Physical Sciences and Mathematics Commons^™

Explorations In Homeoviscous Adaptation And Mass Spectral Analysis Of Membrane Lipids, Michael Douglas Timmons

University of Kentucky Doctoral Dissertations

The focus of this dissertation is centered on the mass spectral analysis of lipids and changes occurring in keeping with the concept of homeoviscous adaptation [1]. Homeoviscous adaptation is the process of modification of membrane lipids in response to environmental stimuli [1]. Dissertation investigations applied this concept to prokaryotic and eukaryotic organisms, and expanded the perception of environmental factors from exogenous organic solvents to intracellular environment.

The field of lipidomics deals with the analysis of phospholipid and fatty acid components of membranes the changes that occur due to environmental stimuli and their biological significance [2-6]. The high sensitivity of mass …

Provenance Of The Neoproterozoic Ocoee Supergroup, Eastern Great Smoky Mountains, Suvankar Chakraborty

University of Kentucky Doctoral Dissertations

The Ocoee Supergroup is a sequence of Neoproterozoic, immature, continental rift facies clastic sediments. Potential source rocks were tested by analyzing modes of detrital framework minerals, detrital mineral chemistry, whole rock geochemistry and detrital zircon U/Pb geochronology by LA-ICP-MS for Ocoee siltstone-sandstone dominated formations. Ocoee units are arkosic to subarkosic siltstones/sandstones, and ternary tectonic discrimination diagrams confirm a continental basement uplift source. Alkali feldspar predominates over plagioclase feldspar. Detrital feldspar compositions of Ocoee sediments as a group are similar to feldspar in local basement granitic rocks except for high-Ca plagioclase grains present locally in basement granitic rocks. The high alkali …

Studies Toward The Total Synthesis Of (±)-Α-Yohimbine By Double Annulation, Raghu Ram Chamala

University of Kentucky Doctoral Dissertations

The indole alkaloids, a class of natural products, have received much synthetic attention for years due to their diverse structures and interesting biological properties. We are particularly interested in synthesizing some of the yohimbine alkaloids extracted from the bark of a tall evergreen African tree (Corynanthe yohimbe, commonly known as fringe tree). Yohimbine and its stereoisomers have been tempting targets for synthetic organic chemists for more than fifty years. These compounds feature a pentacyclic ring system with two heteroatoms and five stereogenic centers.

Broadly, the fifteen different synthetic approaches that led to the successful completion of yohimbine alkaloids …

Physical Conditions Including Magnetic Fields In Several Star Forming Regions Of The Galaxy, Matt Lykins

University of Kentucky Doctoral Dissertations

This document describes studies of two independent regions of the interstellar medium (ISM). These studies have the common element that both pertain to regions in our Galaxy that are known to be associated with present-day star formation. These studies aim to help us understand the ISM, star formation, and ultimately where we came from, since, after all, our star, the Sun, is itself the product of star formation 4.5 billion years ago. The first project measured the Zeeman Effect on the 21 cm H I absorption line in order to create a map of the line of sight magnetic fields …

Opioid-Cannabinoid Codrugs With Enhanced Analgesic And Pharmacokinetic Profile, Harpreet Kaur Dhooper

University of Kentucky Doctoral Dissertations

The central hypothesis of the dissertation is that “the design and synthesis of a codrug of an opiate and a cannabinoid can be achieved which is stable in the gastrointestinal tract and shows a superior pharmacological and pharmacokinetic profile when compared to a physical mixture of the two parent drugs.” To prove the hypothesis, a series of novel codrugs were prepared by conjugation of the opiate drug codeine with Δ⁹-tetrahydrocannabinol (Δ⁹-THC), cannabidiol, abn-cannabidiol and an opiate prodrug 3-O-acetylmorphine with Δ⁹-THC. Codeine-cannabinoid codrugs were evaluated for analgesic activity in the rat after oral administration. The …

Comparison Of Two Samples By A Nonparametric Likelihood-Ratio Test, William H. Barton

University of Kentucky Doctoral Dissertations

In this dissertation we present a novel computational method, as well as its software implementation, to compare two samples by a nonparametric likelihood-ratio test. The basis of the comparison is a mean-type hypothesis. The software is written in the R-language [4]. The two samples are assumed to be independent. Their distributions, which are assumed to be unknown, may be discrete or continuous. The samples may be uncensored, right-censored, left-censored, or doubly-censored. Two software programs are offered. The first program covers the case of a single mean-type hypothesis. The second program covers the case of multiple mean-type hypotheses. For the first …

