run three-dimensional turbulent non-ideal magnetohydrodynamic simulations (with ambipolar diffusion) to see the effect of magnetic fields on the evolution of the column density probability distribution function (PDF). Our results indicate a systematic dependence of the column density PDF of molecular clouds on magnetic field strength and turbulence, with observationally distinguishable outcomes between supercritical (gravity dominated) and subcritical (magnetic field dominated) initial conditions. We find that most cases develop a direct power-law PDF, and only the subcritical clouds with turbulence are …

Finding Nonlinear Relationships In Functional Magnetic Resonance Imaging Data With Genetic Programming, James Hughes

Electronic Thesis and Dissertation Repository

The human brain is a complex, nonlinear dynamic chaotic system that is poorly understood. When faced with these difficult to understand systems, it is common to observe the system and develop models such that the underlying system might be deciphered. When observing neurological activity within the brain with functional magnetic resonance imaging (fMRI), it is common to develop linear models of functional connectivity; however, these models are incapable of describing the nonlinearities we know to exist within the system.

A genetic programming (GP) system was developed to perform symbolic regression on recorded fMRI data. Symbolic regression makes fewer assumptions than …

Local Higher Category Theory, Nicholas Meadows

Electronic Thesis and Dissertation Repository

The purpose of this thesis is to give presheaf-theoretic versions of three of the main extant models of higher category theory: the Joyal, Rezk and Bergner model structures. The construction of these model structures takes up Chapters 2, 3 and 4 of the thesis, respectively. In each of the model structures, the weak equivalences are local or ‘stalkwise’ weak equivalences. In addition, it is shown that certain Quillen equivalences between the aforementioned models of higher category theory extend to Quillen equivalences between the various models of local higher category theory.

Throughout, a number of features of local higher category theory …

Optimization Studies And Applications: In Retail Gasoline Market, Daero Kim

Electronic Thesis and Dissertation Repository

The study of the retail gasoline market is of great interest in financial economics, since it allows many theories about price formation, oligopolistic markets, and consumer search to be tested. In addition, the risk management of gasoline prices is an important instance of the management of any consumable commodity cost. For the retailer, the tool of dynamic pricing may be found to be useful.

This thesis contributes to the study of retail gasoline markets in three main ways, each in its own paper. The first paper tests various economic models to confirm earlier results about pricing behavior in retail gasoline …

Baseline Assisted Classification Of Heart Rate Variability, Elham Harirpoush

Electronic Thesis and Dissertation Repository

Recently, among various analysis methods of physiological signals, automatic analysis of Electrocardiogram (ECG) signals, especially heart rate variability (HRV) has received significant attention in the field of machine learning. Heart rate variability is an important indicator of health prediction and it is applicable to various fields of scientific research. Heart rate variability is based on measuring the differences in time between consecutive heartbeats (also known as RR interval), and the most common measuring techniques are divided into the time domain and frequency domain. In this research study, a classifier based on analysis of HRV signal is developed to classify different …

Sedimentology And Stratigraphy Of The Upper Cretaceous Puskwaskau Formation In North-Central Alberta, Western Canada Foreland Basin, Omar Al-Mufti

Electronic Thesis and Dissertation Repository

The Santonian to early Campanian mudstone-dominated Puskwaskau Formation was correlated throughout a study area of 50,000 km² in north-central Alberta using 988 well logs. Fourteen informal allomembers, established by previous studies, are bounded by regionally-mappable marine flooding and/or transgressive surfaces that are traceable for hundreds of kilometres within the study area. These laterally continuous bounding surfaces are parallel to very gently converging, and mostly terminate by onlap onto underlying surfaces. Observations in thin section and in SEM revealed ten mudstone microfacies, grouped into five microfacies associations. The facies preserve evidence for repeated storm-generated reworking of the seafloor. The Puskwaskau …

The Incorporation Of Phosphorus Into Block Copolymers And Their Self-Assembly, Benjamin F. Hisey

Electronic Thesis and Dissertation Repository

The content of this thesis focuses on the incorporation of phosphorus into amphiphilic block copolymers (BCPs) for the realization of novel properties in the solution phase self-assembled materials derived from the BCPs. The incorporation was achieved through either attaching phosphorus to the terminus of already existing BCPs or the synthesis of novel BCPs from prepared or commercially available phosphorus containing monomers. The phosphorus containing polymers exhibited properties dependent on the existence of the phosphorus species in the BCPs. The first example of this is the modification of poly(ethylene oxide)-b-poly(ε-caprolactone) (PEO-b-PCL) copolymers by the attachment of tetraalkyl …

Defect-Related Magnetic Properties Of Nanostructured Nickel Oxide Thin Films For Solar Cell Applications, Angela E. Ezugwu

Electronic Thesis and Dissertation Repository

Transparent conducting oxides (TCOs) are extensively investigated because of their applications as transparent electrodes in solar cells and light-emitting devices. TCOs of interest include indium-tin oxide, aluminum-doped zinc oxide, nickel oxide (NiO), and their combinations. There is strong interest in NiO because no heteroatoms are required to “dope” it at high transparency levels. It has been speculated that paramagnetic defects due to Ni³⁺ centers and O interstitials are responsible for the electrical conductivity of otherwise insulating and antiferromagnetic NiO, but direct investigation of such defects has been limited. Here, the electrical conductivity in nanostructured NiO thin films is investigated …

Microclimate Variability Of Select Toronto Neighbourhoods Under Hot Summertime Conditions, Timothy Wiechers

Electronic Thesis and Dissertation Repository

Micrometeorological variability within cities has important implications for urban air and water quality, building energy consumption, and human health and thermal comfort. However, the monitoring of microscale climate is not routinely conducted. In most instances, primary meteorological observations are made under reproducible standard conditions (typically at an airport); but these open field observations tend to be unrepresentative of the intra-urban meteorological conditions.

