Physical Sciences and Mathematics Commons^™

Mild Deprotection Of The N-Tert-Butyloxycarbonyl (N-Boc) Group Using Oxalyl Chloride, Nathaniel George, Samuel Ofori, Sean R. Parkin, Samuel G. Awuah

Chemistry Faculty Publications

We report a mild method for the selective deprotection of the N-Boc group from a structurally diverse set of compounds, encompassing aliphatic, aromatic, and heterocyclic substrates by using oxalyl chloride in methanol. The reactions take place under room temperature conditions for 1–4 h with yields up to 90%. This mild procedure was applied to a hybrid, medicinally active compound FC1, which is a novel dual inhibitor of IDO1 and DNA Pol gamma. A broader mechanism involving the electrophilic character of oxalyl chloride is postulated for this deprotection strategy.

Testing Interpretations Of The Displacement Magnitude Of The Teton Fault And Uplift Of The Teton Range, Wyoming With Integrated Flexural-Kinematic And Thermal Modeling, Autumn Helfrich

Theses and Dissertations--Earth and Environmental Sciences

The Teton fault is a range-front normal fault in northwestern Wyoming. Previous estimates of the maximum displacement (D_max) on the Teton fault cover a wide range (2 - 11 km). Discrepancies also exist regarding the slip onset timing, which spans 2 - 13 Ma. To address these discrepancies, the exhumation history of the Teton Range is here investigated using forward flexural-kinematic (Move) and thermal-kinematic (Pecube) models that can be compared with previously reported apatite fission track (AFT) and apatite (U-Th)/He (AHe) ages from Mount Moran, which has been previously hypothesized to represent the …

Sample Size Calculation And Blinded Recalculation For Analysis Of Covariance Models With Multiple Random Covariates, Georg Zimmermann, Meinhard Kieser, Arne C. Bathke

Statistics Faculty Publications

When testing for superiority in a parallel-group setting with a continuous outcome, adjusting for covariates is usually recommended. For this purpose, the analysis of covariance is frequently used, and recently several exact and approximate sample size calculation procedures have been proposed. However, in case of multiple covariates, the planning might pose some practical challenges and pitfalls. Therefore, we propose a method, which allows for blinded re-estimation of the sample size during the course of the trial. Simulations confirm that the proposed method provides reliable results in many practically relevant situations, and applicability is illustrated by a real-life data example.

Quantum Phases And Phase Transitions In Designer Spin Models, Nisheeta Desai

Theses and Dissertations--Physics and Astronomy

This work focuses on numerical studies of quantum spin systems. These simple models are known to exhibit a variety of phases, some of which have no classical counterpart. Phase transitions between them are driven by quantum fluctuations and the unconventional nature of some such transitions make them a fascinating avenue of study.

Quantum Monte Carlo (QMC) is an indispensable tool in the study of these phases and phase transitions in two and higher dimensions. Nevertheless, we are limited by our inability to simulate models that suffer from the infamous sign problem. While the case of S=1/2 has been studied …

Geologic Characterization, Hydrologic Monitoring, And Soil-Water Relationships For Landslides In Kentucky, Matthew M. Crawford, L. Sebastian Bryson, Zhenming Wang, Edward W. Woolery

Report of Investigations--KGS

Complex spatial and temporal variables control the movement of water through colluvial soils in hillslopes. Some of the factors that influence soil-moisture fluctuation are soil type, thickness, porosity and permeability, and slope morphology. Landslide-characterization and field-monitoring techniques were part of a method to connect hydrologic and geotechnical data in order to monitor long-term hydrologic conditions in three active landslides in Kentucky, establish hydrologic relationships across the slope, and analyze specific soil-water relationships that can predict shear strength. Volumetric water content, water potential, and electrical conductivity were measured between October 2015 and February 2019. The duration and magnitude of drying and …

Characterization Of Rare Earth Elements In The Illinois Basin Coals, Alireza Valian

Theses and Dissertations--Mining Engineering

The purpose of this study is to characterize the distribution and occurrence of rare earth elements (REEs) in the coal and coal-related material from the Illinois Basin. For characterizing the distribution of REEs, 17 core samples were investigated from various parts in the basin. Also, several individual samples from coal preparation plants and isolated geological occurrences were included in the study. In result, the average REE concentrations were calculated on a bed-to-bed basis, although the distribution of REEs in the coal beds was found laterally and vertically heterogeneous. A number of trends were found that describe the variations. Most importantly, …

