Chemistry Commons^™

The Effects Of Membrane Physicochemical Properties On Huntingtin Membrane Association And Downstream Aggregation, Maryssa Beasley

Graduate Theses, Dissertations, and Problem Reports (ETD)

Huntington’s Disease (HD) is a fatal neurodegenerative disorder caused by an expanded glutamine repeat region (polyQ) within the huntingtin protein (htt). As a result of the expanded polyQ domain, htt associates into a variety of toxic aggregate species. The polyQ domain of htt is flanked at the N-terminal end by 17 amino acids (Nt17) that adopt an amphipathic α-helical structure in the presence of binding partners such as lipid membranes. In addition to comprising a lipid binding domain, the Nt17 amphipathic α -helix has been directly implicated in htt aggregation initiation via self-association with other Nt17 α -helices. Due to …

Synthesis, Structures, Optical And Electronic Properties Of Functional Inorganic And Hybrid Materials, Sura Menda Ginting

Graduate Research Theses & Dissertations

Synthesis of complex functional inorganic and hybrid material is desirable because complex composition allows more degree of freedom and tunable materials where the properties differ from those of their parent components. As a test of concept, we have synthesized a series of LnMOFs with the general formula of [Ln(NDC)(DMA)2(NO3)]n (Ln=Ce, Nd, Sm, Eu, Tb, Yb). These materials are isostructural, adopting the orthorhombic P b c a space group. They are relatively stable under drying and heating treatment and have more metal coordination numbers compared to transition metal MOFs. There are theoretically sizable channels and free space inside the structure, allowing …

Screening Of Catalysts For The Subcritical Water Depolymerization Of Lignin, Balawanthrao Jadhav

Electronic Theses and Dissertations

The current world population is completely rely on the non-renewable resources such as coal, fossils, and natural gas to get the energy, fuel and value-added chemicals. The increasing the demand of utilizing non renewable resources leads to severe problems such as global warming, climate changes, and environmental pollution. The renewable resources such as wind, solar energy, and biomass is an alternative sources to overcome these problems and to save the environment. Biomass made up with the cellulose, hemicellulose, and Lignin. Lignin is a copolymer of phenolic monomers and inexpensive naturally occurring complex material to produce the value-added chemicals and various …

Development And Validation Of Advanced Analytical Methods For Pesticides, Per- And Polyfluoroalkyl Substances, And Opioids In Soil And Drinking Water, Christopher Skaggs

Electronic Theses and Dissertations

Environmental pollution from contaminants is a serious concern in a world where more and more pesticides and pharmaceuticals are being used, sometimes improperly and in excess. Since pesticides are used on practically every crop on Earth, it’s no surprise that these compounds are detected in soil, water, and processed agricultural commodities meant for human consumption. Additionally, because of the ubiquity of pharmaceuticals, specifically opioids, and their inherent addictive properties, these compounds are being over-consumed. Because current waste-water treatments can be insufficient to remove them from water sources, this consumption has led to the detection of these compounds in drinking water. …

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.

Structural Annotation Of Electro- And Photochemically Generated Transformation Products Of Moxidectin Using High-Resolution Mass Spectrometry, Lisa Kotthoff, Sarah-Louise O'Callaghan, Jan Lisec, Tanja Schwerdtle, Matthias Koch

Articles

Moxidectin (MOX) is a widely used anthelmintic drug for the treatment of internal and external parasites in food-producing and companion animals. Transformation products (TPs) of MOX, formed through metabolic degradation or acid hydrolysis, may pose a potential environmental risk, but only few were identified so far. In this study, we therefore systematically characterized electro- and photochemically generated MOX TPs using high-resolution mass spectrometry (HRMS). Oxidative electrochemical (EC) TPs were generated in an electrochemical reactor and photochemical (PC) TPs by irradiation with UV-C light. Subsequent HRMS measurements were performed to identify accurate masses and deduce occurring modification reactions of derived TPs …

September 2019 Therapeutic Delivery Update, Elaine Harris

Articles

No abstract provided.

