Physical Sciences and Mathematics Commons^™

Ultra-Stable Protein-Polymer Bioconjugates, Kyle S. Cole

Master's Theses

No abstract provided.

Water-Soluble Deep-Cavity Cavitands: Synthesis, Molecular Recognition, And Interactions With Phospholipid Membranes, Sarah E. Ioup

University of New Orleans Theses and Dissertations

Water-soluble deep-cavity cavitands provide a rare opportunity to study self-assembly driven by the hydrophobic effect. These molecular hosts dimerize in the presence of certain guest molecules to form water-soluble molecular capsules. These systems have given rise to numerous novel chemical phenomena and have potential use in drug delivery. The host octaacid (OA) has been particularly well-characterized, but studies are limited to basic pH because of limited host solubility.

Herein we report an improved synthesis of OA and the syntheses of three new water-soluble deep-cavity cavitands. The new hosts are soluble at neutral pH, increasing relevance for biological studies. The new …

Synthesis And Characterization Of Complexes Of [Rh2(Nphcoch3)4] And Nitriles., Jennie Tan

Undergraduate Honors Theses

The rhodium carboxamide [Rh2(NPhCOCH3)4]L (L=axial ligand), has applications as a catalyst for carbenoid transformations. To explore the nature of the rhodium-carbene bond, studies between Rh2(NPhCOCH3)4 and nitriles were proposed. Trials of the benzonitrile, o-tolunitrile, and m-tolunitrile have been performed and characterized on the 2,2-trans [Rh2(NPhCOCH3)4] complex via NMR spectroscopy, IR spectroscopy, and X-ray crystallography.

Impact Of Post-Synthesis Modification Of Nanoporous Organic Frameworks On Selective Carbon Dioxide Capture, Timur İslamoğlu

Theses and Dissertations

Porous organic polymers containing nitrogen-rich building units are among the most promising materials for selective CO2 capture and separation applications that impact the environment and the quality of methane and hydrogen fuels. The work described herein describes post-synthesis modification of Nanoporous Organic Frameworks (NPOFs) and its impact on gas storage and selective CO2 capture. The synthesis of NPOF-4 was accomplished via a catalysed cyclotrimerization reaction of 1,3,5,7-tetrakis(4-acetylphenyl)adamantane in Ethanol/Xylenes mixture using SiCl4 as a catalyst. NPOF-4 is microporous and has high surface area (SABET = 1249 m2 g-1). Post-synthesis modification of NPOF-4 by nitration afforded (NPOF-4-NO2) and subsequent reduction resulted …

An Investigation Of Urban Mobile Source Aerosol Using Optical Properties Measured By Crdt/N: Diesel Particulate Matter And The Impact Of Biodiesel, Monica Elizabeth Wright

Dissertations and Theses

Mobile source emissions are a major contributor to global and local air pollution. Governments and regulatory agencies have been increasing the stringency of regulations in the transportation sector for the last ten years to help curb transportation sector air pollution. The need for regulations has been emphasized by scientific research on the impacts from ambient pollution, especially research on the effect of particulate matter on human health. The particulate emissions from diesel vehicles, diesel particulate matter (DPM) is considered a known or probable carcinogen in various countries and increased exposure to DPM is linked to increased cardiovascular health problems in …

Microfluidic Devices With Integrated Sample Preparation For Improved Analysis Of Protein Biomarkers, Pamela Nsang Nge

Theses and Dissertations

Biomarkers present a non-invasive means of detecting cancer because they can be obtained from body fluids. They can also be used for prognosis and assessing response to treatment. To limit interferences it is essential to pretreat biological samples before analysis. Sample preparation methods include extraction of analyte from an unsuitable matrix, purification, concentration or dilution and labeling. The many advantages offered by microfluidics include portability, speed, automation and integration. Because of the difficulties encountered in integrating this step in microfluidic devices most sample preparation methods are often carried out off-chip. In the fabrication of micro-total analysis systems it is important …

Acid-Base Catalysis In Proton-Coupled Electron Transfer Reactions (Pcet): The Effects Of Brönsted Bases On The Oxidation Of Glutathione And Hydroquinone, Ramos Jonnathan Medina

