Chemistry Commons^™

Analytical And Synthetic Methods For Anatoxins., Janet Crowley

Theses

This thesis is focused on the potent cyanobacterial neurotoxins anatoxin-a (AN), its methyl analogue homoanatoxin-a (HMAN) and their non-toxic dihydro- and epoxydegradation products. In commencing the investigation into this area a literature review was performed in order to identify areas where more research and method development was required (Chapter 1). The review highlighted the fact that although a number of analytical methods had been developed for the analysis of AN, there were few methods for the determination of its potent homologue HMAN and their non-toxic degradation products. As these neurotoxins degrade quickly it is important to monitor their degradation products, …

Potential Energy Surface Of The Reaction Of Imidazole With Peroxynitrite: Density Functional Theory Study, Valentin Gogonea

Chemistry Faculty Publications

This article presents a theoretical investigation of the reaction mechanism of imidazole nitration by peroxynitrite using density functional theory calculations. Understanding this reaction mechanism will help in elucidating the mechanism of guanine nitration by peroxynitrite, which is one of the assumed chemical pathways for damaging DNA in cells. This work focuses on the analysis of the potential energy surface (PES) for this reaction in the gas phase. Calculations were carried out using Hartree–Fock (HF) and density functional theory (DFT) Hamiltonians with double-zeta basis sets ranging from 6-31G(d) to 6-31++G(d,p), and the triple-zeta basis set 6-311G(d). The computational results reveal that …

Simulations Of Nanopore Formation And Phosphatidylserine Externalization In Lipid Membranes Subjected To A High-Intensity, Ultrashort Electric Pulse, Q. Hu, R. P. Joshi, K. H. Schoenbach

Bioelectrics Publications

A combined MD simulator and time dependent Laplace solver are used to analyze the electrically driven phosphatidylserine externalization process in cells. Time dependent details of nanopore formation at cell membranes in response to a high-intensity (100kV∕cm), ultrashort (10ns) electric pulse are also probed. Our results show that nanosized pores could typically be formed within about 5ns. These predictions are in very good agreement with recent experimental data. It is also demonstrated that defect formation and PS externalization in membranes should begin on the anode side. Finally, the simulations confirm that PS externalization is a nanopore facilitated event, rather than the …

An Analysis Of The Effect Of Carbon Dioxide On The Decay Rates Of Superoxide, Michael Jay Walsh

Honors Theses

The radical dioxygen anion, superoxide has been shown to react with carbon dioxide in nonprotic and aqueous systems. Indirect evidence suggests that superoxide also reacts with carbon dioxide and carbonate species dissolved in water. This study involved conducting experiments to determine the decay rate of superoxide in the presence of carbon dioxide and carbonate species. Experiments were conducted by sparging an alkaline bicarbonate buffer with carbon dioxide and measuring the decay rate of superoxide added to the solution. Although the specific reaction mechanism and rates have not been determined first order superoxide decay rates as high as 3.8x10-2s-1 were obtained …

The Synthesis And Characterization Of Bicyclooxacalixarenes, Kevin J. Selby

Honors Theses

Bicyclooxacalixarenes were synthesized in high yield via a selective, room temperature Sn Ar reaction of phluoroglucinol with 2,6-dichloropyridines. Functionality on the 2,6-dichloropyridioe was varied by changing the electron-withdrawing groups in the 3 and 5 positions (using chlorine, nitro groups, and cyano groups) and the side-chains in the 4-position (using ethyl, butyl, phenyl and ρ-tolyl groups). The resulting cage-like molecules were studied by X-ray crystallography and tested for metal complexation.

Characterization Of Black Deposit Associated With Rock Paintings In Little Lost River Cave, Idaho Using Pyrolysis Gc, Sarah Therese Fezzey

Master's Theses and Doctoral Dissertations

A black, shiny coating overlies rock paintings in Little Lost River Cave no. 1, located in southeastern Idaho. If this coating is the result of human activity within the cave – a condensate from cooking fires, for example – then a radiocarbon date on the coating would provide a minimum age for the underlying paintings. The work reported here was undertaken to test the assumption that the coating has an anthropomorphic origin. Using pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) and thermally-assisted hydrolysis/methylation-GC-MS, we have compared samples of the black coating from Idaho to humic acid, a geologic material; an experimental cooking residue; …

An Investigation Into The Ring-Enlargement Reactions Of Boron Subphthalocyanine And Boron Subnaphthalocyanine, Andrew Jeremiah Jones

