Physical Sciences and Mathematics Commons^™

Dinitrogen Functionalization Using A Molybdenum Atom: Bridging The Gap Between Small And Coordination Complexes Via Quantum Mechanical Methods, Maria Virginia White

Doctoral Dissertations

Chemistry devotes a significant amount of its research to understanding small molecule activation from an electronic structure perspective to help with the investigation of the reaction pathways of catalytically active substances that can promote biomimetic catalysis. A large portion of the energy used annually in our planet is used for the artificial nitrogen fixation (Haber-Bosch process), which renders dinitrogen activation a subject of study. Molybdenum, a fourth row transitional metal, has demonstrated its effectiveness as an essential component of the dinitrogen reduction catalytic process. To better understand the multiple dinitrogen molybdenum binding modes, the work described herein combines wave function …

Expression And Purification Of Polyketide Synthase Domains To Investigate Protein-Protein Interactions In Polyketide Biosynthetic Pathways, Mujeeb Adeyinka Wakeel

Masters Theses

Polyketide synthases (PKSs) are multienzyme proteins catalyzing the production of the polyketide class of natural products with vast structural diversity. Type II PKSs catalyze polyketide biosynthesis using discrete (standalone) enzymes (domains), while type I PKSs use covalently linked enzymes arranged in a module to catalyze polyketide production. It is hypothesized that type II PKSs are the precursors to type I PKSs, proposing that the genes encoding individual discrete enzymes in type II PKSs fused to give the multienzyme modules of type I PKSs. We reasoned that the intramolecular-like reactions occurring in type I PKS modules might be a driving force …

Sub-Chandrasekhar Type Ia Supernovae Scenarios With Increased Pathways For Neutronization, Fernando Hernan Rivas

Doctoral Dissertations

Type Ia supernovae are thermonuclear explosions of white dwarfs (WD), electron-degenerate cores of old intermediate mass stars(under 8$M_{\odot}$). Reaching energies of $10^{51}$\si{\erg}, they outshine whole galaxies as they synthesize and distribute most of the iron group elements (IGE; V, Cr, Mn, Fe, Co, Ni) into the interstellar medium, thus being one of the main agents in cosmic chemical evolution. Also, given their notably homogeneous lightcurves, they form the last step in the cosmic distance ladder outdistancing Cepheid variables by orders of magnitude. Though calibration of said lightcurves is dependent on a high number of confirmed events, the limits of statistical …

Synthesizing, Purifying, And Characterizing Molten Chloride Salts, Phillip W. Halstenberg

Doctoral Dissertations

Molten chloride salts have vast potential as heat transfer fluids with both nuclear and concentrated solar power applications. For application in energy systems, the characteristics that govern these systems must be well understood. This work focuses on inorganic molten chloride salts with a special emphasis on the experimental aspect of chemical research. Chapter 2 covers the synthetic approaches for the formation of molten chloride mixtures. Many salts can be purchased from industrial suppliers, but most must be purified therefore, Chapter 3 evaluates various methodology developed for removal of impurities in salt mixtures. Once the salt of proper content and purity …

Mechanochemical Synthesis Of Task-Specific Conjugated Porous Networks Towards Enhanced Energy Storage, Juntian Fan

Doctoral Dissertations

Conjugated scaffolds with high electronic conductivity, high surface area, etc. are promising materials for diverse technological applications, especially in the electrochemical field. However, the current synthesis methods are still limited to the traditional solution-based method or the ionothermal method, which always require an inert atmosphere shield, large amounts of organic solvents, noble catalysts, long reaction time up to days, and high temperatures, etc. Therefore, there is a common goal of developing conjugated scaffolds through facile, green, straightforward pathways. Mechanochemistry, which is an efficient, sustainable, solvent-free methodology, could provide a unique reaction environment to synthesize this kind of functionalized materials, resulting …

Space-Angle Discontinuous Galerkin Finite Element Method For Radiative Transfer Equation, Hang Wang

