Chemistry Commons^™

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Final Report #1, 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.

Laboratory of Applied Mineralogy and Radiogeochemistry of the V.G. Khlopin Radium Institute carries out …

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

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal is for renewal of the UNLV portion of a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF₄, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and …

Development Of Fluorapatite As A Waste Form: Progress Report 1-2, Boris E. Burakov

Separations Campaign (TRP)

In the framework of this stage of research the samples of Sr-fluorapatite synthesized earlier had to be studied using different methods.

These are samples of the following desired compositions:

1) Sr₁₀(PO₄)₆F₂ from precipitated precursor;

2) Sr₁₀(PO₄)₆F₂ from precipitated precursor and adding Sr(NO₃)₂;

3) Sr₈CsNd(PO₄)₆F_2.3;

4) Initial precursor for the synthesis of un-doped Sr-fluorapatite.

Development Of Fluorapatite As A Waste Form: Progress Report 1-3, Boris E. Burakov

Separations Campaign (TRP)

In the framework of this stage of research we had to carry out synthesis and study of fluorapatite doped with fission product elements including Cs, Sr, noble metals and Zr. During previous reporting period different samples of ceramics based on Sr-fluorapatite have been synthesized. Sample of Cs-Nd-doped ceramic has been recognized as the most interesting for detailed examination by SEM and EMPA methods.

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

Separations Campaign (TRP)

Research on the apatite family of minerals to determine their suitability in the Flouride Extraction (FLEX) Process, which is part of the radioactive waste management stream.

1) KRI has fabricated and tested special high temperature furnace for fluorapatite synthesis. This equipment might be installed into glove box in order to carry out experiments with real actinides and technetium. The same equipment might be fabricated and installed in Actinide laboratory at HRC by KRI technical staff;

2) Samples of undoped polycrystalline apatite, Ca₅(PO₄)₃F, of low porosity were successfully obtained by sintering in air at 1300°C. …

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

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane- 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 …

Performance Characteristics Of Beamline 6.3.1 From 200 Ev To 2000 Ev At The Advanced Light Source, Ponnusamy Nachimuthu, J. H. Underwood, C. D. Kemp, Eric M. Gullikson, Dennis W. Lindle, David K. Shuh, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

Bend magnet beamline 6.3.1 at the Advanced Light Source operates from 200 eV to 2000 eV, primarily used for x-ray absorption fine structure investigations. The beamline optics consist of a compact, entrance-slitless, Hettrick-Underwood type variable-line-spacing plane-grating monochromator and refocusing mirrors to provide a 25 μm × 500 μm spot at the focal point in the reflectometer end station. Wavelength is scanned by the simple rotation of the grating and illuminates a fixed exit slit. The LabView based beamline control and data acquisition computer code has been implemented to provide a convenient interface to the user. The dedicated end station is …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion, 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, we intend to assess the chemical state of some of the metal fission products. The findings are expected to give valuable information about failure mechanisms of TRISO particles and fission product transport. Secondly, through simulating …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 3rd Quarter Report, 2004, Clemens Heske

Fuels Campaign (TRP)

The goal of this project, which started in May 2004, 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.

In detail, this project is devoted to studying the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. Using the TRISO coating materials and single crystal references as …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 4th Quarter Report, 2004, Clemens Heske

Fuels Campaign (TRP)

The goal of this project, which started in May 2004, 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. In detail, this project is devoted to studying the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. In order to study the properties of the relevant interfaces, …

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, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10 % of ²³⁹Pu. Ceramics will be synthesized and characterized based on the reactor physics results. The solubility the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, will be investigated in a manner to provide …