Theses and Dissertations

This thesis presents the results and discussion of the investigation of the effects of Brönsted bases on the kinetics and thermodynamics of two proton-coupled electron transfer processes: the mediated oxidation of glutathione and the electrochemical oxidation of hydroquinone. Proton-coupled electron transfer (PCET) is the name given to reactions that involve the transfer of electron(s) accompanied by the exchange of proton(s). PCETs are found in many chemical and biological processes, some of current technological relevance such as the oxygen reduction reaction in fuel cells, which involves the transfer of four electrons and four protons (4e-, 4H+); or the splitting of water …

Charge, Bonding, And Magneto-Elastic Coupling In Nanomaterials, Qi Sun

Doctoral Dissertations

Phonons are exquisitely sensitive to finite length scale effects in a wide variety of materials because they are intimately connected to charge, structure, and magnetism, and a quantitative analysis of their behavior can reveal microscopic aspects of chemical bonding and spin-phonon coupling. To investigate these effects, we measured infrared vibrational properties of bulk and nanoscale MoS₂ [molybdenum disulfide], MnO [manganese(II) oxide], and CoFe₂O₄ [cobalt iron oxide]. From an analysis of frequencies, oscillator strengths, and high-frequency dielectric constants, we extracted Born and local effective charges, and polarizability for MoS₂ and MnO. For MoS₂ nanoparticles, in …

Charge-Lattice-Spin Interactions In Molecule-Based Magnets, Tatiana Vladimir Brinzari

Doctoral Dissertations

Many of the most attractive properties of multifunctional materials can be traced to the competition between charge, structure, and magnetism. The discovery that these interactions can be tuned with various physical stimuli has accelerated interest in their behavior under extreme conditions. In this dissertation I present a spectroscopic investigation of several model molecule-based magnets under external stimuli of magnetic field and temperature. The compounds of interest include M^II[N(CN)₂]₂ (M=Mn, Co) and [Ru₂(O₂CMe)₄]₃[Cr(CN)₆]. These materials are attractive for their subtle interplay between electronic, magnetic and structural …

Exploring Computational Chemistry On Emerging Architectures, David Dewayne Jenkins

Doctoral Dissertations

Emerging architectures, such as next generation microprocessors, graphics processing units, and Intel MIC cards, are being used with increased popularity in high performance computing. Each of these architectures has advantages over previous generations of architectures including performance, programmability, and power efficiency. With the ever-increasing performance of these architectures, scientific computing applications are able to attack larger, more complicated problems. However, since applications perform differently on each of the architectures, it is difficult to determine the best tool for the job. This dissertation makes the following contributions to computer engineering and computational science. First, this work implements the computational chemistry variational …

Confinement Effects Of Solvation On A Molecule Physisorbed On A Metal Particle, Jacob Fosso Tande

Doctoral Dissertations

We describe and present results of the implementation of the surface and volume polarization for electrostatics~(SVPE) and the iso-density surface solvation models. Unlike most other implementation of the solvation models where the solute and the solvent are described with multiple numerical representation, our implementation uses a multiresolution, adaptive multiwavelet basis to describe both solute and the solvent. This requires reformulation to use integral equations throughout as well as a conscious management of numerical properties of the basis.

Likewise, we investigate the effects of solvation on the static properties of a molecule physisorbed on a spherical particle, modeled as a polarizable …

Boron And Metal Catalyzed C-C And C-H Bond Formation, Adam Barret Pippin

Doctoral Dissertations

Research efforts focused on the use of boron and metals to form new carbon-carbon and carbon-hydrogen bonds are summarized in this dissertation. Several novel reactions have been developed. These include: the deoxygenation of benzylic alcohols using chloroboranes; alkenylation of benzylic alcohols using boron trichloride; and dialkynlation of aryl aldehydes using dialkynylboron chloride. Numerous applications of these novel reactions have been developed. These include alternate routes to diphenylmethanes and 1,4-diynes from easily prepared dialkynylboron chlorides. In addition, E and Z alkenyl halides can now be prepared using boron trichloride without the use of butyllithium. The stereochemistry of the alkenyl halide can …

Synthesis, Evaluation And Applications Of Biologically Significant Molecules And Their Analogues, Sneha Ashesh Belapure

Doctoral Dissertations

Synthetic chemists are always looking for challenging problems to solve. Design and synthesis of novel molecules that can act as agents of chemical and biological modification are one of the foremost goals of a synthetic chemist. This dissertation describes advances and efforts made in this area.