Doctoral Dissertations

Radiative transfer theory describes the interaction of radiation with scattering and absorbing media. It has applications in neutron transport, atmospheric physics, heat transfer, molecular imaging, and others. In steady state, the radiative transfer equation is an integro-differential equation of five independent variables, which are 3 dimensions in space and 2 dimensions in the angular direction. This high dimensionality and the presence of the integral term present serious challenges when solving the equation numerically. Over the past 50 years, several techniques for solving the radiative transfer equation (RTE) have been introduced. These include, but are certainly not limited to, Monte Carlo …

Utilizing Ultra-Performance Chromatography High-Resolution Mass Spectrometry To Investigate Fatty Acid Mediated Antibiotic Tolerance, Brittni Woodall

Doctoral Dissertations

The lipid membrane is the first component necessary to sustain life. To maintain homeostasis, segregate cellular machinery, provide protection from the environment, and reproduce, an organism must establish a boundary in which the processes can occur. Throughout the last two decades, research has propelled our knowledge of lipid membranes much beyond original hypotheses. Once thought of to be static and uniform, the understanding of the lipid membrane has evolved to encompass a structure that is responsive, unique, and intricately constructed by the organism itself. By chance or by choice, organisms adapt the lipid membrane according to the environment for which …

Fabrication, Measurements, And Modeling Of Semiconductor Radiation Detectors For Imaging And Detector Response Functions, Corey David Ahl

Doctoral Dissertations

In the first part of this dissertation, we cover the development of a diamond semiconductor alpha-tagging sensor for associated particle imaging to solve challenges with currently employed scintillators. The alpha-tagging sensor is a double-sided strip detector made from polycrystalline CVD diamond. The performance goals of the alpha-tagging sensor are 700-picosecond timing resolution and 0.5 mm spatial resolution. A literature review summarizes the methodology, goals, and challenges in associated particle imaging. The history and current state of alpha-tagging sensors, followed by the properties of diamond semiconductors are discussed to close the literature review. The materials and methods used to calibrate the …

Path Integral Monte Carlo For Entanglement In Bosonic Lattices At T = 0, Emanuel Casiano-Diaz

Doctoral Dissertations

Path-Integral Monte Carlo Worm Algorithm is one of many Quantum Monte Carlo (QMC) methods that serve as powerful tools for the simulation of quantum many-body systems. Developed in the late 90’s, this algorithm has been used with great success to study a wide array of physical models where exact calculation of observables is not possible due to the exponential size of the Hilbert space. One type of systems that have eluded PIMC-WA implementation are lattice models at zero temperature, which are of relevance in experimental settings, such as in optical lattices of ultra-cold atoms. In this thesis, we develop a …

Pointing Control And Stabilization Of The High-Energy Uv Laser For Laser-Assisted Charge Exchange, Martin Joseph Kay

Doctoral Dissertations

Laser-Assisted Charge Exchange (LACE) is an experimental method of charge exchange injection into a proton accumulator ring that is being developed at the Spallation Neutron Source (SNS) in Oak Ridge National Laboratory (ORNL) as an alternative to hazardous injection foils. The current scheme of LACE requires a high-energy, low-repetition-rate UV (355 nm) laser beam (140 mJ pulses at 10 Hz) to be transported over 65 meters to the laser-particle interaction point (IP) in a high-radiation area of the accelerator. Thermal effects and other disturbances along the free-space laser transport line cause the beam to slowly drift away from the IP …

Total Absorption Spectroscopy Of Mo-106 And Tc-106, Michael Cooper

Doctoral Dissertations

Total absorption spectroscopy is a method of gamma-ray spectroscopy that has gained prominence in the past several decades, as nuclear data revisions are performed on older nuclear data, which is often incomplete. A strong understanding of underlying nuclear data, particularly fission and beta decay data, is essential for nuclear reactors and nuclear fuel decay heat. This PhD work involves the analysis of fission fragments 106Mo [Mo-106] and 106Tc [Tc-106]. These neutron rich isotopes contribute upwards of 6% of the cumulative fission yield of 241Pu [Pu-241] fission, and 4% of 239Pu [Pu-239] fission. Prior data for these two fission fragments only …

Large-Scale Volcanism On The Terrestrial Planets, Keenan Ben Golder

Doctoral Dissertations

Evidence for mafic volcanism has been found on each planet in the inner Solar System. Lava flows on these planets range in size from 10s to 1000s of kilometers in extent. I investigated large-scale lava flows on Mercury, Earth, and Mars throughout the chapters in this dissertation. Each of these lava flows provides an avenue to study the emplacement and evolution of lava on various planets and under differing conditions, the factors that affect their overall extent, and potential source areas.