Algorithms For Upper Bounds Of Low Dimensional Group Homology, Joshua D. Roberts

University of Kentucky Doctoral Dissertations

A motivational problem for group homology is a conjecture of Quillen that states, as reformulated by Anton, that the second homology of the general linear group over R = Z[1/p; ζ_p], for p an odd prime, is isomorphic to the second homology of the group of units of R, where the homology calculations are over the field of order p. By considering the group extension spectral sequence applied to the short exact sequence 1 → SL₂ → GL₂ → GL₁ → 1 we show that the calculation of the homology …

Nonparametric Estimation Of Derivatives With Applications, Benjamin Hall

University of Kentucky Doctoral Dissertations

We review several nonparametric regression techniques and discuss their various strengths and weaknesses with an emphasis on derivative estimation and confidence band creation. We develop a generalized C(p) criterion for tuning parameter selection when interest lies in estimating one or more derivatives and the estimator is both linear in the observed responses and self-consistent. We propose a method for constructing simultaneous confidence bands for the mean response and one or more derivatives, where simultaneous now refers both to values of the covariate and to all derivatives under consideration. In addition we generalize the simultaneous confidence bands to account for heteroscedastic …

Upper Bounds On The Splitting Of The Eigenvalues, Phuoc L. Ho

University of Kentucky Doctoral Dissertations

We establish the upper bounds for the difference between the first two eigenvalues of the relative and absolute eigenvalue problems. Relative and absolute boundary conditions are generalization of Dirichlet and Neumann boundary conditions on functions to differential forms respectively. The domains are taken to be a family of symmetric regions in Rⁿ consisting of two cavities joined by a straight thin tube. Our operators are Hodge Laplacian operators acting on k-forms given by the formula Δ^(k) = dδ+δd, where d and δ are the exterior derivatives and the codifferentials respectively. A result …

In Vivo Oxidative Stress In Alzheimer Disease Brain And A Mouse Model Thereof: Effects Of Lipid Asymmetry And The Single Methionine Residue Of Amyloid-Β Peptide, Miranda Lu Bader Lange

University of Kentucky Doctoral Dissertations

Studies presented in this dissertation were conducted to gain more insight into the role of phospholipid asymmetry and amyloid-β (Aβ)-induced oxidative stress in brain of subjects with amnestic mild cognitive impairment (aMCI) and Alzheimer disease (AD). AD is a largely sporadic, age-associated neurodegenerative disorder clinically characterized by the vast, progressive loss of memory and cognition commonly in populations over the age of ~65 years, with the exception of those with familial AD, which develop AD symptoms as early as ~30 years-old. Neuropathologically, both AD and FAD can be characterized by synapse and neuronal cell loss in conjunction with accumulation of …

Building Sustainable Societies: Exploring Sustainability Policy And Practice In The Age Of High Consumption, Cindy Isenhour

University of Kentucky Doctoral Dissertations

This dissertation is an attempt to examine how humans in wealthy, post-industrial urban contexts understand sustainability and respond to their concerns given their sphere of influence. I focus specifically on sustainable consumption policy and practice in Sweden, where concerns for sustainability and consumer-based responses are strong. This case raises interesting questions about the relative strength of sustainability movements in different cultural and geo-political contexts as well as the specific factors that have motivated the movement toward sustainable living in Sweden.

The data presented here supports the need for multigenic theories of sustainable consumerism. Rather than relying on dominant theories of …

Palinspastic Reconstruction Around A Thrust Belt Recess: An Example From The Appalachian Thrust Belt In Northwestern Georgia, Brian Stephen Cook

University of Kentucky Doctoral Dissertations

In a well-defined subrecess in the Appalachian thrust belt in northwestern Georgia, two distinct regional strike directions intersect at approximately 50°. Fault intersections and interference folds enable tracing of both structural strikes. Around the subrecess, tectonically thickened weak stratigraphic layers—shales of the Cambrian Conasauga Formation—accommodated ductile deformation associated with the folding and faulting of the overlying Cambrian–Ordovician regional competent layer. The structures in the competent layer are analogous to those over ductile duplexes (mushwads) documented along strike to the southwest in Alabama.

The intersection and fold interference exemplify a long-standing problem in volume balancing of palinspastic reconstructions of sinuous thrust …

Inadequate Health Numeracy Affects Cancer Screening Practices In Vulnerable Populations, Sherrine Eid Mph, Dorothy Faulkner Phd

Administration & Leadership

No abstract provided.

Resin-Modified Glass-Ionomer Setting Reaction Competition, David W. Berzins, S. Abey, M. C. Costache, Charles A. Wilkie, H. W. Roberts

Chemistry Faculty Research and Publications

Resin-modified glass ionomers (RMGI) set by at least 2 mechanisms dependent upon reactant diffusion prior to gelation. Each reaction’s kinetics and setting mechanism may rely on and/or compete with the other. In this study, we investigated RMGI setting reaction interactions using differential scanning calorimetry (DSC) by varying light-cure initiation times. A RMGI was analyzed with isothermal and dynamic temperature scan DSC with light-curing occurring immediately, or at 5 or 10 minutes after mixing as well as without light-activation. Results show that as time allowed for the acid-base reaction increased, the light-activation polymerization exotherm decreased. Conversely, analysis of DSC data suggests …

Thermal Degradation Studies On Pmma–Het Acid Based Oligoesters Blends, Thangamani Rajkumar, Chinnaswamy Thangavel Vijayakumar, Palanichamy Sivasamy, Bojja Sreedhar, Charles A. Wilkie

Chemistry Faculty Research and Publications

Imparting thermal stability to polymethyl methacrylate (PMMA) without affecting its optical clarity is attempted by incorporating HET acid based oligoesters. Pure PMMA and PMMA containing five and 20 wt% of four different oligoesters are separately prepared using bulk polymerization. The thermal properties of the materials studied using DSC, TG, TG–FTIR and Pyr–GC–MS are presented. The main volatile degradation products identified are CO, HCl, CO₂, H₂O, hexachlorocyclopentadiene, hexachloroendomethylene tetrahydrophthalic acid/anhydride and methyl methacrylate. A detailed mechanism for the influence of the degradation products of HET acid based oligoesters on the thermal degradation of PMMA is also presented.

Ecological Method Development For Detecting N-Nitrosodimethylamine In Water Using Hplc-Pdad, Jolisa Mcday

Master's Theses and Doctoral Dissertations

Using ethanol, a sustainable reversed-phase high-performance liquid chromatographic method with photo-diode array detection (HPLC-PDAD) was investigated to detect sub-parts per billion concentrations of N-nitrosodimethylamine (NDMA) in drinking water and environmental water samples. This presents a practical and “green” option to analytical methods that require laborious derivatization, expensive detectors and unecological solvents.

Mobile phase characteristics, instrument operating parameters, and sample preparation were investigated. Selectivity for NDMA was evaluated using three different C18 columns. Optimal peak resolution and detection were achieved at 231 nm. The limit of detection and quantitation for NDMA was 0.29 μg/mL and 0.96 μg/mL, respectively, with an ethanol …

Quantification Of Short-Chain Fatty Acids In Cecal Material By Gas Chromatography-Mass Spectrometry, Charles Harrison

Master's Theses and Doctoral Dissertations

Probiotic bacteria in the human colon that produce C₂ – C₄ short chain fatty acids (SCFA) and Lactobacillus species that produce lactate in addition to SCFAs are known to have positive health benefits. These organic acids were extracted with ether from murine cecal material (from Dr. Gary Huffnagle, Univ. of Mich.) and derivatized for quantitative measurement by gas chromatography-mass spectrometry. Antibiotic-treated animals gavaged with Candidaalbicans had a lower level of cecal butyrate relative to untreated animals, but a higher level of butyrate when treated mice were also administered Lactobacillus johnsonii NF-1. More recent studies have demonstrated a butyrate-lowering …

Effects Of Silver Nanoparticles On Photochemical Processes Focusing On Luminol Chemiluminescence, Scott Milam

Master's Theses and Doctoral Dissertations

Silver nanoparticles of varying sizes were synthesized. Their effects on enhancing or quenching the photochemical processes of tryptophan fluorescence, a ruthenium complex decay constant and chemiluminescence of luminol and ferricyanide, were studied. The tryptophan fluorescence was slightly enhanced by smaller nanoparticles and showed slight quenching in the presence of larger nanoparticles. The tris (2,2’-bipyridyl ruthenium (II) chloride) complex was excited using a 532 nm laser, and the decay constant was measured. Neither gold nor silver nanoparticles showed an impact on this process. The luminol chemiluminescence was studied with an emphasis on holding the concentration of nanoparticles, surface area, and silver …

Analysis Of The Effect Of Various Ligands On The Hydrolysis Of Ruthenium (Iii) Complexes And Interpretation Of Kinetics Of Hydrolysis Profiles By Uv-Visible Spectrophotometry, Sudheer Koneru

Master's Theses and Doctoral Dissertations

Cancer is one of the major causes of death in the world. Discovery of platinum metal-based drugs like cisplatin and carboplatin have proved to be successful in cancer treatment. Due to subsequent development of resistance, side effects, and fewer toxic effects of these drugs, the usage of these drugs has been limited. Novel drugs were being synthesized utilizing the transition metals like ruthenium, osmium, and copper.

In this research, ruthenium metal complexes of the formula HL[RuCl4L2] (where L= ligand) were synthesized. These ruthenium-based drugs exist in prodrug forms which are activated into antitumor drugs by means of hydrolysis, redox reactions, …

Characterization Of The Binders In The Rock Art Of Cueva La Conga, Nicaragua, Ran Li

Master's Theses and Doctoral Dissertations

Cueva La Conga is the only known painted cave in Nicaragua, in a part of that country about which little is known archaeologically. The rock art, which includes carved rock formations as well as paintings and handprints, may provide clues about the past people and culture of this area. Archaeologists want to know if the paintings were influenced by the Maya to the north, or the Caribbean cultures to the east, or were a purely indigenous development. Determining the age of the paintings will help to understand the possible cultural relationships between known cultures and the rock art of Cueva …

Influence Of Metal Nanoparticles On Fluorescence Properties, Vamsi K. Kandimalla

Master's Theses and Doctoral Dissertations

In this project, we studied the effect of silver and gold nanoparticles of various sizes on the fluorescence properties of tris (2, 2-bipyridyl) dichloro ruthenium (II) hexahydrate (Ru (bpy)3 2+), tryptophan and phenylalanine. For (Ru (bpy)3 2+) absorbed on silver and gold nanoparticles, the fluorescence intensity was quenched and showed a significant increase in the fluorescence lifetimes. These quenched intensities were due to energy transfer processes from the donor (Ru (bpy)3 2+) to the metal nanoparticles. Conversely, tryptophan showed enhanced fluorescence intensities with an increase in the size of the nanoparticles, which may be attributed to the effect of fluorescence …

Structure-Activity Relationships Of Pai-1 Inhibitors, Karen Sanders

Master's Theses and Doctoral Dissertations

The inhibition of plasminogen activator inhibitor-1 (PAI-1) is anticipated to increase our understanding of various human ailments with which high levels of PAI-1 have been associated, including diabetes, stroke, and atherosclerosis. Previous accounts have reported the synthesis of inhibitors that bind to PAI-1 with a low affinity, inhibit the serpin plasma protein antithrombin III, and/or fail to inhibit PAI-1 when vitronectin, a cofactor of PAI-1 is present. The synthesis of small-molecule inhibitors of PAI-1 that improve upon these properties has been the main goal of this research. Research efforts focused on examining changes in inhibitor potency based on the manipulation …

[Introduction To] Ordinary And Particial Differential Equations: An Introduction To Dynamical Systems, John W. Cain, Angela M. Reynolds

Bookshelf

Differential equations arise in a variety of contexts, some purely theoretical and some of practical interest. As you read this textbook, you will find that the qualitative and quantitative study of differential equations incorporates an elegant blend of linear algebra and advanced calculus. This book is intended for an advanced undergraduate course in differential equations. The reader should have already completed courses in linear algebra, multivariable calculus, and introductory differential equations.

Tricarbonylrhenium(I) And Manganese(I) Complexes Of 2-(Pyrazolyl)-4-Toluidine, Brendan J Liddle, Sarath Wanniarachchi, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A series of tricarbonyl rhenium(I) and manganese(I) complexes of the electroactive 2-(pyrazolyl)-4-toluidine ligand, H(pzAn^Me), has been prepared and characterized including by single crystal X-ray diffraction studies. The reactions between H(pzAn^Me) and M(CO)₅Br afford fac-MBr(CO)₃[H(pzAn^Me)] (M = Mn, 1a; Re, 1b) complexes. The ionic species {fac-M(CH₃CN)(CO)₃[H(pzAn^Me)]}(PF₆) (M = Mn, 2a; Re, 2b) were prepared by metathesis of 1a or 1b with TlPF₆ in acetonitrile. Complexes 1a and 1b partly ionize to {M(CH₃CN)(CO)₃[H(pzAn^Me)]^{+ …}