This thesis used an alternative approach of conducting mobile traverse measurements using vehicle-mounted sensors to characterize the microclimates of Toronto, ON under hot, summertime weather conditions. Sampling occurred along two routes and incorporated sampling 8 intra-urban neighbourhoods with …

Total Synthesis Of (±)-Isodihydrokoumine, (±)-(19z)-Taberpsychine, And (±)-Isodihydroukoumine N4 Oxide, Jeff Kerkovius

Electronic Thesis and Dissertation Repository

We report the total synthesis of the natural products (±)-isodihydrokoumine, and (±)-(19Z)-taberpsychine in 11 steps each, and (±)-isodihydrokoumine N₄-oxide in 12 steps from commercially available starting materials. The key reactions include an intramolecular [3+2] nitrone cycloaddition, and Lewis acid mediated cyclizations of a common intermediate to provide the core structures of either (19Z)-taberpsychine or isodihydrokoumine. Both failed and successful routes will be discussed.

Evaluation Of Raman Spectroscopic Geothermometry Of Graphitic Carbon As A Mineral Exploration Tool. A Case Study Of The San Sebastian Au-Ag Mine, Durango, Mexico, Justin Daniel Rumney

Electronic Thesis and Dissertation Repository

While visually similar to graphite, graphitic carbon is disordered rings of carbon whereas graphite is the pure-carbon crystalline form. As graphitic carbon is heated, it undergoes an irreversible graphitization process which can be observed using Raman spectroscopy and determine the maximum temperature that a rock was exposed to. Samples of sedimentary rocks, taken from the Au-Ag San Sebastian mine in Durango Mexico, containing graphitic carbon located from positions in contact with mineralized veins were used in developing a low-cost protocol for Raman spectroscopic analysis of drill core. The samples were cut and then polished to provide a smooth surface, so …

Integrating Petrophysics And Allostratigraphy To Find Sweet Spots In The Upper Cretaceous Belle Fourche And Second White Specks Alloformations, West-Central Alberta, Canada, Kienan P. Marion

Electronic Thesis and Dissertation Repository

The Upper Cretaceous Second White Specks Formation – an organic-rich, calcareous mudrock succession within the lower Colorado Group – is a prolific self-sourcing tight oil reservoir in Alberta. Due to the low porosity and permeability of this interval, localized natural fracture networks have previously provided the only means for oil to flow at economic rates. This study, focused in west-central Alberta, used allostratigraphic methods to subdivide the Second White Specks Formation into allomembers that define hydraulic flow units. The petrophysical properties (porosity, organic content, clay volume, and brittleness) of each allomember were modelled using a basic suite of geophysical wireline …

Modelling The Thermal Transport Of A Thawing Permafrost Plateau, Joelle E. Langford

Electronic Thesis and Dissertation Repository

Permafrost covers approximately 24% of the Northern Hemisphere and is in a state of decay which has large implications. To characterize the processes involved in the transitional period of permafrost decay, a three-dimensional finite element numerical model is developed. The model is based on the Scotty Creek Research Basin in the Northwest Territories, Canada (61°18'N, 121°18'W). FEFLOW groundwater flow and heat transport modelling software is used in conjunction with the piFreeze plug-in, to account for phase changes between ice and water. As transiently simulating actual permafrost evolution would require 100’s of years of climate variations over an evolving landscape, whose …

Word Blending And Other Formal Models Of Bio-Operations, Zihao Wang

Electronic Thesis and Dissertation Repository

As part of ongoing efforts to view biological processes as computations, several formal models of DNA-based processes have been proposed and studied in the formal language literature. In this thesis, we survey some classical formal language word and language operations, as well as several bio-operations, and we propose a new operation inspired by a DNA recombination lab protocol known as Cross-pairing Polymerase Chain Reaction, or XPCR. More precisely, we define and study a word operation called word blending which models a special case of XPCR, where two words x w p and q w y sharing a non-empty overlap part …

Three Essays On Structural Models, Xinghua Zhou

Electronic Thesis and Dissertation Repository

My thesis includes three papers on contingent claims valuation of corporate securities using structural models of credit risk. Our study focuses on structural models and their applications in estimating damages in security class actions, option pricing and warrant pricing. Securities class actions typically involve some misrepresentation by a firm that overstates its true value. In securities class actions econometric models are used to assess damages to shareholders. However, studies on measuring damages for debt-holders are limited. My first paper uses a modified Merton framework to measure the impact of misrepresentation on the value of other components (e.g., debt, warrants) of …

Glycopolymer Functionalization Of Polymersomes, Josh Jadischke

Electronic Thesis and Dissertation Repository

Carbohydrates are important to cellular communication, recognition, and pathogenesis, making them a useful synthetic target for application in therapeutics and diagnosis. Synthetic carbohydrate presenting scaffolds can replicate or interrupt the binding interactions that occur in nature. Due to the weak nature of the monosaccharide-protein bond, most carbohydrate presenting scaffolds display saccharides in a multivalent manner to improve binding. Recently there has been an effort to combine carbohydrate containing scaffolds with polymersomes (vesicles composed of polymers), due to the structural resemblance of polymersome membranes to biological membranes. This thesis describes the progress towards functionalizing polymersomes with linear glycopolymers as a potential …