Chemistry Commons^™

Determination Of Anthropogenic Radionuclides In Ocean Water Using Extraction Chromatography, Jaimie Daum

UNLV Theses, Dissertations, Professional Papers, and Capstones

In the aftermath of the reactor accident in Fukushima, it has become obvious that there is a severe lack in methods that would allow for the rapid determination of anthropogenic radionuclides in ocean water. Current radioanalytical techniques for the determination of radionuclides in natural waters have a number of disadvantages including the fact that they are time consuming, generate a substantial amount of waste, and are typically multi-step processes. Additionally, the elevated amount of dissolved ions in ocean water imparts a complex matrix that can interfere with the rapid separation and determination of anthropogenic radionuclides. Therefore, due to the size, …

Breaking The Language Barrier: Equitable Assessment In General Chemistry, Eshani Lee

UNLV Theses, Dissertations, Professional Papers, and Capstones

Because language provides the framework through which knowledge is constructed, it is crucial to consider the ways in which students with limited English proficiencies are able to express their understanding. English language learners (ELLs) make up a significant portion of the student body in the education system and represent many ethnic and racial minorities in STEM (Science, Technology, Engineering & Mathematics) fields (Burke & Mattis, 2007). Despite the national push to build a more diversified, STEM-ready workforce, there is little research that considers the way ELLs are assessed in STEM courses at the postsecondary level. Literature reports that science tests …

Solvent Extraction And Extraction Chromatography Of Homologs And Pseudohomologs Of Rutherfordium Using Teha And Tehp, Jeffrey Rolfes

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studies of the chemical properties of the heaviest elements have always been difficult due to the short half-lives and low cross sections involved. To solve this problem, atom-at-a-time methods are necessary to determine the properties of these short-lived isotopes. Extremely fast kinetics for the chemical reactions studied (on the same order as the nuclide’s half-life) are required, and the system should have the potential for automation. Solvent extraction, with its selectivity and quick kinetics, has historically been used for these investigations into characteristics of super heavy elements. Another technique, extraction chromatography, offers potentially a way of investigating rutherfordium’s properties, without …

Separation Of Neighboring Trivalent Lanthanides For Neutron Capture Cross Section Measurements, Balazs Jozsef Bene

UNLV Theses, Dissertations, Professional Papers, and Capstones

The determination of the low-energy neutron capture cross-section of 171Tm with greater accuracy is important for both astrophysics and Stockpile Stewardship. Thulium-171 is a branching point in the s-process of stellar nucleosynthesis. Branching point nuclei, with half-lives in the order of 1 – 100 years are places where neutron capture and beta decay competes. This isotope is also the second order (n, γ) reaction product of 169Tm, which was used as a radiochemical detector in nuclear weapon experiments. It was placed at strategic locations in nuclear devices. Following the test, samples were analyzed in the collected samples for products of …

Use Of Sodium Bismuthate Chromatography For Separation Of Americium From Curium And Other Elements In Spent Nuclear Fuel, Jason Michael Richards

UNLV Theses, Dissertations, Professional Papers, and Capstones

A novel method for partitioning americium from curium has been developed using sodium bismuthate as both an oxidant and a separation medium. The presence of americium and curium in nuclear waste increases the heat load in geological repositories and leads to larger waste volumes. These elements are also the source of most of the long-term radiotoxicity of the waste. However, the heat load and long-term radiotoxicity contribution from americium is much greater than that from curium. The contribution of curium to the heat load and radiotoxicity of the waste is significant on the same time scale as longer-lived fission products …

Applications Of Nanoporous Materials In Gas Separation And Storage, Amit Sharma

UNLV Theses, Dissertations, Professional Papers, and Capstones

Past decades in the field of gas separation and storage utilized the concepts of both cryogenic distillation and non-cryogenic methods such as high-pressure cylinders but few concerns – efficiency, energy intensiveness, cost associated, risk of failure always existed. Recent advances in the field focuses on using porous materials especially nanoporous materials. Nanoporous materials, due to their well-defined structure, range of pore diameters, and striking surface chemistry hold over traditional porous materials for gas separation and storage. With pore diameter less than 2 nm and abundance of energetically favorable sites (such as unsaturated metal sites, channels, cages, cavities etc.), these materials …

Methylated Dnmt1 And E2f1 Are Targeted For Proteolysis By L3mbtl3 And Crl4dcaf5 Ubiquitin Ligase, Feng Leng, Jiekai Yu, Chunxiao Zhang, Salvador Alejo, Nam Hoang, Hong Sun, Fei Lu, Hui Zhang