Master's Theses and Doctoral Dissertations

Ring enlargement syntheses of axially substituted boron subphthalocyanine and boron subnaphthalocyanine were investigated. The trihexylsiloxy derivatives of subphthalocyanine and subnaphthalocyanine were synthesized. These derivatives were then used in the ring-enlargement trials. Symmetrical and asymmetrical ring-enlargement reactions were carried out in a mixture of toluene and dimethylsulfoxide at room temperature. This study represents the first synthesis of boron subphthalocyanine with trihexylsiloxy group in the axial position and the first investigation into the ring enlargement of boron subnaphthalocyanine in which the axial ligand is a trihexylsiloxy group. Precipitates were formed, and it is believed that the precipitates are the metalfree ring-enlarged products. …

Studies Of Unusual Packing And Of Polymorphism In Two Crystal Systems, Xiang Hao

University of Kentucky Doctoral Dissertations

Crystal structures of anhydrous pinacol, the hexagonal pinacol, pinacol monohydrate, and pinacol hexahydrate were studied. In all the structures crystal packing is unusual and complicated. The origin of the complexity may be the difficulty in filling space densely and while also satisfying the H-bonding requirements when the molecule has few internal degrees of freedom.

Five 15-crown-5 complexes of M(NO₃)₂ (M = Cu, Zn, Mg, Co, Mn) were synthesized and characterized using X-ray diffraction and differential scanning calorimetry. The system is rich in polymorphs. Nine definite solid-state phases were identified. More phases probably exist in the solid state …

University Of Nevada, Las Vegas Transmutation Research Program: Annual Report Academic Year 2004-2005, Anthony Hechanova, Kathy Lauckner

Transmutation Research Program Reports (TRP)

It is my pleasure to present the UNLV Transmutation Research Program’s fourth annual report that highlights the academic year 2004 – 2005. Supporting this document are the many technical reports and scientific papers that have been generated over the past three years.

In the fourth year of our program, we added 11 new research tasks and saw the conclusion of 8 of the initial 16 independent student research tasks started in 2001 and 2002. In all, the program has sponsored to their conclusion 28 M.S. and 2 Ph.D. degrees. The program supported 58 graduate students and 13 undergraduates in 6 …

Corrosion Of Steel By Lead Bismuth Eutectic, John Farley, Allen L. Johnson, Dale L. Perry

Transmutation Sciences Materials (TRP)

There is an active international interest in lead-bismuth eutectic and similar liquid lead systems because of the relevance to the transmutation of nuclear waste, fast reactors, and spallation neutron sources.

Materials in these systems must be able to tolerate high neutron fluxes, high temperatures, and chemical corrosion. For lead bismuth eutectic (LBE) systems, there is an additional challenge because the corrosive behaviors of materials in LBE are not well understood. Most of the available information on LBE systems has come from the Russians, who have over 80 reactor-years experience with LBE coolant in their Alpha-class submarine reactors. The Russians found …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials, Ajit K. Roy

Transmutation Sciences Materials (TRP)

The primary objective of this task was to evaluate the effects of environmental and mechanical parameters on environment induced degradations of candidate target structural materials for applications in spallation-neutron-target systems. The materials selected for evaluation and characterization were martensitic stainless steels including Alloys HT-9, EP-823, and 422.

Accelerator-driven transmutation systems involve bombarding a target material such as molten lead-bismuth-eutectic (LBE) by a proton beam, thereby producing neutrons. The molten LBE target will be contained in a subsystem structural container made of a suitable material such as Alloys HT-9, EP-823, and 422. During the transmutation process, the target structural material may …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The corrosion of structural materials is a major concern for the use of lead-bismuth eutectic (LBE) systems for nuclear applications such as in transmuter targets or fast reactors. Corrosion in liquid metal systems can occur through various processes, including, for example, dissolution, formation of inter-metallic compounds at the interface, and penetration of liquid metal along grain boundaries. Predicting the rate of these processes depends on numerous system operational factors: temperature, system geometry, thermal gradients, solid and liquid compositions, and velocity of the liquid metal, to name a few. Corrosion, along with mechanical and/or hydraulic factors, often contributes to component failure. …

Development Of A Systems Engineering Model Of The Chemical Separations Process, Yitung Chen, Darrell Pepper, Sean Hsieh

Separations Campaign (TRP)

The chemical processing of used nuclear fuel is an integral component of any strategy for the transmutation of nuclear waste. Due to the large volume of material that must be handled in this first step of the transmutation process, the efficiency of the separations process is a key factor in the potential economic viability of transmutation strategies. The ability to optimize the chemical separation systems is vital to ensure the feasibility of the transmutation program.

