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Analysis Of Novel Cyanide Antidote Dimethyl Trisulfide For Pharmacokinetic Studies, And Sulfur Mustard Metabolites For Identification Of Biomarker Of Inhaled Dose, Erica Manandhar Jan 2017

Analysis Of Novel Cyanide Antidote Dimethyl Trisulfide For Pharmacokinetic Studies, And Sulfur Mustard Metabolites For Identification Of Biomarker Of Inhaled Dose, Erica Manandhar

Electronic Theses and Dissertations

Cyanide poisoning by accidental or intentional exposure poses a severe health risk. The current FDA approved antidotes for cyanide poisoning can be effective, but each suffers from specific major limitations. Dimethyl trisulfide (DMTS), a sulfur donor that detoxifies cyanide by converting it into thiocyanate, is a promising next generation cyanide antidote. Although a validated analytical method to analyze DMTS is not currently available from any matrix, one will be vital for the approval of DMTS as a therapeutic agent against cyanide poisoning. Hence, a stir bar sorptive extraction (SBSE) gas chromatography – mass spectrometry (GC-MS) method was developed and validated …


Mechanistic Insights Into The Radical S-Adenosyl L-Methionine Enzyme Mftc, Bulat Khaliullin Jan 2017

Mechanistic Insights Into The Radical S-Adenosyl L-Methionine Enzyme Mftc, Bulat Khaliullin

Electronic Theses and Dissertations

Mycofactocin is a putative peptide-derived redox cofactor in Mycobacterium family. Its putative biosynthetic pathway is encoded by the operon mftABCDEF. The initial step of this pathway is a posttranslational modification of a peptide precursor MftA, which is catalyzed by MftC enzyme. This modification only occurs in the presence of chaperone MftB. Here, we demonstrate that MftC is a radical S-adenosyl L-methionine (SAM) enzyme and we examine its catalytic mechanism. We show that the modification of MftA requires two equivalents of SAM and is implemented in two steps: (i) the decarboxylation of a C-terminal tyrosine, resulting in formation of an …


Sequential Growth Of Molecular Complexity Via Alternating Ground State And Photochemical Reactions, Haibo Li Jan 2017

Sequential Growth Of Molecular Complexity Via Alternating Ground State And Photochemical Reactions, Haibo Li

Electronic Theses and Dissertations

A new strategy of increasing molecular complexity by post photochemical oxidation followed by secondary intramolecular photochemical reaction is developed. It is based on the mild oxidation of photochemical generated alcohol by primary intramolecular cycloaddition of aromatic o-aminoaldehydes and a secondary intramolecular cycloaddition of aromatic o-aminoketone. Both cycloadditions are triggered via excited-state intramolecular proton transfer (ESIPT). Additionally, an efficient continuous reaction of photocatalyzed 2-nitrobenzyl alcohol intramolecular reduction and aryl nitroso Diels-Alder (NDA) reaction was discovered.


Improved Characterization And Analysis Strategies For Uv-Lif Bioaerosol Instrumentation: Lab And Field Application, Nicole Justine Savage Jan 2017

Improved Characterization And Analysis Strategies For Uv-Lif Bioaerosol Instrumentation: Lab And Field Application, Nicole Justine Savage

Electronic Theses and Dissertations

Atmospheric particles of biological origin, also referred to as bioaerosols or primary biological aerosol particles (PBAP), are important to various human health and environmental systems. There has been a recent steep increase in the frequency of published studies utilizing commercial instrumentation based on ultraviolet laser/light-induced fluorescence (UV-LIF), such as the WIBS (wideband integrated bioaerosol sensor), for bioaerosol detection both outdoors and in the built environment. Significant work over several decades supported the development of these technologies, but efforts to systematically characterize the operation of new commercial sensors has remained lacking. Specifically, there are gaps in the understanding of how different …


Quantification Of Airborne Fungal Spores Comparing Molecular Tracers Via Ion Chromatography And Uv-Lif Methods, Marie Ila Gosselin Jan 2017

Quantification Of Airborne Fungal Spores Comparing Molecular Tracers Via Ion Chromatography And Uv-Lif Methods, Marie Ila Gosselin

Electronic Theses and Dissertations

Fungal spores represent an understudied subcategory of bioaerosols that can impact human health as pathogenic and allergenic particles. Fungal spores also have been shown to act as effective ice nuclei and giant cloud condensation nuclei in some cases. This has implications on the hydrological cycle on local and regional scales by impacting the formation and evolution of clouds and precipitation. The quantification of fungal spores has been limited in the past due to methods that were costly and that suffered from poor time resolution. The most commonly applied methods for airborne fungal spore analysis have traditionally included microscopy and culturing, …