Determination Of Upconversion Quantum Yields Using Charge-Transfer State Fluorescence Of Heavy-Atom-Free Sensitizer As A Self-Reference, Natalia Kiseleva, Dmitry Busko, Bryce Richards, Mikhail Filatov, Andrey Turshatov

Articles

The efficiency of photon upconversion via triplet–triplet annihilation is characterized by an upconversion quantum yield (Φ_UC); however, uncertainties remain for its determination. Here, we present a new approach for the relative measurement of Φ_UC for green-to-blue upconversion using BODIPY–pyrene donor–acceptor dyad (BD1) as a heavy-atom-free triplet sensitizer. This new approach exploits broad fluorescence from a charge-transfer (CT) state of BD1, which possesses (i) a significant Stokes shift of 181 nm in dichloromethane and (ii) a comparably high CT-fluorescence quantum yield (Φ_ref = 7.0 ± 0.2%), which is independent from oxygen presence and emitter (perylene) concentration while …

Exploration Of Cis-1,2-Diaminocyclohexane-Based Conformationally Locked Chiral Ligands In Asymmetric Synthesis, Carim Van Beek

University of the Pacific Theses and Dissertations

Natural products have been demonstrated to be of great significance to the pharmaceutical industry in the development of new drugs and medicine. Unfortunately, synthetic approaches to obtain these natural products often prove increasingly challenging due to the complexity of synthesizing the target drug in the proper stereochemistry. The availability of enantioselective reactions can play a pivotal role in overcoming this challenge, yielding access to optically pure intermediates and products. Chiral ligands based on a trans-1,2-diaminocyclohexane motif are often employed for this purpose and their complexes with transition metals have been demonstrated to act as efficient chiral catalysts in asymmetric reactions. …

Development And Implementation Of A Novel Voltage-Free Interface For Capillary Electrophoresis-Mass Spectrometry Separations Of Proteins, Courtney J. Kristoff

Graduate Theses, Dissertations, and Problem Reports (ETD)

Capillary electrophoresis-mass spectrometry is a powerful technique for high-throughput and high efficiency separations combined with structural identification. Electrospray ionization is the primary interface used to couple capillary electrophoresis to mass analyzers; however, improved designs continue to be reported. A new interfacing method based on vibrating sharp-edge spray ionization is presented in this work to overcome the challenges of decoupling applied voltages and to enhance the compatibility with separations performed at near-neutral pH. The versatility and ease of use of this ionization source is demonstrated using β-blockers, peptides, and proteins. The cationic β-blocker pindolol was injected electrokinetically and detected at concentrations …

Silver-Mediated Decarboxylation Reactions: Expanding Reaction Scope Through Kinetic Analysis, Robert Anthony Crovak

Graduate Theses, Dissertations, and Problem Reports (ETD)

Transition metal-catalyzed decarboxylative coupling reactions have received considerable attention in recent years as a method to obtain biaryl compounds. However, the oxidative version of this reaction class is still in its infancy, limited to specific substitution patterns on the benzoic acids – ortho-substitution - used in these transformations. This thesis describes our attempts to understand the key decarboxylation step of this important class of reactions. The first chapter of this thesis discusses an introduction into cross-coupling reactions, decarboxylative cross-coupling reactions, and outlines relevant physical organic parameters. The following chapter details the synthesis of a series of (1,10-phenanthroline)silver(benzoate) complexes. This chapter …

Synthesis And Characterization Of Pyridine Dipyrrolide Iron Complexes Relevant To Nitrene And Carbene Group Transfer, Brett M. Hakey

Graduate Theses, Dissertations, and Problem Reports (ETD)

The synthesis and electronic structures of the square-planar high-spin Fe^II complexes (^MesPDP^Ph)Fe(OEt₂) and (^MesPDP^Ph)Fe(thf) were investigated. Analysis of these compounds using a combination of ¹H NMR and ⁵⁷Fe Mössbauer spectroscopies, in conjunction with computational analysis, has resulted in a rationalization for their unusual electronic structures, which arise from the unique coordination environment enforced by the pyridine dipyrrolide chelate ligand.