Fault Identification On Electrical Transmission Lines Using Artificial Neural Networks, Christopher W. Asbery

Theses and Dissertations--Electrical and Computer Engineering

Transmission lines are designed to transport large amounts of electrical power from the point of generation to the point of consumption. Since transmission lines are built to span over long distances, they are frequently exposed to many different situations that can cause abnormal conditions known as electrical faults. Electrical faults, when isolated, can cripple the transmission system as power flows are directed around these faults therefore leading to other numerous potential issues such as thermal and voltage violations, customer interruptions, or cascading events. When faults occur, protection systems installed near the faulted transmission lines will isolate these faults from the …

A Modeling Approach To Understanding Glyphosate Transport In The Belize River Watershed, Barbara Anmei Astmann

Theses and Dissertations--Civil Engineering

Glyphosate is the most widely used herbicide worldwide and is often transported from application areas to surface water when solubilized in runoff or sorbed to eroded sediment. There is evidence that suggests both glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) may pose a risk to human health, as well as cause adverse effects in the environment. However, consistent monitoring data is still limited, especially in developing countries. Belize is a developing nation with agriculture being a major sector of its economy and is heavily reliant on glyphosate. The widespread use of glyphosate in Belize may be resulting in glyphosate …

North Fork: Whitesburg Tributaries Watershed Plan, Letcher County, Ky, Kentucky Water Resources Research Institute

KWRRI Research Reports

Crafts Colly, Sandlick, and Dry Fork are tributaries to the North Fork of the Kentucky River. The three tributaries are located immediately north of the North Fork of the Kentucky and flow southward into the river within or near the City of Whitesburg in Letcher County, Kentucky. Letcher County is found in the Appalachian coalfields of southeastern Kentucky.

To improve water quality in the Kentucky River, water quality impairments in the upper reaches of the watershed must be addressed. In focusing efforts in Crafts Colly, Sandlick, and Dry Fork, three headwater tributaries of the North Fork Kentucky River, pollution loading …

Temporal Data Extraction And Query System For Epilepsy Signal Analysis, Yan Huang

Theses and Dissertations--Computer Science

The 2016 Epilepsy Innovation Institute (Ei2) community survey reported that unpredictability is the most challenging aspect of seizure management. Effective and precise detection, prediction, and localization of epileptic seizures is a fundamental computational challenge. Utilizing epilepsy data from multiple epilepsy monitoring units can enhance the quantity and diversity of datasets, which can lead to more robust epilepsy data analysis tools. The contributions of this dissertation are two-fold. One is the implementation of a temporal query for epilepsy data; the other is the machine learning approach for seizure detection, seizure prediction, and seizure localization. The three key components of our temporal …

Tracing Source Contributions To Assess Spatial Patterns Of Erosion In A Mixed Land Use Environment: Otter Creek Catchment, Fort Knox, Kentucky, Cara Peterman

Theses and Dissertations--Earth and Environmental Sciences

There is an inherent difficulty in predicting source contributions of fine-grained fluvial sediment in mixed land-use watersheds. Over a 56-week period, the spatial and temporal variability in sediment-source contributions and water quality was monitored at three sites along Otter Creek in Hardin and Meade counties, Kentucky (USA). The 203-km² study area drains rural and agricultural lands and includes Fort Knox Army Post’s tracked-vehicle training areas. The main objectives for sediment source apportionment were to 1) identify and differentiate characteristics of civilian and military source soils to Otter Creek and 2) to apportion sediment at locations along Otter Creek to …

A Multi-Method Investigation Of The Modern Sedimentation And Late Holocene Paleolimnology Of June Lake (Mono County, Ca), And A Survey-Based Analysis Of Ninth Graders’ Attitudes Towards Geology, Eva Lyon

