Chemistry Commons^™

Metabolite Analysis Of Clostridium Thermocellum Using Capillary Electrophoresis Based Techniques, Anup P. Thakur

University of Kentucky Doctoral Dissertations

Clostridium thermocellum is a thermophilic bacterium that converts biomass to ethanol directly; however, high sensitivity of this bacterium toward ethanol limits its commercial utility. To elucidate the effect of ethanol on the growth of this bacterium a metabolite analysis of C. thermocellum was performed. The hypothesis of the project was that exogenous ethanol alters the metabolite profile of C. thermocellum. For metabolite analysis, capillary electrophoresis-electrospray ionization-mass spectrometry method (CE-ESI-MS) was developed due to highly polar and charged nature of metabolites. To increase the sensitivity of CE-ESI-MS, several parameters at the ESI interface were optimized. The application of 50% isopropanol …

Regulation Of L-Type Voltage-Dependnet Calcium Channels By The Rem Gtpase, Chunyan Pang

University of Kentucky Doctoral Dissertations

The Rem, Rem2, Rad, and Gem/Kir GTPases, comprise a novel subfamily of the small Ras-related GTP-binding proteins known as the RGK GTPases, and have been shown to function as potent negative regulators of high voltage-activated (HVA) Ca²⁺ channels upon overexpression. HVA Ca²⁺ channels modulate Ca²⁺ influx in response to membrane depolarization to regulate a wide variety of cellular functions and they minimally consist of a pore-forming α1 subunit, an intracellular β subunit, and a transmembrane complex α₂/δ subunit. While the mechanisms underlying RGK-mediated Ca²⁺ channel regulation remain poorly defined, it appears that both membrane …

Carbon Nanotube Supported Metal Catalysts For NoX Reduction Using Hydrocarbon Reductants, Eduardo Santillan-Jimenez

University of Kentucky Doctoral Dissertations

Nitrogen oxides (NO_x) are atmospheric pollutants that pose a serious threat to both the environment and human health. Although catalytic deNO_x technologies for engines working under stoichiometric air-to-fuel ratios (i.e., most gasoline engines) are already available, their performance is unsatisfactory under excess air conditions like those under which diesel engines operate.

The selective catalytic reduction of NO_x with hydrocarbon reductants (HC-SCR) is a potential deNO_xsolution for diesel engines, whose operating temperatures are 150-500 ºC. Given that is unlikely for a single catalyst to show acceptable activity throughout this entire temperature span, the use of …

Chiral Ionic Liquids:  Synthesis, Properties, And Enantiomeric Recognition, Shaofang Yu, Sergey V. Lindeman, Chieu D. Tran

Chemistry Faculty Research and Publications

We have synthesized a series of structurally novel chiral ionic liquids which have a either chiral cation, chiral anion, or both. Cations are an imidazolium group, while anions are based on a borate ion with spiral structure and chiral substituents. Both (or all) stereoisomeric forms of each compound in the series can be readily synthesized in optically pure form by a simple one-step process from commercially available reagents. In addition to the ease of preparation, most of the chiral ILs in this series are liquid at room temperature with a solid to liquid transformation temperature as low as −70 °C …

University Of Nevada, Las Vegas Transmutation Research Program Annual Progress Report Academic Year 2007-2008, Anthony Hechanova, Rebecca Paulson

Transmutation Research Program Reports (TRP)

It is my pleasure to present the UNLV Transmutation Research Program’s seventh annual report that highlights the academic year 2007-2008. Supporting this document are the many technical reports and theses that have been generated over the past seven years.