Systems analysis, or total systems modeling, is one of the strongest tools available to researchers for understanding and optimizing complex systems such as chemical separations …

Nuclear Criticality, Shielding, And Thermal Analyses Of Separations Processes For The Transmutation Fuel Cycle, William Culbreth, Denis Beller

Separations Campaign (TRP)

The first step in any transmutation strategy is the separation of radionuclides in used nuclear fuel. The current separation strategy supporting the Advanced Fuel Cycle Initiative (AFCI) program is based on the use of a solvent extraction separation process to separate the actinides, fission products, and uranium from used commercial nuclear fuel, and on the use of pyrochemical separation technologies to process used transmuter fuels. To separate the fission products and transuranic elements from the uranium in used fuel, the national program is developing a new solvent extraction process, the Uranium Extraction Plus, or UREX+, process based on the traditional …

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)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of nuclear waste. Iodine-129, a long-lived fission product formed by both commercial nuclear power generation and nuclear weapons production, is released when reprocessing nuclear fuel. Since iodine can be concentrated in the human thyroid, any uncontrolled release of iodine may result in an increased rate of thyroid cancer in the exposed population. For this reason, recovery of iodine is important for implementing any nuclear transmutation strategy.

The stability of the association of iodine with FCC and NOM products are studied. Product …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Report #1-4, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

During current reporting period the experiments on synthesis of ceramic-like material by conversion of iodine-doped FCC and activated carbon to Si_xC_y have been completed. Cold pressed granules of FCC and activated carbon were rinsed in water-ethanol solution of tetraethoxysilane (TEOS), Si(OC₂H₅)₄, and then used for further synthesis. All new samples obtained have been studied using precise powder XRD analysis.

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Final Report 2005, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

Immobilization of highly radioactive and long-lived isotope of ¹²⁹I, which is a fission product in spent nuclear fuel, requires development of new durable host-materials.

Iodine is a very volatile chemical element, and even its chemically strong compounds such as AgI and CuI are not stable under ultraviolet irradiation or oxidizing conditions. Therefore, development of host materials for iodine immobilization is based on unusual approach – the search and testing of new compounds which were not studied before in respect of iodine sorption and strong fixation.

Although FCC material demonstrated high loading capacity to iodine sorption it is necessary to …

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, or 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 …

Development Of Fluorapatite As A Waste Form: Final Report #280204-1, Boris E. Burakov

Separations Campaign (TRP)

In the framework of Agreement #280204 (first year) it was necessary to review methods of apatite synthesis; identify optimal procedure of precursor preparation; obtain and study first fluorapatite samples. Although, some apatite-based ceramics were successfully synthesized using co-precipitated precursors and sintering method, there are still a lot of uncertainties related to optimal apatite doping with different radionuclides and non-radioactive elements. It is necessary to provide complete incorporation of waste elements into apatite crystalline structure avoiding formation of separate phases of radionuclides. Also, it is important to note that real waste streams might contain radionuclides with essentially different chemical features such …

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

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with our DOE collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing our ability to selectively target and sequester individual species from mixtures.

The following were specific goals for this year:

• To develop a fundamental understanding of the thermodynamic properties of actinide and lanthanide species such as Cm, Am, Ce, Nd, …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quarterly Report, Kenneth Czerwinski, Cynthia-May Gong, Amber Wright

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBPdodecane- nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30 % TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number …

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

Separations Campaign (TRP)

The research objectives of this project are as follows:

• 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 (by the addition of NaNO₃), 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 Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Anion And Cation-Yield Spectroscopy Of Core-Excited Sf6, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, M. M. Sant'anna, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We report an extensive study on total and partial-ion-yield spectroscopy around both the S 2p and F 1s thresholds in SF₆. All positive and negative single-ion channels have been measured. Below the F 1s threshold we detect a large variation in relative intensity of the resonant structures according to the specific channel monitored, indicating selective fragmentation. Above threshold, at variance with previous cases described by us, we detect high-intensity structures related to shape resonances not only in the cation channels but also for the anions. We discuss the applicability and limits of a model we …

2005- 2008 Unlv Mcnair Journal, Valerie Avery, Shana Bachus, Karmen K. Boehlke, Andrea Flores, Alden Kelly, Erick Lopez, Carol Preussler, Heather Shay, Ava Bookatz, Shaun Elsasser, Veronica Hicks, Shaida A. Jetha, Anthony Quinn, Thurithabhani Seneviratne, Teddy Boado Sim Jr., Liza Ward, Amris Henry-Rodgers, Jacquelynn Kaaa-Logan, Jason Orozco, Juan C. Plata, Bonnie Bartlett, Kathleen Bell, Vacheral M. Carter, Nydia Diaz, Kimberly Hackstock, Julio A. Luna, Charles Mao, Sandra Ramos, Precious Rideout, Benjamin Lee Watrous, Chet R. Whitley