Chemistry and Biochemistry Faculty Research

Many non-histone proteins are lysine methylated and a novel function of this modification is to trigger the proteolysis of methylated proteins. Here, we report that the methylated lysine 142 of DNMT1, a major DNA methyltransferase that preserves epigenetic inheritance of DNA methylation patterns during DNA replication, is demethylated by LSD1. A novel methyl-binding protein, L3MBTL3, binds the K142-methylated DNMT1 and recruits a novel CRL4DCAF5 ubiquitin ligase to degrade DNMT1. Both LSD1 and PHF20L1 act primarily in S phase to prevent DNMT1 degradation by L3MBTL3-CRL4DCAF5. Mouse L3MBTL3/MBT-1 deletion causes accumulation of DNMT1 protein, increased genomic DNA methylation, and late embryonic lethality. …

Syntheses, Raman Spectroscopy And Crystal Structures Of Alkali Hexa-Fluoridorhenates(Iv) Revisited, James Louis-Jean, Samundeeswari Mariappan Balasekaran, Dean Smith, Ashkan Salamat, Chien Thang Pham, Frederic Poineau

Chemistry and Biochemistry Faculty Research

The A2[ReF6] (A = K, Rb and Cs) salts are isotypic and crystallize in the trigonal space group type P\overline{3}m1, adopting the K2[GeF6] structure type. Common to all A2[ReF6] structures are slightly distorted octa­hedral [ReF6]2− anions with an average Re—F bond length of 1.951 (8) Å. In those salts, symmetry lowering on the local [ReF6]2− anions from Oh (free anion) to D3d (solid-state structure) occur. The distortions of the [ReF6]2− anions, as observed in their Raman spectra, are correlated to the size of the counter-cations.

Controlled Electrochemical Reduction Of Gold And Palladium Metal Precursors In Polyaniline, Nicole Goodwin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Polyaniline (PANI) has been extensively studied due to its unique electrochemical properties. The conjugated polymer is conductive with high chemical stability below 100°C, mechanical strength, and large surface area. The applications of PANI have included chemical sensing, corrosion inhibition coatings, light emitting diode and as a substrate for metal composite catalysts. Both chemical and electrochemical methods have been developed and utilized in the synthesis of PANI/metal composites. The simultaneous reduction of aniline and metal precursor produces a composite of PANI encapsulated metal, reducing the active surface area available for catalysis. Alternatively, chemical reduction of the metal precursor into preformed PANI …

Surface And Interface Characterization Of Solution-Processed Metal Oxides And Pedot:Pss Using Photoelectron Spectroscopy, Lynette M. Kogler

UNLV Theses, Dissertations, Professional Papers, and Capstones

Solution-processed materials are appealing for use in printable electronics as a means to lower production costs, but precise control of the process is crucial for achieving the desired properties in the final materials and their interfaces. Electronic interface properties depend on both the involved materials and their fabrication processes, impacting the development and commercialization of these materials. Analyzing the chemical and electronic structure of these materials, particularly at the surfaces and interfaces, is important not only for insuring that the materials have the desired properties, but also for understanding the effects of the fabrication process and how to modify properties …

The Electrochemical Deposition Of Samarium And Europium Dissolved In Ionic Liquid Solvent, Bea Martinez

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rare-earth elements include the lanthanide series in the periodic table with the addition of scandium and yttrium. China produces approximately 95% of the world’s rare-earths supply and is the largest consumer of the world’s rare earth supply. Domestic production of rare-earth metals is a priority in the US. The domestic demand for rare-earth elements is largely based on their use in electronic devices, catalytic converters, and more importantly defense applications. Therefore, China’s monopoly of rare-earth elements is viewed as a threat to national security. Although capital investments have resulted in an increase in domestic mining and refining of rare-earth materials, …

Synthesis And Electrochemical Characterization Of Pani/Ni And Pani/Au/Ni Composites, Morgan Emily Pacini

UNLV Theses, Dissertations, Professional Papers, and Capstones

The purpose of this research is to show that the electrochemically controlled formation of monometallic and bimetallic catalysts in polyaniline (PANI) can directly influence the efficiency and reproducibility of the catalytic oxidation of methanol. PANI is a conductive polymer that provides a three-dimensional template for the metallic catalysts deposition at nitrogen sites. The controlled deposition of metallic species can be achieved using the normal oxidation/reduction cycles of PANI. The deposition of metallic species relies on anion precursors that are electrostatically bound by the polymer during the oxidation cycle. The precursor is reduced directly at the nitrogen sites in the polymer …