Theses and Dissertations--Earth and Environmental Sciences

Three distinct manuscripts comprise this dissertation. The first analyzes the modern sedimentary basin of June Lake, a small glacial lake in the eastern Sierra Nevada of California (USA) using a number of data sets, including bathymetry, surface sediment composition, and seismic stratigraphy. The seismic survey revealed sublacustrine morphological features that suggest the basin originated due to ice scour, as well as four acoustically distinct stratigraphic units that reflect the history of sedimentation following glacial scouring. Corroborating the seismic record, sediment cores from the youngest unit are composed of hemipelagically deposited, organic-rich, laminated diatomaceous oozes alternating with coarse tephra beds. The …

Identification Of The Causes And Extent Of Elevated Methane Concentrations In The Groundwater Of Eastern Kentucky, Cristopher Alvarez Villa

Theses and Dissertations--Earth and Environmental Sciences

Recent development of unconventional oil and gas (UOG) resources has prompted concerns about its potential impact on public health and the quality of water and air resources. Elevated dissolved methane concentrations (> 1 mg/L) have been associated with proximity to UOG development and stray gas, but also with natural microbial activity. Baseline gas data, local hydrogeology and geochemistry context can aid assessment of methane sources and interactions. Methane concentrations in eastern Kentucky groundwater are above the “immediate action” level in some private/domestic water wells, show wide variations over small distances, and have been hypothesized to have different relationships to mining. …

Isotopic And Geochemical Tracers Of Groundwater Flow In The Shivwits Plateau, Grand Canyon National Park, Jonathan W. Wilson

Theses and Dissertations--Earth and Environmental Sciences

As the impacts of global climate change on water resources continue to become more apparent, proper understanding and management of groundwater resources will be needed as supplies become more strained. Traditional methods of characterizing groundwater systems are time-intensive, costly, and can be difficult to complete in remote areas. Using ambient geochemical tracers from discrete sampling could aid in characterizing spring systems through determining flow paths, recharge areas, and carbon cycling. However, using discrete seasonal samples to understand the hydrogeology of complex, mixed-lithology aquifers has not been extensively examined. Here we explore using δ¹³C of dissolved organic carbon (DOC), …

A Csi Detector Array For The Ndtgamma Test Measurement, Diana V. Sahibnazarova

Oswald Research and Creativity Competition

No abstract provided.

Development Of A Robust Treatment Delivery Framework For Stereotactic Body Radiotherapy (Sbrt) Of Synchronous Multiple Lung Lesions, Lana Catherine Critchfield

Theses and Dissertations--Radiation Medicine

Stereotactic body radiation therapy (SBRT) of lung tumors uses high doses of radiation to deliver high biological effective doses (BED) in very few fractions (1-5). With the use of highly conformal fields to cover the tumor without depositing large doses to non-cancerous structures, this technique has proven time and again to be successful at achieving high local control. However, frequently patients receiving SBRT are elderly with multiple medical comorbidities who may not tolerate long treatment times. Furthermore, many patients present with oligometastatic or multiple primary lung tumors. The success of SBRT on oligometastatic lung disease relies on physician experience with …

Assessing The Climate Water Balance Model’S Ability To Predict Soil Moisture Variability And Species Distribution Of A Forested Watershed In The Northern Cumberland Plateau, Katherine J. Love

Theses and Dissertations--Forestry and Natural Resources

Spatial patterns of moisture and tree species have been studied using environmental gradients, often represented by terrain attributes in GIS. With climate change, GIS terrain variables, which are static as long as the elevation remains unchanged, will not reflect alterations in temperature, water cycle, and atmospheric conditions. In this thesis, the commonly used terrain variables and climate water balance variables were evaluated and compared for their ability to explain soil moisture and tree species distributions in a forested watershed in the Northern Cumberland Plateau. The results suggest that GIS terrain variables generally perform better than climate water balance variables, however, …

Statistical Intervals For Various Distributions Based On Different Inference Methods, Yixuan Zou

Theses and Dissertations--Statistics

Statistical intervals (e.g., confidence, prediction, or tolerance) are widely used to quantify uncertainty, but complex settings can create challenges to obtain such intervals that possess the desired properties. My thesis will address diverse data settings and approaches that are shown empirically to have good performance. We first introduce a focused treatment on using a single-layer bootstrap calibration to improve the coverage probabilities of two-sided parametric tolerance intervals for non-normal distributions. We then turn to zero-inflated data, which are commonly found in, among other areas, pharmaceutical and quality control applications. However, the inference problem often becomes difficult in the presence of …