Chapter One investigates large-scale lava flows in the Cerberus region on Mars, specifically to understand their emplacement history, material …

The Novel Chlorination Of Zirconium Metal And Its Application To A Recycling Protocol For Zircaloy Cladding From Spent Nuclear Fuel Rods, Breanna K. Vestal

Doctoral Dissertations

A novel protocol has been developed for the chemical removal of zirconium alloy (Zircaloy) cladding from spent nuclear fuel rods and subsequent isolation and purification of nuclear-grade zirconium chloride derived therefrom. This protocol is based on the chemistry developed from two new scientific findings.

First, two new oxidative chlorination reactions have been discovered for zirconium metal. In both solvents, zirconium can be quantitatively chlorinated at temperatures less than 150°C, with the operative equations seen below. In sulfur monochloride, the reaction is completed in 2 – 4 hours via surface etching, exhibiting 0^th order kinetic behavior. The elemental sulfur byproduct …

Climatological Analysis Of Tropical Cyclone Occurrence Dates And Landfall Characteristics In The North Atlantic And Eastern North Pacific, Nicholas Sava Grondin

Doctoral Dissertations

Tropical cyclones (TCs) are significant hazards to coastal and inland regions across the globe, especially in North America. North America is affected by TCs from two basins, the North Atlantic (NATL) and eastern North Pacific (ENP), with the former being the predominate focus of past research. In this dissertation, I present three studies that directly compare TCs in the NATL and ENP by using the same methods for each basin in studying occurrence dates and intraseasonal variability, effects of environmental parameters on occurrence dates and seasonal forecasting, and the behavior of TCs during the final 36 hours before landfall in …

Neutrino Physics At A Research Reactor: Backgrounds And Analysis, Blaine Alexander Heffron

Doctoral Dissertations

The field of neutrino physics has a rich history and is currently the subject of much active research. The discovery of neutrino oscillations led to the conclusion that neutrinos have mass which was in contradiction to the Standard Model. Now researchers are investigating a number of open questions regarding neutrino properties such as their mass values or the existence of CP violation in the weak interaction. In order to answer these questions experimental and analytical techniques of neutrino detection are becoming more advanced, entering into an era of precision neutrino detection.

Nuclear reactors as a source of antineutrinos have played …

Understanding And Simulating Wildfire Changes Using Advanced Statical And Process-Oriented Models, Rongyun Tang

Doctoral Dissertations

This study aims to investigate the spatiotemporal dynamic of global wildfires, their underlying climate-driving mechanisms, and their predictability by utilizing multiple data sources (both process-based model simulations and satellite-based observations) and multiple analytical methods including machine learning techniques (MLTs).

We first explored the global wildfire interannual variability (IAV) and its climate sensitivity across nine biomes from 1997 to 2018, leveraging the state-of-art U.S. Department of Energy’s Energy Exascale Earth System Model (E3SM) land component (ELM-v1) simulations with six sets of climate forcings. Results indicate that 1) ELM simulations could reproduce the IAV of wildfire in terms of magnitudes, distribution, bio-regional …

Evaluating Bulk Carbon And Nitrogen Isotope Compositions Of Acidic Hydrothermal Sediments On Earth– Implications For Mars Astrobiology, Chance Sturrup

Masters Theses

Carbon isotopes have been widely used as unique biosignatures because biologic processes commonly result in distinctive negative delta ¹³C values (-35 to -10 ‰) within organic material on Earth. However, the bulk delta ¹³C analysis in Gale crater sediments on Mars revealed a wider range of values, from -25 to +56 ‰ (Franz et al., 2020), which suggests a more complex origin. To determine if bulk isotope analysis can be successfully used to detect a microbial signature in a martian analog environment, we analyzed concentrations and isotope compositions of C within hydrothermal sediments in Iceland (Námafjall, Krýsuvík, Hveragerdi) …