Investigating The Atmospheric Production Of Perchlorate: Inference From Polar Ice Cores, Thomas S. Cox Jan 2017

Investigating The Atmospheric Production Of Perchlorate: Inference From Polar Ice Cores, Thomas S. Cox

Electronic Theses and Dissertations

Perchlorate (ClO4) in the environment is of concern, because of potential health risks to humans, among other reasons. Evidence suggests that the majority of environmental perchlorate is formed in the atmosphere (likely in the stratosphere), in chemical processes involving ozone and stratospheric chlorine. A lack of knowledge in regards to the processes has resulted in a limited understanding of the environmental conditions and variables that influence perchlorate production and consequently perchlorate prevalence and variability in the environment. In this study, perchlorate was measured, using an established ion chromatography-­‐electrospray ionization-­‐tandem mass spectrometry (IC-­‐ESI-­‐ MS/MS) technique, in over 1,600 snowpit …


Improvement And Development Of Analytical Forensic Methods: Arson Investigation And Drug Detection In Fingerprints And Hair, Sarah Anne Glenn Jan 2017

Improvement And Development Of Analytical Forensic Methods: Arson Investigation And Drug Detection In Fingerprints And Hair, Sarah Anne Glenn

Electronic Theses and Dissertations

Forensic science is the cornerstone of criminal investigations. Due to the overexposure of forensic science in the media, the true nature of forensic science is often overlooked. Forensic science is a rigorous exacting science that applies methods developed in the wider scientific community to the analysis of evidence collected from crime scenes. As far back as the 6th century people were using forensics to solve crimes. Since then the science behind forensic science has increased exponentially with new methods being researched and developed. This research aims to address two of the larger subsections of forensic science, arson and drug detection. …


Detection Of Inorganic Phosphate In Environmental Water Samples Using A Terbium And Gold Nanoparticle-Based Fret Chemosensor, Madeleine Johnson Jan 2017

Detection Of Inorganic Phosphate In Environmental Water Samples Using A Terbium And Gold Nanoparticle-Based Fret Chemosensor, Madeleine Johnson

Electronic Theses and Dissertations

A novel chemosensor for the detection of inorganic phosphate (Pi) in environmental water samples is outlined. The sensing solution is comprised of a luminescent lanthanide, terbium (Tb3+), chelated to ethylenediaminetetraacetic acid (EDTA) acid in solution with cetyltrimethylammonium bromide (CTAB)- capped gold nanoparticles (AuNPs). The Tb-EDTA and AuNPs undergo a Fluorescence resonance energy transfer (FRET) mechanism in which the Tb3+ luminescence is quenched. Upon the addition of inorganic phosphate (Pi), the AuNPs begin to aggregate and precipitate out of solution. The aggregation of AuNPs results in the restoration of the Tb-EDTA signal which can then be correlated to Pi concentration in …


A Deoxyribozyme Sensor And Isothermal Amplification For Human Sex Determination, Alexandra Smith Jan 2017

A Deoxyribozyme Sensor And Isothermal Amplification For Human Sex Determination, Alexandra Smith

Electronic Theses and Dissertations

Ribozymes are known to catalyze biochemical reactions and behave like enzymes. They are naturally occurring and have very diverse functions within a cell. After investigating ribozymes that next step was to find if DNA can exhibit the same characteristics since RNA and DNA only differ by a ribose 2'-hydroxyl group. This evolution in curiosity gave rise to artificial DNA enzymes that can catalyze certain reactions and have been created by in vitro selection methods. Due to the ability to manipulate and control DNA hybridization, the deoxyribozyme is advantageous to the field of molecular diagnostics. Other hybridization probes like Taqman for …


Design, Synthesis And Biological Screening Of Novel Cucsinspired Estrone Analogues Towards Treatment Of Hepatocellular Carcinoma, Mater Hussen Mahnashi Jan 2017

Design, Synthesis And Biological Screening Of Novel Cucsinspired Estrone Analogues Towards Treatment Of Hepatocellular Carcinoma, Mater Hussen Mahnashi

Electronic Theses and Dissertations

Cucurbitacins (CUCS) are natural products with highly oxygenated tetracyclic triterpenes produced mostly by Cucurbitaceae family plant. They are known for their therapeutic efficiency with different biological activities, such as anti-inflammatory, hepatoprotective and anti-cancer. Hepatocellular carcinoma (HCC) is the third leading cause of death worldwide. Previous reports have shown the ability of CUCS to inhibit the growth of hepatocellular carcinoma cell lines (HepG-2) significantly. Structural activity relationship studies suggested the potential of the 23, 24 enone side chain of CUCS to bind to the Epidermal Growth Factor Receptor (EGFR). Due to the limited quantities of CUCS upon isolation and the challenges …