Block Copolymer Stabilized Self-Assembled Magnetic Nanoparticles, Li Zhang

Electronic Theses and Dissertations

Magnetic materials are currently being developed in the areas of pharmacology and medicinal chemistry for use in applications such as drug delivery and magnetic resonance imaging. Magnetic fluids are being used in audio equipment and hard disk drives. Their suspension in a particular fluid is promoted by the adsorption or reaction of steric or electrostatic stabilizers, which are appropriate for the particular medium. Critical to the success of these magnetic fluids is the development of the steric stabilizers, which must prevent the coagulation of the metal particles. Polymeric materials are one of the most suitable nonmagnetic media to disperse the …

The Design And Development Of A Comprehensive 49 Locus Y-Str Database For Major U.S. Populations, Paulina Niki Berdos

Electronic Theses and Dissertations

The establishment of a U.S. National Y-STR reference database from a variety of geographically and ethically diverse populations is essential to facilitate the generation of reliable estimates of Y-STR haplotype frequencies. Such multi-locus haplotype frequencies are required to provide a statistical estimate of the significance of a match. Y-STR loci, unlike traditional STR markers, are not independent of one another and are co-inherited as extended haplotypes of linked markers. The estimation of the frequency of occurrence of a particular haplotype therefore necessitates the use of a counting method, which means that the significance of many matches is dependent upon the …

Mitochondrial Dna Analysis By Pyrosequencing, Patsy-Ann Susan Hastings

Electronic Theses and Dissertations

Mitochondrial DNA (deoxyribo nucleic acid) is typically used in forensic casework when small quantities of high molecular weight quality DNA is not expected to be present thus negating the chances of obtaining usable nuclear DNA. Typical samples that utilized mitochondrial DNA analysis are: hair, bones, teeth, ancient remains (samples or remains that are at least 100 years old) or very old samples (samples that are less than 100 but greater than 10 years old). The current method used to evaluate mitochondrial DNA is Sanger sequencing. Although robust, it is also time consuming and labor intensive, on the other hand pyrosequencing …

Stability And Recovery Of Rna In Biological Stains, Mindy Eileen Setzer

Electronic Theses and Dissertations

In theory, RNA expression patterns, including the presence and relative abundance of particular RNA species, provide cell and tissue specific information that could be of use to forensic scientists. An mRNA based approach could allow the facile identification of the tissue components present in a body fluid stain and conceivably could supplant the battery of serological and biochemical tests currently employed in the forensic serology laboratory. Some of the potential advantages include greater test specificity, and the ability to perform simultaneous analysis using a common assay format for the presence of all body fluids of forensic interest. In this report, …

Electron Transfer In Phosphido-Bridged Complexes, Pradeep N. Perera

Masters Theses

No abstract provided.

Physiology And Biochemistry Of Sclerotinia Sclerotiorum, A Fungal Plant Pathogen, Erastus Gatebe

Masters Theses

No abstract provided.

Experimental Studies On Nucleation, Nanoparticle's Formation And Polymerization From The Vapor Phase, Victor Maher Abdelsayed

Theses and Dissertations

This research is divided into three major parts. In part I, the critical supersaturations required for the homogeneous nucleation of 2,2,2-trifluorothanol (TFE) vapor have been measured over a temperature range (266-296 K) using an upward thermal diffusion cloud chamber (DCC). The measured supersaturations are in agreement with the predictions of both the classical and the scaled theory of nucleation. Moreover, the condensation of supersaturated TFE vapor on laser-vaporized magnesium nanoparticles has been studied under different experimental conditions, such as the supersaturation, the pressure and the electric field. In part II, the laser vaporization controlled condensation (LVCC) technique was used to …

Far-Infrared Spectroelectrochemistry: A Study Of Linear Molybdenum/Iron/Sulfur Clusters, Michael D. Ryan, Lin Li

Chemistry Faculty Research and Publications

The far-infrared spectroelectrochemistry of linear M/Fe/S (M=Mo, W) complexes was investigated in methylene chloride and dichloroethane. With CsI as spectral windows, bands above 200 cm⁻¹ can be observed in methylene chloride, except for a weak methylene chloride band at 450 cm⁻¹. Substitution of dichloroethane for methylene chloride, solvents of nearly identical electrochemical properties, allows one to observe solute bands in the 450-cm⁻¹ region. The far-infrared spectroelectrochemistry of [MoFe₂S₄Cl₄]²⁻ and its tungsten analogue was investigated. The disappearance of the oxidation bands and the appearance of bands due to the reduced …