Synthesis Of Actinide Materials For The Study Of Basic Actinide Science And Rapid Separation Of Fission Products, Jacquelyn M. Dorhout

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation covers several distinct projects relating to the fields of nuclear forensics and basic actinide science. Post-detonation nuclear forensics, in particular, the study of fission products resulting from a nuclear device to determine device attributes and information, often depends on the comparison of fission products to a library of known ratios. The expansion of this library is imperative as technology advances. Rapid separation of fission products from a target material, without the need to dissolve the target, is an important technique to develop to improve the library and provide a means to develop samples and standards for testing separations. …

Thermotropic Liquid-Crystalline Properties Of Extended Viologen Bis(Triflimide) Salts, Pradip K. Bhowmik, Shane T. Killarney, Jessa Rose A. Li, Jung Jae Koh, Haesook Han, Lewis Sharpnack, Deña M. Agra-Kooijman, Michael R. Fisch, Satyendra Kumar

Chemistry and Biochemistry Faculty Research

A series of extended, symmetric viologen triflimides were synthesised by the metathesis reaction of lithium triflimide with the respective viologen tosyalates in methanol. Their chemical structures were characterised by Fourier Transform Infrared, 1H and 13C Nuclear Magnetic Resonance spectroscopy and elemental analysis. Their thermotropic liquid-crystalline (LC) properties were examined by a number of experimental techniques including differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and variable temperature X-ray diffraction. The viologen salts containing alkyl chain of two carbon and three carbon atoms were relatively low melting salts. Those of alkyl chains of four carbon and five carbon atoms formed ionic …

Improved Partial Charge Models In Siliceous Zeolites For The Simulation Of Adsorption And Identification Of Catalytic Sites, Jarod J. Wolffis

UNLV Theses, Dissertations, Professional Papers, and Capstones

Utilization of computational modelling and simulation is expanding as computer processing power has increased and as new tools have been developed. This thesis focuses on efforts to improve the accuracy of simulations in aluminosilicate zeolites, an industrially important category of materials for catalysis and separations. For these sorbents, partial atomic charge represents a critical parameter in molecular mechanics simulations, determining the Coulombic non-bonding interaction. Partial charges may also be used as a measure of important physical parameters of the system such as the degree of covalency or the relative acidity of catalytic sites. We compare several common methods for predicting …

Volatile Technetium Oxides: Implications For Nuclear Waste Vitrification, Bradley Covington Childs

UNLV Theses, Dissertations, Professional Papers, and Capstones

From 1943 to 1987, the Hanford site was the primary location for the production of Pu for military applications in the United States. Decades of Pu production have been accompanied by generation of large amounts of liquid and solid radioactive waste. One of radioelements present in the Hanford wastes is Tc, principally the isotope 99Tc (1500 kg). In the waste, it is primarily present in the heptavalent state as TcO4 - . One option for the management of Tc at the Hanford site is its vitrification into a borosilicate glass. The behavior of Tc during vitrification is problematic, as it …

Synthesis, Characterization And Biological Studies Of Technetium-99m And Rhenium-188 Peptides, Vanessa Anne Sanders

UNLV Theses, Dissertations, Professional Papers, and Capstones

Radiopharmaceuticals are very powerful diagnostic tools for evaluation of a host of medical conditions. These drugs are labeled with radioactive isotopes, which are utilized to create pictures of areas of interest through absorption of the drug. They are currently in high demand due to their ability to image areas that traditional imaging devices cannot. The radioisotope 99mTc, with a half-life of 6.01 hours and a 140 keV gamma emission, is central to many radiopharmaceutical compounds. This isotope is easily obtained from a 99Mo-99mTc generator, through beta decay and column chromatography separations. Very little technetium, less than 6 ng, is needed …

Characterization Of Dust On Solar Devices In Southern Nevada, Jason Sylva

UNLV Theses, Dissertations, Professional Papers, and Capstones

Dust can impact the efficiency of solar energy collection devices, and in some arid environments, dust can reduce solar energy efficiency up to 30%. Reducing the impact of dust is therefore critical in the expansion of solar technology throughout regions where solar energy is utilized. Characterization of suspended and settled particulate matter can assist in developing strategies for dust mitigation. With the characterization of suspended and settled particulate in remote, rural, and urban environments, more informed decisions can be made regarding the selection of coating material on solar panels as well as developing cleaning and maintenance procedures. Particulate matter that …

Spectroscopic Signatures Of Uranium Speciation For Forensics, Nicholas Wozniak

UNLV Theses, Dissertations, Professional Papers, and Capstones

Chemical speciation offers opportunities for development of signatures that arise from the production, conversion, and aging processes of nuclear materials. This information has been useful for environmental science and remediation and the ability to measure chemical signatures, from processed materials may be of great use to nuclear forensics. Many nuclear forensics analyses deal with radiochronometry and isotopic analysis, but because processing is chemical in nature, there are opportunities for chemical signatures from the bulk products, reagents, or reaction intermediates to be measured.