The Analysis Of Flavor Compounds In Green Tea Using Ice Concentration Linked With Extractive Stirrer (Icecles), Abdullah H. Alluhayb Jan 2017

The Analysis Of Flavor Compounds In Green Tea Using Ice Concentration Linked With Extractive Stirrer (Icecles), Abdullah H. Alluhayb

Electronic Theses and Dissertations

Sample preparation of target components from food samples is one of the most difficult steps in this type of analysis. Many extraction techniques have been used for this purpose, such as liquid-liquid extraction (LLE), accelerated solvent extraction (ASE), microwave-assisted extraction (MAE), solid-phase extraction (SPE), solid-phase microextraction (SPME), and stir bar sorptive extraction (SBSE). Although each of these techniques works well, they each have a number of disadvantages, including selectivity, relatively high cost, long preparation time, and matrix effects. Ice concentration linked with extractive stirrer (ICECLES) is a promising new sample preparation technique, especially for the extraction of relatively polar compounds, …


The Relationship Between Recollection, Knowledge Transfer, And Student Attitudes Towards Chemistry, Oluwatobi Omobonike Odeleye Jan 2017

The Relationship Between Recollection, Knowledge Transfer, And Student Attitudes Towards Chemistry, Oluwatobi Omobonike Odeleye

Electronic Theses and Dissertations

Certain foundational concepts, including acid-base theory, chemical bonding and intermolecular forces (IMFs), appear throughout the undergraduate chemistry curriculum. The level of understanding of these foundational concepts influences the ability of students to recognize the relationships between sub-disciplines in chemistry. The purpose of this study was to investigate the relationship between student attitudes towards chemistry and their abilities to recollect and transfer knowledge of IMFs, a foundational concept, to their daily lives as well as to other classes. Data were collected using surveys, interviews and classroom observations, and analyzed using qualitative methods. The data show that while most students were able …


Α-Eleostearic Acid Extraction By Saponification Of Tung Oil And Its Subsequent Polymerization, Amanda Murawski Jan 2017

Α-Eleostearic Acid Extraction By Saponification Of Tung Oil And Its Subsequent Polymerization, Amanda Murawski

Electronic Theses and Dissertations

The goal of environmentally sound research is to provide alternatives that are more sustainable and renewable, such as vegetable oil-based polymers, than the current petroleum-based products. Vegetable oil-based polymers have received a lot of attention recently due their multifaceted properties, which are simply achieved by adjusting the monomer or resin composition. The carbon-carbon double bonds in unsaturated oils are ideal reactive sites for the free radical or cationic polymerizations. Most vegetable oils must be modified before polymerization due to the low reactivity of their non-conjugated fatty acid chains. Tung oil (TO) contains ~83% of a triply conjugated fatty acid ( …


Investigation Of The Effects Of Ionic Interactions In Peptide And Protein Structure, Aimee Lorts Jan 2017

Investigation Of The Effects Of Ionic Interactions In Peptide And Protein Structure, Aimee Lorts

Electronic Theses and Dissertations

Proteins and their unique structures are important due to their involvement in every cellular task, but the protein can only function properly when it is in the correct fold. β-sheet peptides and collagen were observed via structural studies. Circular dichroism (CD) determines a protein’s secondary structure. WKWK, a beta-sheet peptide, is known to dissolve in aqueous solutions. However, WKWK was observed to precipitate out of deionized water. To investigate the cause of this precipitation, Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) was used to determine the ion content of the water. Elevated sodium ion concentrations were found to disrupt the stabilizing …


Assessment Of Short-Term Toxicity Of Titanium Dioxide Nano Fiber (Tdnf) In Sprague Dawley Rats, Daniel A. Hunter Jan 2017

Assessment Of Short-Term Toxicity Of Titanium Dioxide Nano Fiber (Tdnf) In Sprague Dawley Rats, Daniel A. Hunter

Electronic Theses and Dissertations

Nanotechnology is easily becoming one of the fastest growing markets around the globe. Synthetic nanomaterials have many unique chemical and physical properties, mainly due to their huge specific surface area and chemical makeup. Specifically, titanium dioxide (TiO2) nanomaterials have high stability, anticorrosive and photocatalytic properties. These nanomaterials have applications for semiconductor photocatalysis, treatment of water, as a photoactive material in nanocrystalline solar cells, and medicine. However, not much is known about the toxicity of TiO2 in the nanofiber form. The objective of the present study is to investigate the adverse effects associated with acute ingestion of TiO …