McNair Journal

Journal articles based on research conducted by undergraduate students in the McNair Scholars Program

Table of Contents

Biography of Dr. Ronald E. McNair

Statements:

Dr. Neal J. Smatresk, UNLV President

Dr. Juanita P. Fain, Vice President of Student Affairs

Dr. William W. Sullivan, Associate Vice President for Retention and Outreach

Mr. Keith Rogers, Deputy Executive Director of the Center for Academic Enrichment and Outreach

McNair Scholars Institute Staff

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 2nd Quarter Report, 2005, Clemens Heske

Fuels Campaign (TRP)

The goal of our project is to investigate interface corrosion processes in TRISO nuclear fuel particles. For this purpose, we are undertaking a detailed study of the interface formation between potential candidates for metallic fission products (Pd, Ag, and Cs), likely to diffuse from the kernel of the TRISO particles, with the TRISO coating layers. As a starting point, we are investigating the Pd/SiC interface and will extend our studies to Ag/SiC during our current summer research campaign. The experimental approach comprises the preparation of metal/SiC interfaces in-situ in our ultra-high vacuum system by electron-beam deposition. In order to understand …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 1st Quarter Report, 2005, Clemens Heske

Fuels Campaign (TRP)

In this project we utilize a combination of state-of-the-art soft X-ray spectroscopies to understand the chemical bonding between metal fission products (Pd and Ag) with coating layers in TRISO fuel particles (SiC and pyrocarbon). We are primarily focusing on an analysis of intermediate chemical phases at the interface, the intermixing/diffusion behavior, and the electronic interface structure as a function of material choice (metal and coating materials), temperature, and external stress. In the current first project year, we are beginning these investigations with the Pd/SiC interface, as discussed in the previous two quarterly reports. Our first experiments (both using our lab …

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

Fuels Campaign (TRP)

The goal of this project is to elucidate the chemical bonding and interface formation of metal fission products with the coating materials used in state-of-the-art TRISO fuel particles. Particular emphasis is placed on an analysis of intermediate chemical phases at the interface, the intermixing/diffusion behavior, and the electronic interface structure as a function of material choice (metal and coating materials), temperature, and external stress. Furthermore, the chemical state of some of the metal fission products will be assessed.

This project studies the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. Using the TRISO coating materials (and …

Identification And Recovery Of An Asymmetric Calix[4]Arene Tetranitrile Derivative Using Liquid Chromatography And Mass Spectrometry, Benjamin Schazmann, Dermot Diamond

Articles

A simple analytical LC-MS (Liquid Chromatography Mass Spectrometry) method and associated instrumentation has been adapted for use by the organic chemist to yield mg quantities of target compound from a reaction mixture. Calix[4]arene 3 was identified as representing 51% of total peak area of a reaction mixture containing no less than 10 components, using LC-MS. This peak corresponded to a mass of 878.8, equivalent to a complex of 3 and an ammonium cation. Molecular models further rationalise this observation by showing that the asymmetric binding cavity of 3 is suitable for binding tetrahedral guests like the ammonium ion. By scaling …

A Study Of Epoxyolefin Cyclizations Catalyzed By Bismuth Trifluoromethanesulfonate And Other Metal Triflates, Ram Mohan, Joshua Lacey, Peter Anzalone, Christopher Duncan, Matthew Hackert

Scholarship

Epoxyolefin cyclizations have attracted considerable interest due to their importance in biosynthetic pathways. Bismuth trifluoromethanesulfonate as well as several other metal triflates are shown to be highly effective (0.1 mol %) catalysts for the cyclization of geraniolene oxide. The product composition is found to be more dependent on solvent and substrate concentration than on the nature of the metal triflate. Cyclization products are favored in CH₂Cl₂ and under high dilution conditions. Ether solvents favored acyclic products.

Methyl Methacrylate Oligomerically-Modified Clay And Its Poly (Methyl Methacrylate) Nanocomposites, Xiaoxia Zheng, David D. Jiang, Charles A. Wilkie

Chemistry Faculty Research and Publications

A methyl methacrylate oligomerically-modified clay was used to prepare poly(methyl methacrylate) clay nanocomposites by melt blending and the effect of the clay loading level on the modified clay and corresponding nanocomposite was studied. These nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis and cone calorimetry. The results show a mixed intercalated/delaminated morphology with good nanodispersion. The compatibility between the methylacrylate-subsituted clay and poly(methyl methacrylate) (PMMA) are greatly improved compared to other oligomerically-modified clays.