The reactivity of (^MesPDP^Ph)Fe(thf) with organic azides has been probed and resulted in the isolation of an array of products that are consistent with …

Protein/Peptide Characterization Using Mass Spectrometry And Molecular Dynamics Simulations, Ahmad Kiani Karanji

Graduate Theses, Dissertations, and Problem Reports (ETD)

Mass spectrometry (MS) based-techniques and molecular dynamics (MD) simulations have been used to characterize protein/peptide structure as well as their interactions with lipid vesicles and detergents. Chapter 1 introduces an introduction to the concepts and tools that were used in this work. In Chapter 2, the dominant gas-phase conformer of [M+3H]3+ ions of the model peptide Acetyl-PSSSSKSSSSKSSSSKSSSSK are examined with ion mobility spectrometry (IMS), gas-phase hydrogen deuterium exchange (HDX), and mass spectrometry (MS) techniques. This section furthers the development of a protein structural prediction tool by providing information about gas-phase ion conformers of two model peptides having different solution conformational …

Synthesis Of Graphene Using Plasma Etching And Atmospheric Pressure Annealing: Process And Sensor Development, Andrew Robert Graves

Graduate Theses, Dissertations, and Problem Reports (ETD)

Having been theorized in 1947, it was not until 2004 that graphene was first isolated. In the years since its isolation, graphene has been the subject of intense, world-wide study due to its incredibly diverse array of useful properties. Even though many billions of dollars have been spent on its development, graphene has yet to break out of the laboratory and penetrate mainstream industrial applications markets. This is because graphene faces a ‘grand challenge.’ Simply put, there is currently no method of manufacturing high-quality graphene on the industrial scale. This grand challenge looms particularly large for electronic applications where the …

The Development Of Pet Imaging Agents For Neurodegenerative Disorders, Christine Morgan Kinstedt

Browse all Theses and Dissertations

With the intent to synthesize a potent and viable PET imaging agent for Alzheimer’s disease and/or Parkinson’s disease utilizing tau protein aggregates or alpha-synuclein aggregates as the ailments’ respective targets, researchers in this investigation synthesized derivatives of the chalcone scaffold in order to determine a lead molecule for further drug development. This molecular structure, which due to its ability to cross the blood brain barrier (BBB), has demonstrated efficiency in a number of neurodegenerative diseases and constitutes a convenient starting point for the development of potential imaging agents for Alzheimer’s and Parkinson’s diseases. Since simple chalcones have been demonstrated to …

Capillary Electrophoresis Analysis Of Proteins Using Phospholipid Based Materials, Cassandra L. Crihfield

Graduate Theses, Dissertations, and Problem Reports (ETD)

Capillary electrophoresis has many advantages that make it a powerful technique for the analysis of proteins, which is challenging due to the natural heterogeneity of proteins. The small sample volume required for each analysis (nano- and pico-liter), fast separation times (<30 >min), and ability to couple the separation to mass spectrometry are all factors that make capillary electrophoresis an ideal technology for protein separations. Capillary zone electrophoresis and capillary gel electrophoresis are the two most commonly employed modes for protein analysis and allow for rapid, high resolution separations that can be automated. This makes capillary electrophoresis ideal for meeting the …

Genetic And Biochemical Characterization Of Ergot Alkaloid Synthesizing Fungi And Their Symbionts, Matthew Duane Maust

Graduate Theses, Dissertations, and Problem Reports (ETD)

Ergot alkaloids are fungal tryptophan derived toxins which affect mammalian circulation and neurotransmission. These compounds are biosynthesized by a conserved genetic pathway, known as the ergot alkaloid synthesis (EAS) pathway by fungi belonging to the ascomycete families Trichocomaceae and Clavicipitaceae. Several Ipomoea species and related plants in the morning glory family harbor vertically transmitted symbiotic fungi in the genus Periglandula, also members of Clavicipitaceae, that produce ergot alkaloids. Metabolomic analysis of seeds identified a previously uncharacterized glycoside form of the pharmaceutically important ergot alkaloid, ergonovine. Several species belonging to the fungal genus Metarhizium have recently been shown to have the …

Cobalt-Catalyzed Aerobic Oxidative Cyclization Reactions Of Bisnucleophiles: New Methodologies And The Role Of Bisnucleophiles In O2 Activation, Jiaqi Liu