Asymmetric Membranes For High Capacity Lithium-Ion Battery Electrodes, Ian Byrd Jan 2017

Asymmetric Membranes For High Capacity Lithium-Ion Battery Electrodes, Ian Byrd

Electronic Theses and Dissertations

Lithium-Ion Batteries (LIBs) have broad applications such as portable electronic devices, electric vehicles, and for green energy storage from intermittent sources. Current LIBs are limited by their low capacity materials at both the anode and cathode. At the anode, graphite suffers from a low capacity of only 372 mAh g-1. The most commonly used cathode material is LiCoO2 which has a meager capacity of 140 mAh g-1. Thereby the broader applications of LIBs are limited due to these low capacities. It is imperative to develop higher capacity materials to further improve the performance of LIBs. …


Relationship Of The Fractal And Chemical Characteristics Of Self-Assembled Natural Organic Matter, Dennis K. Gibson Jan 2017

Relationship Of The Fractal And Chemical Characteristics Of Self-Assembled Natural Organic Matter, Dennis K. Gibson

Electronic Theses and Dissertations

Natural Organic Matter (NOM) is a heterogeneous mixture formed by the degradation of organic substances during early diagenesis in surficial environments. It has been shown that the interaction of the components that comprise this mixture has a significant impact on its microbial mineralization to CO2. The extent of NOM selfassembly is emerging as an important factor in understanding its role in the global geochemical carbon cycle, and it is beginning to appear that it may be more important than the chemical composition of a sample. The overall goal of this research is to establish NOM’s self-assembled “architecture” and …


Self-Assembled Architecture Of Natural Organic Matter, Cynthia Johnson-Edler Jan 2017

Self-Assembled Architecture Of Natural Organic Matter, Cynthia Johnson-Edler

Electronic Theses and Dissertations

This investigation focuses on the determination of the architecture of the natural organic matter (NOM) contained within a soft coal-like material, an agricultural soil and a peat material. NOM has been extracted from bulk materials, fractionated, reassembled, then characterized by 13C Solid State NMR, Pulsed-Field Gradient NMR (PFG-NMR), and Small Angle Neutron Scattering (SANS). Interpretation of the data obtained by SANS has established that the majority of the components of NOM are mass fractals in solution and surface fractals in the solid state. Surface-to-volume ratios calculated with PFGNMR data indicate the NOM components studied have varying disk-like shapes. These …


Deep Eutectic Solvents Synthesis, Characterization And Applications In Pretreatment Of Lignocellulosic Biomass, Ganesh Degam Jan 2017

Deep Eutectic Solvents Synthesis, Characterization And Applications In Pretreatment Of Lignocellulosic Biomass, Ganesh Degam

Electronic Theses and Dissertations

There has been an increased interest in green solvents and biofuels with the growing environmental awareness across the globe. Conventional methods of biofuel production involve the use of large quantities of molecular solvents and ionic liquids (ILs), but they have the drawbacks of high vapor pressure (organic solvents), toxicity, and recyclability in terms of a sustainability point of view. Deep eutectic solvents (DESs) have recently emerged as green alternatives to molecular solvents and ionic liquids (ILs). They are defined as eutectic mixtures formed between quaternary ammonium, phosphonium or sulfonium salts and hydrogen bond donors (HBDs) with the freezing temperature lower …


Comprehensive Structural, Thermal And Toxicological Characterization Of 1-Ethyl-3-Methylimidazolium Alkylbenzenesulfonate Ionic Liquids, Hiranmayee Kandala Jan 2017

Comprehensive Structural, Thermal And Toxicological Characterization Of 1-Ethyl-3-Methylimidazolium Alkylbenzenesulfonate Ionic Liquids, Hiranmayee Kandala

Electronic Theses and Dissertations

Synthesis and characterization of 1-ethyl-3- methylimidazolium alkylbenzenesulfonate ionic liquids for extraction of lignin from prairie cord grass have been studied. The ionic liquids (ILs) 1-ethyl-3- methylimidazolium benzenesulfonate (EBS), 1-ethyl-3- methylimidazolium toluenesulfonate (ETS) and 1-ethyl-3- methylimidazolium xylenesulfonate (EXS) have been synthesized in this research. An extensive structural, physical, thermal and toxicological characterization has been performed to understand the behavior of these ionic liquids. The reaction yield for the synthesis of EBS, ETS, and EXS ionic liquids was determined to be 91.2 ± 1.5 %, 96.1 ± 0.7 %, 99.0 ± 0.5 % respectively. Spectral analysis using NMR and FTIR confirms the …