Obesity is one of the critical problems of the modern age. Molecules that can remediate this condition are highly sought after. The first chapter of this dissertation describes synthetic strategies explored to prepare these valuable natural products along with their structural and stereochemical analogues to study structure and activity relationships (SAR). This method gives …

The Path To An Orally Administered Protein Therapeutic For The Treatment Of Diabetes Mellitus, Susan Clardy James

Chemistry - Dissertations

Protein therapeutics like insulin and glucagon-like peptide-1 analogues are currently used as injectable medications for the treatment of diabetes mellitus. An orally administered protein therapeutic is predicted to increase patient adherence to medication and bring a patient closer to metabolic norms through direct effects on hepatic glucose production. The major problem facing oral delivery of protein therapeutics is gastrointestinal tract hydrolysis/proteolysis and the inability to passage the enterocyte. Herein we report the potential use of vitamin B₁₂ for the oral delivery of protein therapeutics.

We first investigated the ability of insulin to accommodate the attachment of B₁₂ at …

Synthesis, Design, And Biological Evaluation Of Inhibitors And Activators Of Src Homology 2 Domain-Containing Inositol Phosphatase (Ship) And Synthetic Studies Of Apicularen A And Maoecrystal V, Dennis Racca Viernes

Chemistry - Dissertations

This dissertation involves work both on the syntheses of small molecules with potential therapeutic applications and synthetic studies on natural products with unusual core skeletons.

The first part of this work involves the synthesis, design, and biological evaluation of aminosteroids as inhibitors for the SH2-containing inositol phosphatase 1 (SHIP1). SHIP1, a 145 kDa protein, is involved in regulating the formation of new blood cells. High- throughput screening identified several SHIP inhibitors including NSC23922, a mixture of 3a- and 3β-aminocholestane. Both 3a- and 3β-aminocholestane were synthesized from dihdyrocholesterol and the 3a- form was verified as …

Refractive Index Chemical Sensing With Noble Metal Nanoparticles, Phillip Blake

Graduate Theses and Dissertations

Chemical sensing is a key component in modern society, especially in engineering applications. Because of their widespread impact, improvements to chemical sensors are a significant area of research. One class of sensors, plasmonic sensors, is being heavily researched because of their ability to detect low levels of analyte in near real time without destroying the analyte. This work studies a new class of plasmonic sensor that utilizes diffractive coupling to improve sensor performance. Specifically, this work outlines the first study of diffractive coupling sensors with typical nanoparticle shapes. Sensitivity of this new class of sensor is directly compared to typical …

Synthesis And Biological Activity Of Aminoglycosides And 1,4-Naphthoquinone Derivatives, Marina Fosso Yatchang

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research described in this dissertation is at the interface of organic chemistry and biology, and it aimed at designing and synthesizing biologically active molecules for the possible development of therapeutic agents.

Spinal muscular atrophy is an incurable disease that affects 1 in every 6000 babies, making it the leading genetic cause of infant mortality. While no treatment is available, efforts are being taken to solve this issue. Part of the work outlined in this dissertation was carried out in collaboration with researchers from the University of Missouri to investigate a potential therapeutic for this disease.

In addition, the continuous …

In Situ Measurements Of Electron-Beam-Induced Surface Voltage Of Highly Resistive Materials, Joshua Hodges

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Surface charging and subsequent electrostatic discharge due to interactions with the space environment is one of the primary concerns of spacecraft charging studies. Laboratory measurements of the evolution of surface voltages and dissipation currents under simulated space conditions are the primary method used to determine the response of key spacecraft materials to diverse incident fluxes. Increasing the database of information for the electronic properties of insulating materials can assist spacecraft designers in mitigating the harsh effects of the space environment.

The Utah State Materials Physics Group, with the funding of the NASA James Webb Space Telescope project and personnel support …

Fundamental And Applied Studies Of Metal Ion Extraction By Crown Ethers Into Imidazolium-Based Room Temperature Ionic Liquids, Cory Hawkins

Theses and Dissertations

Growing recognition of the extraordinary physicochemical properties and unique solvation environment afforded by ionic liquids (ILs) has drawn increasing attention to these solvents as media for chemical separations. Until recently, little was known about how ionic liquids behave as solvents in this application, particularly in the extraction of ionic solutes such as metal ions. In contrast to the single pathway observed using molecular diluents (i.e., neutral complex extraction), metal ion extraction in these systems has been shown to proceed through as many as three competing pathways over a wide range of conditions. Despite this added complexity, the favorable physicochemical characteristics …