Many spectroscopic techniques can be utilized in a remote setting outside of the laboratory, with minimal or no …

Interference Effects Of Urban Rubble On The Radioanalytical Analysis Of Strontium, Derek Roger Mclain

UNLV Theses, Dissertations, Professional Papers, and Capstones

Most current radioanalytical protocols have been developed for the analysis of air, water, soil and bioassay samples. While these protocols build the foundation of operational environmental monitoring, they are not necessarily suitable for the analysis of samples that will be encountered in the aftermath of a nuclear incident. In such a situation, it will be important to characterize the isotopes of interest present in the affected area to obtain signatures for nuclear forensics and ensure the appropriate response. Specifically, this research is aimed at the determination of strontium-90 and its separation from zirconium-90 in a post-detonation situation.

Strontium-90’s relatively long …

Structural Behavior Of Nbsexte2-X Superconductors Under High Pressure, Vahe Mkrtchyan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Niobium chalcogenide compounds have recently gained a great deal of interest due to the fact that a superconducting phase coexists with the charge density wave state (CDW), as well as their potential for numerous applications. Two superconducting compositions, NbSexTe2-x (x=2, 1.5) were prepared by solid state route using high purity Nb, Se, and Te powders. Powder X-ray diffraction patterns collected at ambient conditions for NbSe2 and NbSe1.5Te0.5 showed a single phase with hexagonal crystal structure, with space group P63mmc. High-pressure X-ray diffraction measurements were performed at the Advanced Photon Source at Argonne National Laboratory to investigate structural stability up to …

Novel Pathways To High-Efficiency Chalcopyrite Photovoltaic Devices: A Spectroscopic Investigation Of Alternative Buffer Layers And Alkali-Treated Absorbers, Michelle Mezher

UNLV Theses, Dissertations, Professional Papers, and Capstones

Within the past few years, breakthroughs in Cu(In,Ga)Se₂ (CIGSe) thin-film photovoltaic device efficiencies (on a laboratory scale) were achieved utilizing alkali-treated (KF) absorbers. Na incorporation in the CIGSe absorber, either diffused from the substrate or deliberately deposited, affects the surface electronic properties of the CIGSe absorber. The role of Na, however, is still not fully understood with some studies suggesting that Na also passivates defects at the grain boundaries. Replacing Na with K offered an efficiency boost resulting in KF treatments becoming the new “hot topic” in the chalcopyrite field, both in terms of understanding how the treatment changes …

Ionic Polymer-Metal Composite Actuators Based On Nafion Blends With Functional Polymers, Jungsoo Nam

UNLV Theses, Dissertations, Professional Papers, and Capstones

Ionic polymer metal composites (IPMCs) have been an attractive research subject for use in underwater robotic applications, biomedical and biomimetic application owing to their great potential as actuators, artificial muscles, and more. IPMC is synthetic composite nanomaterial of ion exchange membranes and metal electrode. Although both components are important, the properties of ion exchange membranes should be emphasized since it is responsible of the path for the mobile ions to migrate when voltage is applied to exhibit deformation. Most of the researches that have been done on IPMCs used commercially available Nafion as their ion exchange membranes. However, its high …

Forcing Cesium Into Higher Oxidation States Via Useful Hard X-Ray Induced Chemistry At Extreme Conditions, Daniel Thomas Sneed

UNLV Theses, Dissertations, Professional Papers, and Capstones

Recent theoretical work published in Nature Chemistry postulates the existence of cesium in high oxidation states when bonding with fluorine. It is thus predicted to behave as a p-block element (such as xenon) at pressures above 5 GPa. At these pressures, fluorine atoms may bond with the inner p-shell electrons forming CsFn, where n may vary from 2 up to 6; thus the oxidation state of Cs may change up to 6+. My research focused on physically synthesizing these compounds and to verify that, given the right conditions, bonding doesn't only occur with valence electrons, but with the inner p-shell …

The Proof Is In The Pots: Residue Analysis Of Virgin Branch Puebloan Ceramics, Brenna Lynn Wilkerson

UNLV Theses, Dissertations, Professional Papers, and Capstones

This study focuses on better understanding diet and subsistence strategies among Virgin Branch Puebloan groups living in the Moapa Valley in southern Nevada and on the Shivwits Plateau in northwestern Arizona. Gas chromatography-mass spectrometry (GC-MS) was used to identify absorbed food residues in three types of Virgin Branch Puebloan ceramics (Moapa Gray Ware, Shivwits Ware, and Tusayan Virgin Series). The data produced by the residue analysis were used to compare patterns of subsistence between Virgin Branch Puebloan sites in the lowlands along the Muddy River and at upland sites on the Shivwits Plateau as these two areas have different environments …

The San1 Ubiquitin Ligase Functions Preferentially With Ubiquitin-Conjugating Enzyme Ubc1 During Protein Quality Control, Rebeca Lea Ibarra

UNLV Theses, Dissertations, Professional Papers, and Capstones

Protein quality control (PQC) is a critical process wherein misfolded or damaged proteins are cleared from the cell to maintain protein homeostasis. In eukaryotic cells, the removal of misfolded proteins is primarily accomplished by the ubiquitin-proteasome system (UPS). In the UPS, ubiquitin-conjugating enzymes and ubiquitin ligases append poly-ubiquitin chains onto misfolded protein substrates signaling for their degradation. The kinetics of protein ubiquitylation are paramount since a balance must be achieved between the rapid removal of misfolded proteins versus providing sufficient time for protein chaperones to attempt refolding. To uncover the molecular basis for how PQC substrate ubiquitylation rates are controlled, …

Strategic Molecular Design To Engineer The Electron Affinity Of Self-Assembling Organic Semiconductors, Kelly Nicole Zaugg

UNLV Theses, Dissertations, Professional Papers, and Capstones

Development of electron-accepting (n-type) semiconductors used in organic photovoltaic cells and field effect transistors has been an area of research with less advancement compared to their electron-donating (p-type) counterparts. Currently, the highest performing n-type semiconductor is a fullerene-based derivative (PCBM) with a favorable ELUMO of -4.08 eV. However, PCBM has limited absorption in the visible region and fixed electron affinity. This work focuses on the development of self-assembling n-type materials with controllable electronic properties by strategically lowering ELUMO to a level comparable to PCBM. Molecular design follows an acceptor-acceptor'-acceptor (A-A'-A) configuration; with A being two 2,3-dioctyloxyphenazine substituents connected to A’ …

Direct Dissolution And Electrochemical Investigation Of Cerium And Uranium In Ionic Liquid, Janelle Droessler

UNLV Theses, Dissertations, Professional Papers, and Capstones

The solubility, coordination and speciation of f-elements in ionic liquids (ILs) has been the focus of numerous studies because the purely ionic systems have unique physical properties that can be exploited in comparison to aqueous, organic, or molten salt systems. Ionic liquids are thermally stable, have negligible vapor pressure, and are electrochemically stable at negative potentials that encompass the reduction potential of actinide species. Literature has suggested that the properties of ILs could potentially be utilized in the nuclear fuel cycle for separations and reprocessing. However, the solubility of f-elements in ILs has been significantly lower compared to traditional solvents. …

Chemical And Electronic Structure Of Surfaces And Interfaces In Cadmium Telluride Based Photovoltaic Devices, Douglas Arthur Duncan

UNLV Theses, Dissertations, Professional Papers, and Capstones

The surface and interface properties are of the upmost importance in the understanding, optimization, and application for photovoltaic devices. Often the chemical, electronic, and morphological properties of the films are empirically optimized, however when progress slows, a fundamental understanding of these properties can lead to breakthroughs. In this work, surfaces and interfaces of solar cell-relevant films are probed with a repertoire of X-ray analytical and microanalysis techniques including X-ray photoelectron (XPS), X-ray excited Auger electron (XAES), X-ray emission (XES) spectroscopies, and atomic force (AFM) and scanning electron (SEM) microscopies.

Silicon-based devices currently dominate the solar market, which is rather inflexible …

Hydrothermal Routes To Technetium Cluster Compounds, William M. Kerlin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Transition metals of groups six through nine exhibit unique direct multiple metal-metal bonding cores. Technetium is a group seven transition metal and is the lightest radioelement in the periodic table. Technetium exhibits nine oxidation states (from -I to VII) and an extensive set of mixed oxidation states due to bi- or poly- nuclear complex formation. Technetium has no stable isotopes and thirty four technetium isotopes have been discovered. Two main isotopes are of great importance ⁹⁹Tc and its metastable nuclear isomer ^99mTc. The isotope ^99mTc (T_1/2 = 6.01 hours, γ = 140.5 keV) is used in …