In the seventh year of our program, we continued to see growth in the Radiochemistry Ph.D. program with a total of 20 students in the fourth year of the program (we anticipated twelve in the program proposal). Since our inception, the program has sponsored to their conclusion 48 M.S. and 6 Ph.D. degrees. The program supported 53 graduate students, 11 undergraduates, …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process (FLEX). The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the actinides …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU; includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership (GNEP). In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in …

F-Element Electrochemistry In Rtil Solutions: Electrochemical Separation Of Lanthanides And Actinides, David W. Hatchett

Separations Campaign (TRP)

Electrochemical methods can be used to effectively separate actinide and lanthanide species from complex mixtures. This is based on the unique electrochemical properties of each specific target species. In studies it has been found that, with the exception of Ce, aqueous solutions provide unsuitable electrochemical windows to effectively evaluate the thermodynamic properties that are useful for chemical separations. Therefore, a more novel approach was examined which eliminated the aqueous solution with a room temperature ionic liquid (RTIL) solution. RTIL solutions do not suffer from the side reactions that are prominent in aqueous environments. In addition, the potential window is much …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Separation Of Technetium From Uranium And Waste Form Synthesis, Kenneth Czerwinski

Waste Forms Campaign (TRP)

In this project, systematic investigations on the Tc-Zr binary metal system will be evaluated for the first time. The synthesis of metallic Tc as well as its alloys with Zr will be evaluated. In order to provide valuable data to AFC R&D, the thermodynamic equilibrium phases, as well as their performance under repository conditions, will be examined.

The research objectives of this project are as follows:

• Evaluate anion exchange methods for achieving the separation of Tc from U.

• Synthesize metallic Tc from the separated product.

• Synthesize and characterize Tc alloys.

• Investigate Tc-corrosion and Tc-leaching of binary …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic and microscopic methods, intermediate chemical phases at the interface, intermixing/diffusion behavior, and the electronic interface structure for different coating materials and metals are examined.

In detail, the project studies the interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon. Using SiC single crystals and highly-ordered pyrolytic carbon (HOPG) as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert fuels containing ZrO₂ and MgO as the inert matrix. Ceramics with this inert matrix, Ce, U and eventually Pu will be synthesized and examined. While the Advanced Fuel Cycle Initiative focus is on inert fuels with Pu as the fissile component, this task will perform initial laboratory experiments with Ce and U. The initial work with Ce will be performed early in the project with results used as a basis for U studies. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf. …

Impact Of The Synthesis Process On Structure Properties For Afci Fuel Candidates, Kenneth Czerwinski

Fuels Campaign (TRP)

The research objectives are:

• To explore a low-temperature fluoride route to synthesize actinide nitrides. • To characterize actinide nitrides structurally and thermally.

• To use high resolution TEM techniques to explore the microstructure of the radioactive samples.

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Tyler A. Sullens

Fuels Campaign (TRP)

One of the original synthetic routes devised for the synthesis of U (III)N involved the entire reaction taking place in liquid ammonia. Several experimental reactions were conducted in an attempt to synthesize the UI₃(NH₃)_x and U(NH₂)₃(NH₃)_x precursors of U(III) N. Each attempt involved cleaning of the uranium metal to remove the oxide coating of the metal reagent with 3 washes of concentrated nitric acid, each followed by a rinse with liquid ammonia. Success of this cleaning procedure was varied, with a majority of cleaned metal oxidizing rapidly once …

Improved High-Temperature Stability And Sun-Light-Driven Photocatalytic Activity Of Sulfur-Doped Anatase Tio2, Suresh Pillai, Declan Mccormack, Pradeepan Periyat, John Colreavy, Steve Hinder

Articles

No abstract provided.

Fourier-Transform Microwave Spectroscopy Of Cyclopropylmethylgermane And Van Der Waals Complexes Of Fluorinated Methanes, Michal M. Serafin

Masters Theses

Background theory and instrumentation utilized in the Fourier-transform microwave spectroscopy technique is first introduced followed by the structural and dynamic determination of cyclopropylmethylgermane and two weakly bound van der Waals complexes (difluoromethane-OCS, and fluoromethane-OCS). The minimum energy configuration has been determined for cyclopropylmethylgermane molecule, which has been shown to be the gauche configuration. Internal rotation parameters have been obtained from the rotational spectra of cyclopropylmethylgermane. The rotational spectra have been acquired for difluoromethanecarbonyl sulfide and fluoromethane-carbonyl sulfide and experimental structures have been determined for these weakly bound complexes. Evidence for a very low barrier to internal rotation has been observed …