Measuring Change: Prediction Of Early Onset Sepsis, Aric Schadler

Theses and Dissertations--Statistics

Sepsis occurs in a patient when an infection enters into the blood stream and spreads throughout the body causing a cascading response from the immune system. Sepsis is one of the leading causes of morbidity and mortality in today’s hospitals. This is despite published and accepted guidelines for timely and appropriate interventions for septic patients. The largest barrier to applying these interventions is the early identification of septic patients. Early identification and treatment leads to better outcomes, shorter lengths of stay, and financial savings for healthcare institutions. In order to increase the lead time in recognizing patients trending towards septicemia …

Nonparametric Tests Of Lack Of Fit For Multivariate Data, Yan Xu

Theses and Dissertations--Statistics

A common problem in regression analysis (linear or nonlinear) is assessing the lack-of-fit. Existing methods make parametric or semi-parametric assumptions to model the conditional mean or covariance matrices. In this dissertation, we propose fully nonparametric methods that make only additive error assumptions. Our nonparametric approach relies on ideas from nonparametric smoothing to reduce the test of association (lack-of-fit) problem into a nonparametric multivariate analysis of variance. A major problem that arises in this approach is that the key assumptions of independence and constant covariance matrix among the groups will be violated. As a result, the standard asymptotic theory is not …

Solutions To Systems Of Equations Over Finite Fields, Rachel Petrik

Theses and Dissertations--Mathematics

This dissertation investigates the existence of solutions to equations over finite fields with an emphasis on diagonal equations. In particular:

1. Given a system of equations, how many solutions are there?
2. In the case of a system of diagonal forms, when does a nontrivial solution exist?

Many results are known that address (1) and (2), such as the classical Chevalley--Warning theorems. With respect to (1), we have improved a recent result of D.R. Heath--Brown, which provides a lower bound on the total number of solutions to a system of polynomials equations. Furthermore, we have demonstrated that several of our lower bounds …

Graph-Theoretic Simplicial Complexes, Hajos-Type Constructions, And K-Matchings, Julianne Vega

Theses and Dissertations--Mathematics

A graph property is monotone if it is closed under the removal of edges and vertices. Given a graph G and a monotone graph property P, one can associate to the pair (G,P) a simplicial complex, which serves as a way to encode graph properties within faces of a topological space. We study these graph-theoretic simplicial complexes using combinatorial and topological approaches as a way to inform our understanding of the graphs and their properties.

In this dissertation, we study two families of simplicial complexes: (1) neighborhood complexes and (2) k-matching complexes. A neighborhood complex is a simplicial …

Laser Ablation In Liquid For The Controlled Production Of Photoluminescent Graphene Quantum Dots And Upconverting Nanoparticles, Rosemary Lynn Calabro

Theses and Dissertations--Chemistry

Photoluminescent­ (PL) nanomaterials play an important role in areas including displays, sensing, solar, photocatalysis, and bio applications. Traditional methods to prepare PL materials suffer many drawbacks such as harsh chemical precursors, complicated synthetic steps, and production of many byproducts. Laser ablation in liquid (LAL) has emerged as a promising alternative to prepare materials that is single-step, fast, uses fewer precursors, produces fewer side products, and has simple purification steps. During LAL, a solid target is irradiated with a pulsed laser source. The laser pulses cause plasma plumes of the target material to form which are cooled, condensed, and can react …

Analysis Of Magnetization Directions Of Lunar Swirls, Lillie Cole

Lewis Honors College Capstone Collection

Lunar Swirls are high albedo markings on the Moon that exist in the regions of some crustal magnetic anomalies. The precise mechanism responsible for the swirl features is unknown but a prevailing theory is solar wind standoff, where the magnetic field from subsurface magnetized sources protects the lunar surface from solar wind ions, leading to their lesser maturation and brighter appearance. If this theory is correct, the magnetic field of the anomalies should heavily influence the appearance of the swirl. To better understand the cause of swirls, the magnetization direction of the source creating the field is analyzed. This study …

Study Of Cell Charging Effects For The Neutron Electric Dipole Moment Experiment At Oak Ridge National Laboratory, Mark Broering