Additional Xps Studies On The Degradation Of Poly(Methyl Methacryalte) And Polystyrene Nanocomposites, Jianxin Du, Jianqi Wang, Shengpei Su, Charles A. Wilkie

Chemistry Faculty Research and Publications

XPS studies have been undertaken on exfoliated nanocomposites of polystyrene and poly(methyl methacrylate). One can clearly see that carbon is lost and that oxygen, silicon and aluminum accumulate at the surface of the degrading polymer. The concentration of aluminum at the surface is very low at the beginning of the experiment but makes a large jump at the same temperature at which carbon is lost and oxygen begins to accumulate at the surface. It appears that the ratio of silicon to aluminum changes as the polymer is lost. A brief discussion is given to explain the origin of oxygen at …

Thermal Properties Of Thermoplastics, Charles A. Wilkie, Michael A. Mckinney

Chemistry Faculty Research and Publications

No abstract provided.

Polybutadiene Modified Clay And Its Polystyrene Nanocomposites, Shengpei Su, David D. Jiang, Charles A. Wilkie

Chemistry Faculty Research and Publications

Vinylbenzyl chloride was allowed to react with a low-molecular-weight oligomer of butadiene in order to give a material that could then be used to alkylate an amine to form an ammonium salt. This ammonium salt was ion-exchanged onto a clay to give a new organically modified clay, which was used to prepare polystyrene-clay nanocomposites by solution and bulk polymerization and by melt blending. The nanocomposites were characterized by using X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, cone calorimetry, and the evaluation of mechanical properties. These systems show good nanodispersion and improvement in thermal and mechanical properties. J. Vinyl Addit. Technol. …

Synthesis And Antibacterial Assessment Of Water-Soluble Hydrophobic Chitosan Derivatives Bearing Quaternary Ammonium Functionality, Mrunal R. Thatte

LSU Doctoral Dissertations

Chitosan is a naturally occurring, bio-degradable, non-toxic, non-allergenic bio-polysaccharide derived from chitin, found in abundance in nature. Studies aimed at deriving newer applications of chitosan are hence of interest. Among these, one of the focuses of investigations is aimed at excellent antimicrobial activity demonstrated by chitosan. In this context, certain quaternary ammonium derivatives of chitosan have been shown in the past to be highly effective antibacterial materials. In the present study, substituted chitosan derivatives were synthesized and further quaternized using Quat-188 to produce water soluble derivatives at neutral pH. The antibacterial assessments of the quaternized derivatives of substituted chitosan were …

Synthesis, Characterization And Study Of Novel Reagents For The Detection Of Saccharides And Amino Acids, Nadia Nadette St. Luce

LSU Doctoral Dissertations

The design of synthetic receptors for the recognition and sensing of saccharides and amino acids is currently a major challenge. This is due to inherent structural similarity and a lack of chromophoric or fluorophoric properties of these compounds. The synthesis and study of novel detection agents for bioactive molecules as well as mechanistic studies are presented herein. The elucidation of the mechanism by which tetraarylboronic acid resorcinarene interact with sugar molecules and promote a solution color change is explored. This vast collaborative study, reveals that DMSO solutions of boronic acid functionalized resorcinarene macrocycles afford visual color changes upon heating or …

Spectroscopic Investigation Of Nitrogenase: Epr And Mcd Studies Of The Femo Cofactor And The P-Cluster, Robyn B. Broach