Breaking The Cycle: Impact Of Sterically-Tailored Tetra(Pyrazolyl)Lutidines On The Self-Assembly Of Silver(I) Complexes, Tyler James Morin, Andrew Merkel, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A improved preparation of the pentadentate ligand α,α,α′,α′-tetra(pyrazolyl)lutidine, pz₄lut, and the syntheses of three new alkyl-substituted pyrazolyl derivatives pz^4′₄lut (pz4′ = 4-methylpyrazolyl), pz*₄lut (pz* = 3,5-dimethylpyrazolyl), and pz^DIP₄lut (pzDIP = 3,5-diisopropylpyrazolyl) are described. The silver(I) complexes of these ligands were studied to ascertain the impact of pyrazolyl substitution, if any, on their binding modes and on solubility issues. In the solid state, [Ag(pz₄lut)](BF₄) (1), [Ag(pz^4′4lut)](BF4) (2), and [Ag(pz*₄lut)](BF4) (3 …

Computer Simulation Of Ion-Induced Nucleation In The Presence Of Single Ions And Ion Pairs, Samuel Keasler

LSU Doctoral Dissertations

Atmospheric aerosol particles play an important role in climate and human health. Despite their importance, the mechanisms of their formation are still poorly understood. Ion-induced nucleation may play a role in the process, but details are lacking about how the nucleation rate depends on the size, charge, and number of ions in the cluster. In order to better understand the role that ions might play in new particle formation, we have performed a series of AVUS-HR simulations of the water nucleation in the presence of both single ions and ion pairs. These simulations have shown that the location of the …

Studies Of Small Systems In Quantum Information, Sai Vinjanampathy

LSU Doctoral Dissertations

I study two topics in quantum information theory from the perspective of algebra and geometry. The first relates to exploring the geometry of unitary operators for small quantum systems, specifically three-level systems. Such an understanding of the space over which quantum systems evolve is central to understanding the detailed dynamics of quantum systems and to understand the correlation properties of subsystems that compose a given quantum system. The geometry of unitary operators also allows for the calculation of path-dependent phases called geometric phases. These geometric phases are central to understanding a variety of experiments. I present a general technique, called …

Subgroups Of The Torelli Group, Leah R. Childers

LSU Doctoral Dissertations

Let Mod(Sg) be the mapping class group of an orientable surface of genus g, Sg. The action of Mod(Sg) on the homology of Sg induces the well-known symplectic representation:

Mod(Sg) ---> Sp(2g, Z).
The kernel of this representation is called the Torelli group, I(Sg).

We will study two subgroups of I(Sg). First we will look at the subgroup generated by all SIP-maps, SIP(Sg). We will show SIP(Sg) is not I(Sg) and is in fact an infinite index subgroup of I(Sg). We will also classify which SIP-maps are in the kernel of the Johnson homomorphism and Birman-Craggs-Johnson homomorphism.

Then we will …

Cross-Talk-Free Dual-Color Fluorescence Cross-Correlation Spectroscopy For High-Throughtput Screening, Wonbae Lee

LSU Doctoral Dissertations

High throughput processing of chemical/biochemical information is critical in many areas, such as genome sequencing, drug discovery and clinical diagnostics. Integral to collecting information at high rates with the necessary throughput is the development of systems that can not only monitor the results with high precision and accuracy, but also prepare and process samples prior to the analytical measurement. To achieve the required throughput, we have conducted work directed toward developing a system that provides detection sensitivity at the single-molecule detection (SMD) level. The research was first focused on the development of a sensitive strategy for the detection of proteins …

Analysis And Modeling Of Hurricane Impacts On A Coastal Louisiana Lake Bottom, Angelina Freeman

LSU Doctoral Dissertations

Tropical cyclone impacts on wetland, terrestrial, and shelf systems have been previously studied and reasonably delineated, but little is known about the response of coastal lakes to storm events. For the first time, tropical cyclone impacts on a shallow coastal lake in the Louisiana coastal plain have been studied using direct lines of evidence and numerical modeling. Using side-scan sonar, CHIRP subbottom and echo sounder bathymetric profiles, the lake bottom and shallow subsurface of Sister Lake was imaged pre- and post-Hurricanes Katrina and Rita to provide a geologic framework for assessing the effects of these storms. Box cores were collected …