Part 1. Design And Synthesis Of Cysteine/Cystine Prodrugs And Bioisosteres Including Symmetrical And Unsymmetrical Disulfides Designed To Increase Cystine Levels In The Cns In Order To Drive The Cystine/Glutamate Antiporter: A Novel Treatment For Schizophrenia And Drug Addiction. Part 2. Design And Synthesis Of Subtype Selective Ester Bioisosteres Of Bzr Ligands For Gabaa/Benzodiazepine Receptors To Enhance Metabolic Stability, Edward Merle Johnson Ii

Theses and Dissertations

Part 1. Schizophrenia is a debilitating disorder that affects almost 1% of the world's population; pharmacotherapy expenditures for this disorder exceed $10 billion dollars even though existing medications exhibit a poor safety/efficacy profile. It is estimated that 75% of patients discontinue drug treatment, in part due to poor safety/efficacy. The current data set demonstrates that cysteine prodrug NAC reverse the behavioral and neurochemical effects of PCP used to model schizophrenia.

As a result cysteine prodrugs represent a highly novel approach to treating schizophrenia; indeed, these compounds may ultimately be more effective than existing medications because these drugs target the pathology …

Mitochondrial Targeting In Photodynamic Therapy. Metabolic And Drug Structure Requirements For Specific Mitochondrial Localization. A Pilot Investigation, Melissa Rhea Pergande

Theses and Dissertations

Photodynamic therapy (PTD) has shown promise in the treatment of certain types of cancer (Davis et al. 1985, Chen 1988). One appealing strategy under consideration to selectively target tumor cells in PDT is that of mitochondrial targeting (Chen 1988, Chen 1989). The concept of mitochondrial targeting has its origin in the pioneering observation by Chen and colleagues that an enhanced mitochondrial transmembrane potential (ΔΨmito) is a prevalent tumor cell phenotype (Davis et al. 1985, Chen 1988). Because the plasma transmembrane potential is negative on the inner side of the cell, and the mitochondrial transmembrane potential is negative on the matrix …

Molecular Forensic Science Analysis Of Nuclear Materials, Dallas Reilly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Concerns over the proliferation and instances of nuclear material in the environment have increased interest in the expansion of nuclear forensics analysis and attribution programs. A new related field, molecular forensic science (MFS) has helped meet this expansion by applying common scientific analyses to nuclear forensics scenarios. In this work, MFS was applied to three scenarios related to nuclear forensics analysis. In the first, uranium dioxide was synthesized and aged at four sets of static environmental conditions and studied for changes in chemical speciation. The second highlighted the importance of bulk versus particle characterizations by analyzing a heterogeneous industrially prepared …

Elemental Contributions From Minor And Major Constituents Of Bone On The Separation Of Radiostrontium, Ashlee Rae Dailey

UNLV Theses, Dissertations, Professional Papers, and Capstones

While many methods exist to separate and analyze radionuclides from a variety of environmental matrices, the performance of all of these methods is often limited by other interfering constituents that are consistently found in most of these samples. The presence of such constituents can significantly reduce the recovery of the radioisotopes of interests and lead to incomplete separations.

Strontium has the same oxidation state and a similar atomic radius as calcium and is therefore readily able to substitute for calcium in lattice sites. This similarity in behavior leads to the preferential accumulation of strontium in newly formed bone. The study …

The Measure And Instruction Of Scale In Introductory Chemistry, Karrie Linn Gerlach

Theses and Dissertations

As a student, it is fundamental to comprehend how small an atom or molecule is in order to truly understand how the world works. The American Association for the Advancement of Science (AAAS) has determined that scale is a critical theme that pervades through all areas of science and is critical to a deep understanding. This project determined that students, which are more proficient with scale and moving between the macroscopic and particle worlds, were better performers in chemistry classes. Interviews were used to determine what the students understood and what common misconceptions were present. These lead to the development …

Part I. The First Enantiospecific, Stereospecific Total Synthesis Of The Indole Alkaloid Ervincidine. Part Ii. The Synthesis Of Alpha 5 Subtype Selective Ligands For Gaba(A) /Benzodiazepine Receptors, Sundari K. Rallapalli