Cbl And Cbl-B Dictate Csf-1r Endocytic Traffic And Signaling In Macrophages, Lu Huang Jan 2017

Cbl And Cbl-B Dictate Csf-1r Endocytic Traffic And Signaling In Macrophages, Lu Huang

Electronic Theses and Dissertations

Macrophage colony stimulating factor receptor (CSF-1R or MCSFR) is a receptor tyrosine kinase essential for the growth and function of macrophages. Understanding the mechanisms that regulate CSF-1R activation and deactivation will provide insights to clinical treatment of macrophage related diseases including chronic inflammation and cancer. Previously, our laboratory showed that CSF-1R undergoes a novel membrane trafficking route that involves macropinocytosis to deactivate CSF-1R signaling. This thesis makes the discovery that the ubiquitin ligases Cbl and Cbl-b cooperate to regulate CSF-1R endocytosis and traffic to macropinosome in macrophages. Macrophages were derived from mice knocked out for Cbl, Cbl-b or the double …


A Quantum Astrochemical Perspective On The C-C3h Radical With Application To The Interstellar Medium, Matthew Bassett Jan 2017

A Quantum Astrochemical Perspective On The C-C3h Radical With Application To The Interstellar Medium, Matthew Bassett

Electronic Theses and Dissertations

The interstellar medium (ISM) has been an area of focus for astrochemists and quantum chemists for many years, with particular interest in the presence of interstellar molecules and the resulting chemical processes. The c-C3H radical has been detected in the ISM near the dark molecular cloud TMC-1. With the application of ab initio computational methods using coupled-cluster theory at the singles, doubles, and perturbative triples [CCSD(T)] level, highly accurate quartic force fields (QFFs) are constructed to define the electronic wavefunction for the inter nuclear Hamiltonian. The QFF is used to predict the equilibrium geometry and produce vibrational frequencies, rotational constants, …


Synthesis And Biological Activity Of Novel Tu100 Derivatives, Oladotun J. Alao Jan 2017

Synthesis And Biological Activity Of Novel Tu100 Derivatives, Oladotun J. Alao

Electronic Theses and Dissertations

In an attempt to create more effective chemotherapeutic compounds, the naphthoquinone adduct, 12,13-dihydro-N-methyl-6,11,13-trioxo-5H-benzo[4,5]cyclohepta [1,2 b]naphthalen-5,12-imine (hereafter called TU100) was synthesized. Inspired by its unique and novel mechanism of action, a series of structural derivatives were synthesized to explore structure-activity relationships. The analogues exhibited different cytotoxicity profiles, revealing the indicated regions are involved in cell death induction. Furthermore, the analogues had dramatically different effects on cellular ATP production, suggesting different molecular targets. Synthesis, biological activity, and SAR study of these analogues will be revealed.


Approaches Toward Novel 1,2,3-Triazole Sensors For The Detection Of Anions And Heavy Metal Cations, Richard D. Govan Jan 2017

Approaches Toward Novel 1,2,3-Triazole Sensors For The Detection Of Anions And Heavy Metal Cations, Richard D. Govan

Electronic Theses and Dissertations

Cations and anions play pivotal roles in biological and physiological processes, however an imbalance in concentration of any ion can be detrimental. Therefore, research into the selective recognition of anions and heavy metal cations has acquired much attention. One approach involves the use of chemosensors. Upon interaction with targeted analytes, chemosensors produce a distinct response, in some cases a fluorescent or colorimetric signal. The 1,2,3-triazole unit has much potential as a chemical sensor due to its unique photophysical properties. The specificity, selectivity, and signaling mechanism of triazole sensors can be tuned with conjugation in the motif and choice and placement …


Impact Of Timber Harvest On Mercury Mobilization In A Mixed Pine And Hardwood Forest And Adjacent Lake In Mississippi, Mary Kristen Dickerson Jan 2017

Impact Of Timber Harvest On Mercury Mobilization In A Mixed Pine And Hardwood Forest And Adjacent Lake In Mississippi, Mary Kristen Dickerson

Electronic Theses and Dissertations

With 65% of land area covered in forest, Mississippi is a leader in the timber industry. Whereas forestry provides numerous benefits for humans and wildlife, forest harvest has been hypothesized to increase mercury (Hg) mobilization to aquatic systems. In a forest, Hg mostly accumulates in the upper layer of soil, where associates with organic matter. This top soil is exposed after clear-cutting and thus more susceptible to runoff. Harvest may also change the net balance between Hg methylation and demethylation by microorganisms through changes in redox conditions and addition of carbon sources from decaying logging residues. To better understand the …