LSU Doctoral Dissertations

Little is known about substrate binding and reduction of nitrogenase. EPR spectroscopy is used here to observe intermediate states generated by different substrates. Two different spin states (S=3/2 and S=1/2) were exhibited for each substrate, which may result from different binding of the substrate to the cofactor (side-on or terminal binding) or the difference of the substrate binding to either Fe or Mo of the cofactor. Parallel studies were performed on a variant MoFe protein, alpha-195^Gln, which exhibited different signals from the wild-type suggesting that the substituted amino acid maybe necessary to reach some mechanistic states that the …

Spectroscopic And Synthetic Studies Relating To A Dirhodium Hydroformylation Catalyst, Petia Gueorguieva Gueorguieva

LSU Doctoral Dissertations

The main goal of this dissertation research was to further study and characterize our bimetallic hydroformylation catalyst, rac-[Rh₂(nbd)₂(et,ph-P4)](BF₄)₂, and to fully identify the catalytically inactive mono- and dirhodium complexes formed upon fragmentation of the catalyst under hydroformylation conditions. Various in situ NMR methods such as 1D ¹H and ³¹P, and 2D COSY, HMBC, and HMQC were employed and indicated the formation of the key catalyst, [rac-Rh₂H₂(μ-CO)₂(CO)₄(et,ph-P4)]²⁺, 4, and a number of other Rh-phosphine species on and off the catalytic cycle. …

Protein Aggregation Studies: Inhibiting And Encouraging Β-Amyloid Aggregation, Jed Paul Aucoin

LSU Doctoral Dissertations

This work demonstrates peptide-based aggregation mediation of fibril forming peptides, notably β-amyloid (1-40), Aβ_1-40. To achieve the goals of this work, Aβ_1-40 aggregation was governed by ionic strength, temperature, and pH. After controlling and reproducing Aβ_1-40 aggregate formation (fibrils), each peptide-based aggregation mediator was evaluated for its ability to self-aggregate and to possess surface-active properties. The incorporation of these mediators in Aβ_1-40 solutions changed the surface tension and produced aggregate complexes of mediator and Aβ_1-40. Evidence that Aβ_1-40 fibril formation may be mediated by disorder-to-order transitions has been observed by layer formation …

Electronic Structural Investigations Of Bi- And Polymetallic Complexes Using Quantum Mechanical Methods, Zakiya Sheni Wilson

LSU Doctoral Dissertations

Understanding the dynamics influencing chemical reactivity is essential for properly exploiting matter into more useful purposes. In that manner, computational chemistry is a tool frequently used to study chemical properties at the most intimate level, i.e. the single molecule.

With this work, we probe the chemistry governing a variety of multi-faceted bi- and polymetallic compounds. To date our research consists of four major projects: bimetallic rhodium-catalyzed hydroformylation and aldehyde-water shift hydrocarboxylation catalysis; a novel linear M-H-M interaction in a bridged bis(dialkylphosphino)methane complex of nickel; and CeBe₁₃, a heavy fermion conductor. Computational investigations on these systems allow us to …

Structural Effects Of Carbon Monoxide Coordination To Carbon Centers. Π And Σ Bindings In Aliphatic Acyl Versus Aromatic Aroyl Cations, M. G. Davlieva, Sergey V. Lindeman, Ivan S. Neretin, Jay K. Kochi

Chemistry Faculty Research and Publications

The binding of carbon monoxide to carbon centers has been examined with two series of aromatic and aliphatic oxocarbonium ions that are successfully isolated as crystalline and highly reactive (hygroscopic) aroylium and acylium salts with poorly coordinating counteranions. X-Ray crystallographic analyses at −150 °C afford precise structural parameters for the characteristic linear carbonyl bond (r_CO) and the bond to the carbon centers (r_Cα). The correlations of these structural parameters evaluated for alkyl (Me, Et and i-Pr) and aryl (p-Me, 2,4,6-trimethyl, p-MeO and p-fluorophenyl) oxocarbonium ions with the corresponding carbonyl …

Increased Frequency Of The Mthfr A1298c Mutation In An Irish Population, Cathal Mccarthy, Fergus Ryan, Joseph Vaughan

Articles

No abstract provided.