Theses and Dissertations

Part I. The first enantiospecific, stereospecific total synthesis of ervincidine 89 has been accomplished from commercially available D-(+)-tryptophan 37 which has served both as the chiral auxiliary and the starting material. Moreover, this is the first synthesis which unequivocally sets the stereochemistry of the hydroxyl group at C-6 in sterospecific fashion, as well as the C-16 hydroxy methyl group. The stereospecific conversion of D-(+)-tryptophan 37 into the key template (−)-Na-H, Nb-benzyl tetracyclic ketone 49 via the asymmetric Pictet-Spengler reaction (600 gram scale) and Dieckmann cyclization on multi-hundred gram scale was reduced to only two reaction vessels. The optically active tetracyclic …

Rapid Knowledge Assessment (Rka): Assessing Students Content Knowledge Through Rapid, In Class Assessment Of Expertise, Erin Margaret O'Connell

Theses and Dissertations

Understanding how students go about problem solving in chemistry lends many possible advantages for interventions in teaching strategies for the college classroom. The work presented here is the development of an in-classroom, real-time, formative instrument to assess student expertise in chemistry with the purpose of developing classroom interventions. The development of appropriate interventions requires the understanding of how students go about starting to solve tasks presented to them, what their mental effort (load on working memory) is, and whether or not their performance was accurate. To measure this, the Rapid Knowledge Assessment (RKA) instrument uses clickers (handheld electronic instruments for …

Hydrothermal Chemistry Of The M(I,Ii)/Paha/Anion System, Kari Ann Darling

Chemistry - Dissertations

This research encompasses the detailed investigation of the design and synthesis of metal organic framework (MOF) materials involving the M(I,II)/ polyazaheterocycle/anion system in order to expand our understanding of the principles which render the chemistry more controllable and predictable. In addition, this research investigates the development of properties in these classes of compounds. Furthermore, it has been demonstrated that hydrothermal reaction conditions of stoichiometry, pH, and temperature can influence the identity of the products.

The structural versatility of the M(I,II)/polyazaheterocycle/anion system for M = Cu(I,II), Co(II), Ni (II), Zn (II), and Cd(II) and where the anion is F^-, …

Mechanism Of Action And Gold Nanoparticle Delivery Of Pt(Iv) Prodrugs Of Cisplatin, Yi Shi

Chemistry - Dissertations

The antitumor effects of platinum(IV) complexes, considered prodrugs for cisplatin, are believed to be due to biological reduction of Pt(IV) to Pt(II), with the reduction products binding to DNA and other cellular targets. In this work we used pBR322 DNA to capture the products of reduction of oxoplatin, c,t,c-[PtCl₂(OH)₂(NH₃)₂], 2, and a carboxylate-modified analog, c,t,c-[PtCl₂(OH)(O₂CCH₂CH₂CO₂H)(NH₃)₂], 3, by ascorbic acid (AsA) or glutathione (GSH). Since carbonate plays a significant role in the speciation of platinum …

Nucleophilic Carbon-Carbon Bond-Forming Reactions Of 2-Methylenetetrahydropyrans, Laura Jean Bateman

Chemistry - Dissertations

Reactions with 2-methylenetetrahydropyrans are underutilized in the literature, especially with respect to general methods demonstrating their nucleophilic nature. This work provides three general methods toward the synthesis of 2-β-oxygenated pyranyl substrates, which are key structural components of many biologically active polyketides and natural products.

The use of exocyclic enol ethers as nucleophiles was first demonstrated as a general process in three-component coupling reactions with secondary nucleophiles. The 2-β-hydroxy tetrahydropyran products were obtained in good to excellent yields through promotion with stoichiometric levels of titanium(IV) chloride at reduced temperatures. Only activated aldehydes or ketones worked as efficient coupling partners for this …

New Applications Of Mass Spectrometry For Drug And Lipid Analysis, Elizabeth Lauren Emerson

Graduate Theses and Dissertations

Mass spectrometry is an important tool used in many different disciplines and settings that include forensics, drug discovery, environmental analysis, and proteomics. Gas chromatography - mass spectrometry (GC-MS) and matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI - TOF MS) are two of the most important instruments used for analysis of compounds. Chapters 1 and 2 of this discussion use GC-MS for the investigation of synthetic cannabinoids in `K2' incense products and the detection of metabolites in urine samples from individuals suspected of consuming these mixtures. Analytical standards were synthesized and used for identification and confirmation of structures. Detection of …