Theses and Dissertations--Physics and Astronomy

The neutron electric dipole moment (nEDM) collaboration at the Spallation Neutron Source plans to use ultra-cold neutrons in superfluid helium to improve the nEDM limit by about two orders of magnitude. In this apparatus, neutrons are stored in poly(methyl methacrylate), PMMA, cells located in a strong, stable electric field. This electric field is produced by high voltage electrodes located outside of the neutron cells. Several sources generate charged particles inside the neutron cells. The electric field pulls these charges farther apart, attracting each to the oppositely charged electrode. As the charges build up on the cells walls, they create an …

Theoretical Studies Of C And Cp Violation In $\Eta \To \Pi^+ \Pi^- \Pi^0$ Decay, Jun Shi

Theses and Dissertations--Physics and Astronomy

A violation of mirror symmetry in the $\eta\to\pi^+\pi^-\pi^0$ Dalitz plot has long been recognized as a signal of C and CP violation. In this thesis, we show how the isospin of the underlying C- and CP-violating structures can be reconstructed from their kinematic representation in the Dalitz plot. Our analysis of the most recent experimental data reveals, for the first time, that the C- and CP-violating amplitude with total isospin I = 2 is much more severely suppressed than that with total isospin I = 0.

In searching for C- and CP-violating sources beyond the SM, we enumerate the leading-dimension, …

The Impact Of Ryegrass On A Fragipan Soil, Keegan Patrick Smith

Theses and Dissertations--Plant and Soil Sciences

Fragipans are soil horizons which negatively impact row crop yields due to their cemented nature. Annual ryegrass has been proposed as a cover crop to help remediate these dense horizons. The objectives of this study were to (1) evaluate potential ryegrass root exudates and their ability to solubilize proposed fragipan cementing agents, aluminum (Al), iron (Fe), and silica (Si) in stirred-batch reactor studies; and (2) evaluate annual ryegrass’ ability to remediate the fragipan through an 8-week greenhouse growth study using non-destructive, mini-rhizon samplers installed on soil cores for in situ pore water sampling, and non-invasive soil porosity calculations using X-ray …

Geometry Of Linear Subspace Arrangements With Connections To Matroid Theory, William Trok

Theses and Dissertations--Mathematics

This dissertation is devoted to the study of the geometric properties of subspace configurations, with an emphasis on configurations of points. One distinguishing feature is the widespread use of techniques from Matroid Theory and Combinatorial Optimization. In part we generalize a theorem of Edmond's about partitions of matroids in independent subsets. We then apply this to establish a conjectured bound on the Castelnuovo-Mumford regularity of a set of fat points.

We then study how the dimension of an ideal of point changes when intersected with a generic fat subspace. In particular we introduce the concept of a ``very unexpected hypersurface'' …

A Biophysical Investigation Of Stability, Ligand Binding, And Iron State Of Cyp102a1, Catherine A. Denning-Jannace

Theses and Dissertations--Chemistry

Cytochrome P450s (CYPs) are cysteine ligated Fe-heme monooxygenases that are found in all domains of life. In mammals, they have a role in xenobiotic metabolism and steroid synthesis, making them a fundamental requirement for survival. In addition, their ability to perform a variety of chemical reactions on an array of substrates makes CYPs highly sought for biotechnical applications such as wastewater remediation, production of potential drug candidates, and creation of drug metabolites. By mutating specific amino acids, these enzymes can be engineered to change their substrate binding profiles and achieve stereo- and regio-specific chemistry. While these mutations are essential to …

Applications Of Drones In Atmospheric Chemistry, Travis J. Schuyler

Theses and Dissertations--Chemistry

The emission of greenhouse gases (GHGs) has changed the composition of the atmosphere during the Anthropocene. A major technical and scientific challenge is quantifying the resulting fugitive trace gas fluxes under variable meteorological conditions. Accurately documenting the sources and magnitude of GHGs emission is an important undertaking for discriminating contributions of different processes to radiative forcing. Therefore, the adverse environmental and health effects of undetected gas leaks motivates new methods of detecting, characterizing, and quantifying plumes of fugitive trace gases. Currently, there is no mobile platform able to quantify trace gases at altitudes(UASs), or drones, can be deployed on-site in …