Interactive Data Analysis Of Multi-Run Performance Data, Vanessa Lama

Masters Theses

Multi-dimensional performance data analysis presents challenges for programmers, and users. Developers have to choose library and compiler options for each platform, analyze raw performance data, and keep up with new technologies. Users run codes on different platforms, validate results with collaborators, and analyze performance data as applications scale up. Site operators use multiple profiling tools to optimize performance, requiring the analysis of multiple sources and data types. There is currently no comprehensive tool to support the structured analysis of unstructured data, when holistic performance data analysis can offer actionable insights and improve performance. In this work, we present thicket, a …

Survey Of Input Modalities In The Western World, John Ezat Sadik

Masters Theses

Having your account compromised can lead to serious complications in your life. One
way accounts become compromised is through the security risks associated with weak
passwords and reused passwords [22,23]. In this thesis, we seek to understand how
entering passwords on non-PC devices contributes to the problems of weak and reused
passwords. To do so, we conducted a survey that was distributed to people in the
the Western World. In our survey results, we found that users commented about
how the current password model was not created with a variety of device types in
mind, which created frustrations and complexity …

Understanding The Polymerization Of Ethyl Cyanoacrylate In The Superglue Fuming Of Latent Prints To Optimize Print Retrieval, Leondra Shawntae Lawson

Masters Theses

The cyanoacrylate fuming method (CFM) is a widespread process used in forensics to make latent prints visible for detection, acquisition, and analysis. CFM is governed by the reaction of ethyl cyanoacrylate (ECA) with biological components in fingerprints, which serve as initiators for this anionic polymerization. CFM is not a well-controlled polymerization and there are different outcomes that may result from lower temperature, one of which fits the generalization of creating more ion-pair initiators. Another effect could be minimizing termination through suppressing side reactions. Alternatively, when paired with humidity, lower temperatures may cause surface condensation, decreasing the quality of the print. …

Explicit Constructions Of Canonical And Absolute Minimal Degree Lifts Of Twisted Edwards Curves, William Coleman Bitting Iv

Doctoral Dissertations

Twisted Edwards Curves are a representation of Elliptic Curves given by the solutions of bx^2 + y^2 = 1 + ax^2y^2. Due to their simple and unified formulas for adding distinct points and doubling, Twisted Edwards Curves have found extensive applications in fields such as cryptography. In this thesis, we study the Canonical Liftings of Twisted Edwards Curves and the associated lift of points Elliptic Teichmu ̈ller Lift. The coordinate functions of the latter are proved to be polynomials, and their degrees and derivatives are computed. Moreover, an algorithm is described for explicit computations, and some properties of the general …

Analysis Of A Controlled Approximation For Explicit Integrations Of Stiff Thermonuclear Networks, Nicholas Brey

Masters Theses

The current standard method to solve stiff coupled differential equations relies on implicit integration methods. Explicit methods are generally avoided due to the extremely small and limiting timesteps they allow when the equations are stiff. However, implicit methods are computationally expensive because of the complex calculations that need to be done at each time step. An explicit integration method can do these calculations quicker and, if allowed to take comparable timesteps to the implicit ones, would allow the entire calculation to be done faster. Previous work by Dr. Guidry, Dr. Endeve, Dr. Hix and Dr. Billings has shown that, in …

Impact Of Cover Crop Species Diversity On Soil Nutrient Availability And Crop Productivity, Amanda Kramer

Masters Theses

Cover crops provide multiple environmental benefits that improve both soil and water quality; however, farmers only utilize them on approximately 5% of harvested U.S. cropland. Low adoption rates are attributed to yield impact concerns, seed and planting costs, and lack of advocacy. This study, which began in October 2019, assessed the effects of nitrogen rate and cover crop diversity on weed biomass, soil coverage, in-situ residue decomposition, soil nitrogen and phosphorus availability, and cash crop yield to better understand the costs and benefits of cover crop adoption at two locations in Tennessee (Milan and Spring Hill). Treatments were replicated 4 …

Computational Aspects Of Mixed Characteristic Witt Vectors And Denominators In Canonical Liftings Of Elliptic Curves, Jacob Dennerlein

Doctoral Dissertations

Given an ordinary elliptic curve E over a field 𝕜 of characteristic p, there is an elliptic curve E over the Witt vectors W(𝕜) for which we can lift the Frobenius morphism, called the canonical lifting of E. The Weierstrass coefficients and the elliptic Teichmüller lift of E are given by rational functions over 𝔽_p that depend only on the coefficients and points of E. Finotti studied the properties of these rational functions over fields of characteristic p ≥ 5. We investigate the same properties for fields of characteristic 2 and 3, make progress on …

Probing Gas Transport Structure-Property Relationships In Vinyl-Addition Polynorbornenes, Trevor Jonas Wilson

Doctoral Dissertations

Polynorbornenes are ideal materials for systematic structure-property investigations designed to correlate gas-transport properties to polymer structure. The modular nature of norbornene-derived systems provides a facile route towards the synthesis of diverse polymeric materials, whose structure may be systematically altered through targeted design of monomers, alterations in polymerization mechanism, or some combination of these two strategies. Though many valuable correlations between gas-permeability and polynorbornene structure have been summarized in prior literature, many of these efforts have focused on homopolymer materials with structural changes imposed — almost exclusively — through modifications in substituent chemistry, or through targeted modulation of molar ratios in …

Unlocking The Potential Of Machine Learning In The Derivation Of Low-Energy Models For Metallic Magnets, Vikram Sharma

Doctoral Dissertations

Condensed matter physics often grapples with complex many-particle problems lacking definitive closed-form solutions, necessitating approximation strategies to investigate low-energy sectors of the Hilbert space. Perturbation theory, though widely used for this purpose, is limited when expansion terms diverge. This work introduces a machine learning (ML) assisted protocol to extract effective low-energy models for lattice models of fermions interacting with classical fields, specifically focusing on the Kondo Lattice Model (KLM).

Skyrmions, featuring whirling spin texture and topological protection, are promising candidates for future spintronic devices. Materials featuring conduction electrons coupled to localized $f$-electrons' net moment are ideal for realizing skyrmions and …

Development Of Artificial Lipids For Metal Ion-Responsive Liposomes And Related Medicinal Applications, Ruhani Sagar

Doctoral Dissertations

Liposomes are synthetic vesicles made of phospholipids that are effective for wide-ranging applications in drug delivery and studying biological membranes. Understanding and controlling membrane properties such as fluidity and permeability is crucial for designing liposomes for specific biomedical applications. Pathological changes in these properties can also help us gain insights into disease mechanisms and develop effective treatments. In this dissertation, we describe the design, synthesis, and study of several lipid analogs for a range of applications including liposome triggered cargo release and therapeutic treatment related to lipids.

In Chapters 2-3, we developed smart liposome platforms that can respond to changes …

A Machine Learning Approach For Predicting Clinical Trial Patient Enrollment In Drug Development Portfolio Demand Planning, Ahmed Shoieb

Masters Theses

One of the biggest challenges the clinical research industry currently faces is the accurate forecasting of patient enrollment (namely if and when a clinical trial will achieve full enrollment), as the stochastic behavior of enrollment can significantly contribute to delays in the development of new drugs, increases in duration and costs of clinical trials, and the over- or under- estimation of clinical supply. This study proposes a Machine Learning model using a Fully Convolutional Network (FCN) that is trained on a dataset of 100,000 patient enrollment data points including patient age, patient gender, patient disease, investigational product, study phase, blinded …

Anxiety-Like Behavior In C57bl/6j Mice Is Sexually Dimorphic And Altered By Buprenorphine, Ohm Sharma

Chancellor’s Honors Program Projects

No abstract provided.

Development And Study Of Small Database For The Activation Of Nitrous Oxide Towards Formation Of Iron(Iv)-Oxo Species, Tobias Barthalomew Robertson

Masters Theses

Nitrous oxide (N₂O) can undergo an oxygen atom transfer (OAT) reaction resulting in inert nitrogen gas (N₂O) while transferring an oxygen atom to a molecular complex or material. This process is of catalytic importance since this OAT reaction can be leveraged to form iron(IV)-oxo sites, which are known to be catalytic intermediates. Here, an investigation of the ligand field effects on primarily iron(II) complexes for the formation of iron(IV)-oxo sites with nitrous oxide as the oxidant is reported. An initial database of sixty-four molecular complexes with ligand environments varying in field strength and coordination geometry was …