Graduate Theses, Dissertations, and Problem Reports (ETD)

Over the past few decades, transition metals have found wide applications in the development of selective oxidative transformations mediated by molecular oxygen. Due to the benign nature of molecular oxygen as an oxidant and an increasing awareness of green chemistry practice, tremendous progress has been made towards the development of Cu-and Pd-catalyzed aerobic oxidation reactions. As a first-row transition metal alternative to copper, cobalt has been employed in aerobic catalytic transformations for its cost-efficiency and earth abundance; however, redox-active mediators such as benzoquinone (BQ), N-hydroxyphthalimide (NHPI) or salen-type ligands are usually required. To date, reactions mediated by Co/O₂ catalytic …

Design, Synthesis, And Characterization Of Chemical Tools To Study Peroxisomal Import, Jhalak N. Timilsena

Masters Theses

Peroxisomes are dynamic and interconnected single lipid membrane bound organelles found in the eukaryotic cells which are involved in various biochemical processes including the b-oxidation of very long chain and branched chain fatty acids, metabolism of reactive oxygen and nitrogen species, and reduction of hydrogen peroxide among others. These organelles are known to host numerous proteins and enzymes depending on the cellular environment. All of the proteins needed in the peroxisomes are encoded in the nucleus and synthesized in the cytosol which are then transported to the peroxisomes with the help of a sophisticated protein-transport machinery. Pex5 is one of …

Chronic Chemogenetic Stimulation Of The Nucleus Accumbens Produces Lasting Reductions In Binge Drinking And Ameliorates Alcohol-Related Morphological And Transcriptional Changes, Dar'ya Y. Pozhidayeva, Sean Farris, Calla Goeke, Evan Firsick, Kayla G. Townsley, Marina Guizzetti, Angela Ozburn

Chemistry Faculty Publications and Presentations

Binge drinking is a dangerous pattern of behavior. We tested whether chronically manipulating nucleus accumbens (NAc) activity (via clozapine-N-oxide (CNO) and Designer Receptors Exclusively Activated by Designer Drugs (DREADD)) could produce lasting eects on ethanol binge-like drinking in mice selectively bred to drink to intoxication. We found chronically increasing NAc activity (4 weeks, via CNO and the excitatory DREADD, hM3Dq) decreased binge-like drinking, but did not observe CNO-induced changes in drinking with the inhibitory DREADD, hM4Di. The CNO/hM3Dq-induced reduction in ethanol drinking persisted for at least one week, suggesting adaptive neuroplasticity via transcriptional and epigenetic mechanisms. Therefore, we defined this …

Daily Stream Samples Reveal Highly Complex Pesticide Occurrence And Potential Toxicity To Aquatic Life, Julia E. Norman, Barbara J. Mahler, Lisa H. Nowell, Peter C. Van Metre, Mark W. Sandstrom, Mark A. Corbin, Yaorong Qian, James F. Pankow, Wentai Luo, Nicholas B. Fitzgerald, Multiple Additional Authors

Chemistry Faculty Publications and Presentations

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10–14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in …

A Simple Predictive Model For Estimating Relative E-Cigarette Toxic Carbonyl Levels, Shawna Vreeke, Xijing Zhu, Robert Strongin

Chemistry Faculty Publications and Presentations

E-cigarette devices are wide ranging, leading to significant differences in levels of toxic carbonyls in their respective aerosols. Power can be a useful method in predicting relative toxin concentrations within the same device, but does not correlate well to inter-device levels. Herein, we have developed a simple mathematical model utilizing parameters of an e-cigarette’s coil and wick in order to predict relative levels of e-liquid solvent degradation. Model 1, which is coil length/(wick surface area*wraps), performed in the moderate-to-substantial range as a predictive tool (R2 = 0.69). Twelve devices, spanning a range of coil and wick styles, were analyzed. Model …

A Statistical Analysis Of Trans-Resveratrol In Grape Cane From Ten Varieties Of Cultivated Wine Grapes (Vitus Spp.), Harold Rathburn, Peter Bell, Scott Cook, Darrell D. Mayberry, Emryse Geye, Ryann Goodrich