Synthetic Studies Towards The Stellettins, Tung Yin Lin

Masters Theses

The synthesis of the stellettins, differing in the side chain at the C-13 position of the tricyclic region, was attempted by attaching the C-ring to a Wieland-Miescher ketone core using 1,3-bisphosphonoacetone. The decalin precursor was prepared in 35% from condensing ethyl acetate with acrolein, and a MnO2 oxidation, but too little material was obtained to cyclize this into the decalin. An alternative route involving a 2-step Robinson annulation of 2-methyl-1,3 cyclohexanedione with ethyl or methyl vinyl ketone and L-phenylalanine catalysis, followed by protecting C-9 carbonyl with acetal, gave 29% and 14% yields respectively.

1,3-Bisphosphonoacetone was prepared m a 3-step synthesis …

Using Azahetercyclic Electrophiles To Synthesize Novel Bicyclooxacalixarenes And Oxacalix[2]N-Hexylnaphthalimide[2]Naphthyridines, Doug Rooke

Honors Theses

Various bicyclooxacalixarenes, tricyclooxacalixarenes and oxacalix[2]N-hexylnapthalimide[2]naphthyridines are synthesized via SnAr condensation. This research has involved synthesis optimization. The oxacalix[2]N-hexylnaphthalimide[2]naphthyridines have exhibited host-guest binding in fluorescence experiments. These compounds have been characterized by NMR spectroscopy as well as single crystal X-ray diffraction.

The Development Of A "Genetic Eyewitness" Profiling System For Low Template Forensic Specimens: Identification Of Novel Protein, Rna, And Dna Biomarkers, Erin Hanson

Electronic Theses and Dissertations

In many criminal investigations, valuable information regarding the physical appearance of suspected perpetrators or the time and order of events that transpired are provided by eyewitness accounts. However, the information obtained from eyewitnesses is often constrained by human recollection or subjective accounts and provides a biased description of the perpetrator's appearance or an inaccurate time line of events. Additionally, in numerous situations eyewitness accounts may not be available. An increasing reliance therefore is placed on the biological evidence recovered during criminal investigations to act as a silent witness, providing unbiased and scientific information that may aid in the resolution of …

Reactions Of Atomic Carbon With Acid Chlorides, Daniel B. Herrick

Honors Theses

This thesis is the first report of reactions of atomic carbon with acid chlorides. Carbon is known to react with phosgene to afford dichlorocarbene. We report a similar reaction with carbon and acid chlorides, generating alkylchlorocarbenes. We examine both the nature of the carbene products generated through deoxygenation and the general reactivity of carbon with the acid chlorides. We report two ways in which carbon reacts with acid chlorides. First, as expected from prior work with phosgene, carbon deoxygenates the carbonyl group yielding alkylchlorcarbenes, which rearrange as expected. Second, carbon abstracts the chlorine, and generates the acyl radical, which, in …

Mechanistic Investigations Of The Trans Excision-Splicing And Trans Insertion-Splicing Reaction, Perry Patrick Dotson Ii

University of Kentucky Doctoral Dissertations

Group I intron-derived ribozymes are catalytic RNAs that have been engineered to catalyze a variety of different reactions, in addition to the native self-splicing reaction. One such ribozyme, derived from a group I intron of Pneumocystis carinii, can modify RNA transcripts through either the excision or insertion of RNA sequences. These reactions are mediated through the trans excision-splicing (TES) or trans insertionsplicing (TIS) reaction pathways. To increase our current understanding of these reactions, as well as their general applicability, a mechanistic and kinetic framework for the TES reaction was established. Furthermore, additional ribozymes were investigated for their ability to …

Electrical Detection Of The Temperature Induced Melting Transition Of A Dna Hairpin Covalently Attached To Gold Interdigitated Microelectrodes, Greg P. Brewood, Yaswanth Rangineni, Daniel J. Fish, Ashwini Bhandiwad, David R. Evans, Raj Solanki, Albert S. Benight