Chemistry Faculty Publications and Presentations

trans-Resveratrol (resveratrol) has been shown to have various health benefits. As a consequence, there is an effort to determine plentiful sources of this molecule. Certain plants, such as grapes, synthesize resveratrol and therefore appear to be an excellent source of this chemical. Annual pruning of grapevine yields significant amounts of cane material that is normally mulched or simply burned. Previous studies have shown this grape cane to contain economically useful resveratrol. Texas is the seventh largest producer of grapes in the USA with over 162 ha currently under cultivation. As a result it is estimated that more than $3.2 …

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 …

Derivatization Of Stable, Soluble Redox-Active Organic Materials For Non-Aqueous Redox Flow Batteries, Thilini Malsha Suduwella

Theses and Dissertations--Chemistry

In screening active materials for redox flow batteries (RFBs) – in which solubility is important to raise the volumetric energy density – scientists are slave to trial and error, modifying organic molecules in an attempt to optimize (increase) solubility without compromising other important properties such as stability and redox potential. A trained chemist can often predict the trends of solubility with the structural modifications in the neutral state of the materials, but when it’s come to the charged state of the materials, it doesn’t follow the same trend as the neutral species and relative values are hard to predict. The …

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 …

Uncovering Structure-Property Relationships Of Inorganic Nanomaterials Via Transmission Electron Microscopy, Melonie Thomas

Theses and Dissertations--Chemistry

The rapid increase of research in nanoscale devices and nanotechnology in the past few decades has revealed that nanomaterials may possess exceptional properties that are significantly different from the bulk counterpart, due to local rearrangements of the atoms at surfaces and defects. Transmission electron microscopy (TEM) is an indispensable tool when it comes to the characterization of nanomaterials, primarily due to its ability to resolve the local-structure of materials at the atomic-scale. To study dynamic processes, however, regular TEM experiments are inadequate, as they provide only before and after information rather than the real-time data essential to understanding a reaction …

Structure, Surface, And Interfacial Modifications Of Carbon And Supported-Metal Electrodes For Electrochemical Carbon Dioxide Conversion, Namal Wanninayake

Theses and Dissertations--Chemistry

Currently, the global emission of greenhouse CO₂ is over 36 billion tons per year. Consequently, the atmosphere's CO₂ concentrations have exceeded 400 ppm, which is the highest reported in the last three million years. The accumulation of CO₂ is the most critical origin for today's climate change; thus, closing the carbon cycle is vital to reverse the detrimental impacts of climate change. Under this goal, the electrochemical reduction of CO₂ into commodity fuels and chemicals via renewable energy is one of the most promising strategies to recycle CO₂. Despite significant progress made in electrocatalysis, …

Multi-Component Material For Solar Energy Conversion And Fundamentals Of Lead Acid Batteries, Crystal Ferels

Graduate Research Theses & Dissertations

Synthesis of complex inorganic materials is desirable because their complex composition allows more degrees of freedom and tunability, whose properties differ from their parent components. As an expansion on this concept, we synthesized a quinary compound Ce3FeWS3O6, using a molten flux method and a solvothermal method. The compound crystallizes into a hexagonal crystal system with space group P63/m. Its electric partition shows an anion with the form [(Ce3+)3W6+(S2-)3(O2-)6]3- forcing the transition metal Fe3+ state and leaving no conduction electrons, making the material a semiconductor. This compound is the right candidate as photoelectric material capable of absorbing photons from the solar …

Fundamental Study Of Supported Metal Catalysts Prepared By Metal In Lithium Solution For Energy Science, Haiping Xu

Graduate Research Theses & Dissertations

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technique for energy conversion and storage from intermittent electricity sources (ie. wind and solar). By coupling electrochemical CO2 reduction (CO2R) to a renewable energy source atmospheric CO2 could be converted back into a fuel such as ethanol, or a commodity chemical such as ethanol or acetic acid. These products could then be consumed for energy or used to generate more valuable chemical products effectively removing CO2 from the atmosphere. To commercialize this process, it is highly desired to prepare catalysts that selectively reduce CO2 at low overpotential with long durability. Research …