Chemistry Faculty Publications and Presentations

The temperature induced melting transition of a self-complementary DNA strand covalently attached at the 5' end to the surface of a gold interdigitated microelectrode (GIME) was monitored in a novel, label-free, manner. The structural state of the hairpin was assessed by measuring four different electronic properties of the GIME (capacitance, impedance, dissipation factor and phase angle) as a function of temperature from 25 degrees C to 80 degrees C. Consistent changes in all four electronic properties of the GIME were observed over this temperature range, and attributed to the transition of the attached single-stranded DNA (ssDNA) from an intramolecular, folded …

The Cis-Δ2,3-Double Bond Of Phoslactomycins Is Generated By A Post-Pks Tailoring Enzyme, Nadaraj Palaniappan, Mamoun M. Alhamadsheh, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The antifungal phoslactomycins (PLM A-F), produced by Streptomyes sp HK803, are structurally unusual in that three of their four double bonds are in the cis form (Δ^12,13, Δ^14,15, Δ^2,3). The PLM polyketide synthase (PKS) has the predicted dehydratase catalytic domain in modules 1,2 and 5 required for establishing two of these cis double bonds (Δ^12,13Δ^14,15), as well as the only trans Δ^6,7double bond. By contrast, the formation of the cis Δ^2,3 in the unsaturated lactone moiety of PLMs has presented an enigma because the predicted dehydratase domain …

Chromatographic And Mass Spectral Analyses Of Oligosaccharides And Indigo Dye Extracted From Cotton Textiles With Manova And Ano, Jessica Frisch

Electronic Theses and Dissertations

Research was conducted on thirteen 100% cotton denim samples using an acid wash, established by Murray, to extract oligosaccharides from the cellulosic material. The oligosaccharide ion groups (+, +, and +) for molecules with degrees of polymerization between two and seven (DP2-DP7) were analyzed using liquid chromatography coupled to mass spectrometry with an electrospray ionization interface (LC-ESI-MS). The results were compared using the least-squares means in a Multivariate ANOVA (MANOVA) test followed by Univariate ANOVA and Tukey HSD tests and demonstrated that the method could correctly determine that two samples were statistically different 85.9% of the time when analyzing the …

Development And Forensic Application Of Dye Probe Fluorescence Resonance Energy Transfer For Improved Detection Of Changes In Dn, Micah Halpern

Electronic Theses and Dissertations

Discovering, screening, and associating changes in DNA sequence are important to a broad range of disciplines and play a central role in Forensic Science. The typical types of changes include sequence variations [single nucleotide polymorphisms (SNP)] and length variations [short tandem repeats (STR)]. The steps for forensic DNA sample processing are similar for both types of changes but diverge at the point of detection. A number of approaches are being explored for SNP genotyping while STR analysis primarily consists of size-based analysis by capillary electrophoresis. Limitations exist for all current detection methods that pose significant impacts to forensic analysis. Bi-allelic …

The Identification Of Ignitable Liquids In The Presence Of Pyrolysis Products: Generation Of A Pyrolysis Product Database, Joseph Castelbuono

Electronic Theses and Dissertations

The fire debris analyst is often faced with the complex problem of identifying ignitable liquid residues in the presence of products produced from pyrolysis and incomplete combustion of common building and furnishing materials. The purpose of this research is to investigate a modified destructive distillation methodology provided by the Florida Bureau of Forensic Fire and Explosive Analysis to produce interfering product chromatographic patterns similar to those observed in fire debris case work. The volatile products generated during heating of substrate materials are extracted from the fire debris by passive headspace adsorption and subsequently analyzed by GC-MS. Low density polyethylene (LDPE) …

Lignin Degradation In Wood-Feeding Insects, Scott M. Geib, Timothy R. Filley, Patrick G. Hatcher, Kelli Hoover, John E. Carlson, Maria Del Mar Jimenez-Gasco, Akiko Nakagawa-Izumi, Rachel L. Sleighter, Ming Tien

Chemistry & Biochemistry Faculty Publications

The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut …