Physical Sciences and Mathematics Commons^™

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 …

Sequential Birch Reduction-Allylation And Cope Rearrangement Of O-Anisic Acid Derivatives, William Paul Malachowski, Marisha Banerji

Chemistry Faculty Research and Scholarship

A new method for the construction of quaternary centers on cycloalkane rings is reported. The Cope rearrangement of 4-methyl-2-allyl-2-(N-pyrrolidinyl)-carboxaniide-3-cyclohexenone yields 4-methyl-4-allyl-2-(N-pyrrolidinyl)-carboxamide-2-cyclohexenone in high yield. The rearrangement substrates are easily generated from Birch reduction-allylation of o-anisic acid derivatives.

Redox Reactions Of The Pyranopterin System Of The Molybdenum Cofactor, Sharon J. Nieter Burgmayer, Dori L. Pearsall, Shannon M. Blaney, Eva M. Moore, Calies Sauk-Schubert

Chemistry Faculty Research and Scholarship

This work provides the first extensive study of the redox reactivity of the pyranopterin system that is a component of the catalytic site of all molybdenum and tungsten enzymes possessing molybdopterin. The pyranopterin system possesses certain characteristics typical of tetrahydropterins, such as a reduced pyrazine ring; however, it behaves as a dihydropterin in redox reactions with oxidants. Titrations using ferricyanide and dichloroindophenol (DCIP) prove a 2e(-)/2H(+) stoichiometry for pyranopterin oxidations. Oxidations of pyranopterin by Fe(CN)(6)(3-) or DCIP are slower than tetrahydropterin oxidation under a variety of conditions, but are considerably faster than observed for oxidations of dihydropterin. The rate of …

Comparing Models For Measuring Ring Strain Of Common Cycloalkanes, Brad A. Hobbs

The Corinthian

The number of carbon atoms bonded in the ring of a cycloalkane has a large effect on its energy. A molecule's energy has a vast impact on its stability. Determining the most stable form of a molecule is a useful technique in the world of chemistry. One of the major factors that influence the energy (stability) of cycloalkanes is the molecule's ring strain. Ring strain is normally viewed as being directly proportional to the instability of a molecule. It is defined as a type of potential energy within the cyclic molecule, and is determined by the level of "strain" between …

Excimer Emission From Cathode Boundary Layer Discharges, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

The excimer emission from direct current glow discharges between a planar cathode and a ring-shaped anode of 0.75 and 1.5 mm diameter, respectively, separated by a gap of 250 μm, was studied in xenon and argon in a pressure range from 75 to 760 Torr. The thickness of the “cathode boundary layer” plasma, in the 100 μm range, and a discharge sustaining voltage of approximately 200 V, indicates that the discharge is restricted to the cathode fall and the negative glow. The radiant excimer emittance at 172 nm increases with pressure and reaches a value of 4 W/cm² for …

Reduced Acetylcholine Receptor Density, Morphological Remodeling, And Butyrylcholinesterase Activity Can Sustain Muscle Function In Acetylcholinesterase Knockout Mice, Michael Adler, Heather A. Manley, Angela L. Purcell, Sharad S. Deshpande, Tracey A. Hamilton, Robert K. Kan, George Oyler, Oksana Lockridge, Ellen G. Duysen, Robert E. Sheridan

United States Army: Publications

The vertebrate neuromuscular junction is designed for rapid transmission of excitatory signals for initiation of muscle contraction.5 Among the features responsible for the high throughput of this synapse are the close proximity of the presynaptic and postsynaptic membranes,10 the direct coupling of acetylcholine (ACh) binding to the opening of the ion channel associated with the nicotinic acetylcholine receptor (nAChR),27 the brief open time of this channel,21,27 and the presence of cholinesterase (ChE) for hydrolysis of ACh.21,30 At the endplate, there are two distinct ChEs for transmitter hydrolysis: acetylcholinesterase (EC 3.1.1.7, AChE) and butyrylcholinesterase (EC 3.1.1.8, BChE).33 Both enzymes can …

Simple Epoxide Formation For The Organic Laboratory Using Oxone, John J. Esteb

Scholarship and Professional Work - LAS

We present an epoxide formation experiment for a second-semester organic chemistry laboratory. This oxidation utilizes Oxone, a commercially available oxidizing agent, in the industrially relevant process of epoxide formation. The oxidant performing the oxidation is dimethyldioxirane, which is formed in situ. This experiment demonstrates a simple synthesis of an epoxide and formation of a secondary oxidizing agent.

Cautionary Comments (Author Response), John J. Esteb, Anne M. Wilson

Scholarship and Professional Work - LAS

Reply to concerns about a safety factor in the paper, “A Solvent-Free Oxidation of Alcohols in an Organic Laboratory."

A Novel Tiq2-Assisted Solar Photocatalytic Batch-Process Disinfection Reactor For The Treatment Of Biological And Chemical Contaminants In Domestic Drinking Water In Developing Countries, E. F. Duffy, F. Al Touati, S. C. Kehoe, O. A. Mcloughlin, L. W. Gill, W. Gernjak, I. Oller, M. I. Maldonado, S. Malato, John Cassidy, R. H. Reed, K. G. Mcguigan

Articles

he technical feasibility and performance of photocatalytic Ti02 coatings in batch-process solar disinfection (SODIS) reactors to improve potability of drinking water in developing countries have been studied. Borosilicate glass and PET plastic SODIS reactors fitted with flexible plastic inserts coated with Ti02 powder were shown to be 2(Jt1o and 25% more effective, respectively, than standard SODIS reactors for the inactivation of E. coli K12. Isopropanol at 100 ppm concentration levels was observed to be completely photodegraded after 24 h continuous exposure to lOG mW/cm2 simulated sunlight in a similar solar photocatalytic disinfector (SPC-DIS) reactor. The technique for p roducing the …

2,2':6',2"-Terpyridine N,N',N"-Trioxide, Kraig A. Wheeler, Scott E. Mckay, Silas C. Blackstock

Faculty Research and Creative Activity

No abstract provided.

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 …

Chemical Vapor Deposited Diamond Films For Self-Referencing Fiber Optic Raman Probes [Erratum], Sacharia Albin, Jainli Zheng, Bing Xiao, John B. Cooper, Robert B. Jeffers, Sonia Antony

Chemistry & Biochemistry Faculty Publications

No abstract provided.

Binding Studies On Molecularly Imprinted Polymers, Lucy Yue Hu

Dissertations, Theses, and Masters Projects

Molecular imprinting is a rapidly developing technique for preparation of polymeric materials that are capable of molecular recognition for selective separation and chemical identification. to prepare molecularly imprinted polymers (MIPs), a functional monomer and a crosslinker are polymerized in the presence of a template molecule. Then the template is extracted leaving sites which are complementary in both shape and chemical functionality to those of the template. This resin then becomes capable of selectively absorbing the template species. Because of MIPs' stability, predesigned selectivity, and easy preparation, they have been used for separation, sensor, drug development and directed synthesis.;In this study, …

Biologically Important Thiols In Various Vegetables And Fruits, Omca Demirkol, Craig D. Adams, Nuran Ercal

Chemistry Faculty Research & Creative Works

Biological thiols are important antioxidants, and recent studies showed that their contents vary depending on the groups of foodstuffs. Therefore, we investigated the levels of some biological thiols in various vegetables and fruits by using a sensitive high-performance liquid chromatography (HPLC) technique. Biological thiols measured in some vegetables and fruits include glutathione (L-glutamyl-L-cysteinly glycine, GSH), N-acetylcysteine (NAC), captopril [CAP (C9H15NO3S)], homocysteine (HCYS), cysteine (CYS), and -glutamyl cysteine (GGC). Our results show that biological thiol contents are between 3-349 nM/g wet weight in vegetables and 4-136 nM/g wet weight in fruits. CAP is only found in asparagus (28 nM/g wet weight). …

2,4-Dinitrophenylhydrazones Of 2,4-Dihydroxybenzaldehyde, 2,4-Dihydroxyacetophenone And 2,4-Dihydroxybenzophenone, Russell G. Baughman, Kenneth L. Martin, Rajendra K. Singh, James O. Stoffer

Chemistry Faculty Research & Creative Works

In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate (or 4-[(2,4-dinitrophenyl)-hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamide solvate

The Activity Of Silicon Carbide Particles In Al-Based Metal Matrix Composites Revealed By Scanning Electrochemical Microscopy, David O. Wipf, L. Díaz-Ballote, L. Veleva, M. A. Pech-Canul, M. I. Pech-Canul

College of Arts and Sciences Publications and Scholarship

Scanning electrochemical microscopy (SECM) is used to image variations in electrochemical activity over the surface of an aluminum-based metal matrix composite (MMC) in contact with buffered or unbuffered neutral solutions. The composite consists of an Al - 13.5% Si - 9% Mg alloy matrix and reinforcing silicon carbide particles (SiC_p). Feedback mode SECM imaging using ferrocenemethanol as a redox mediator in 0.1 M NaCl solution and in buffer solution (pH 6.8) revealed that the SiC particles are electrochemically active. The data suggest that the electronic conductivity at these sites is higher than that of the Al₂O …

Environment Friendly Organic Synthesis, Russell C. Smith '04

Honors Projects

In recent years, chemists have increasingly focused on environment friendly approaches to organic chemistry. By practicing Green Chemistry, chemists are attempting to reduce the use of hazardous materials and minimize waste. Green chemistry, which involves the design and some times redesign of chemical syntheses that are more environmentally friendly, attempts to lower risk by using inherently less toxic or non-toxic reagents.

The goal of this research was to (1) investigate the use of bismuth triflate as a catalyst for resorcinarene formation as well as the synthesis of homoallyl ethers and (2) to investigate the utility of ionic liquids as solvents …

Bismuth Compounds In Organic Synthesis. Bismuth Nitrate Catalyzed Chemoselective Synthesis Of Acylals From Aromatic Aldehydes, Ram Mohan, David Aggen, Joshua Arnold, Patrick Hayes, Nathaniel Smoter

Scholarship

Aromatic aldehydes are smoothly converted into the corresponding acylals in good yields in the presence of 3–10 mol% Bi(NO3)3•5H2O. Ketones are not affected under the reaction conditions. The relatively non-toxic nature of the catalyst, its ease of handling, easy availability and low cost make this procedure especially attractive for large-scale synthesis.

Environment-Friendly Organic Synthesis Using Bismuth Compounds. Bismuth Triflate Catalyzed Synthesis Of Substituted 3,4-Dihydro-2h-L-Benzopyrans, Ram Mohan, Mai Nguyen, Joshua Arnold, Katherine Peterson

Scholarship

A highly catalytic method for the synthesis of dihydrobenzopyrans from salicylaldehydes has been developed. An extension of this method to the synthesis of a pyrano [2,3,b]benzopyran has also been achieved. Bi(OTf)3.xH2O (1< x < 4) (0.1mol%) smoothly catalyzes the condensation of substituted salicylaldehydes with 2,2-dimethoxypropane to give the corresponding substituted 3,4-dihydro-2H-1-benzopyrans as a mixture of diastereomers (9:1) in moderate yields. The relative configuration of the methoxy groups in the two diastereomers was established by NOE experiments. The advantages of this method include the use of an easy to handle, inexpensive and relatively non-toxic catalyst.

Relation Between Increased Transmision In Xas And Increase In Abrikosov Vortices As T→Tc, J. Chigvinadze, G. Mamniashvilli, Juana Acrivos

Faculty Publications, Chemistry

The increased transmission, observed in the EXAFS region of their X-ray absorption spectra, as cuprate materials go through the superconducting transition temperature Tc is correlated with a critical increase in Abrikosov Vortex expulsion in zero magnetic field as the temperature T →Tc.

Enhanced Resonant Soft X-Ray Scattering Yba2cu3o7-X 50 Nm Thin Films On Bycristalline Substrates, M. Navacerrada, H. Sahibudeen, Jeffrey Kortright, Juana Acrivos

Faculty Publications, Chemistry

No abstract provided.

Theory And Experiments: Scf Calculations/Xrd/Enhanced Scattering/Pld In Ybco7-D Nano Film, H. Sahibudeen, M. Navacerrada, Juana Acrivos

Faculty Publications, Chemistry

X-Ray diffraction above and below the transition temperature to superconductivity Tc are correlated using SCF-MOLECOLE computations that describe the CuO2 layer (fig. 1) in the field of 9 unit cells of YBa2Cu3O7. The MO symmetry, charge transfer and OAOB bond mobility are compared to the data using the highest occupiedmolecular orbitals, MO-i (HOMO=MO0) bases to construct the layer tight-binding extended state.

On-Road Remote Sensing Of Automobile Emissions In The La Brea Area: Year 3, October 2003, Gary A. Bishop, Daniel A. Burgard, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Study Of Structural And Magnetic Properties Of Iron-Rich Mixed Rare-Earth Nddyfe (17-Y-X)Coxsiy Compounds, Kishore Kamaraju, Jinbo Yang, William B. Yelon, Oran Allan Pringle, M. S. Kim, Qingsheng Cai, William Joseph James

Physics Faculty Research & Creative Works

A series of NdDyFe(17-y-x)CoxSiy solid solutions with = 2 and 3 and = 0.5 1.0 and 1.5 were prepared by induction melting stoichiometric amounts of high-purity elements. The postannealed samples consist of two phases belonging to the space groups R3 m and P63 mmc . The lattice parameters and the unit cell volumes were calculated from the refinements of the magnetic and structural unit cells using the FULLPROF version of the Rietveld program. For a fixed content of Co, the maximum Curie temperatures (305 C to 405 C) were observed in samples with = 1 and having two phases, a …

Evaluation Of A Simple Carrier Molecule To Enhance Drug Penetration Of Dermal Layers By Utilizing Multivariate Methods, Structure Property Correlations, And Continuous System Modeling, Ronald Bartzatt

Chemistry Faculty Publications

Nicotinic acid is shown to be comparable to dihydropyridine in its capacity to facilitate penetration of an attached antibacterial drug through dermal layers. Antibacterial drugs examined with nicotinic acid or dihydropyridine carriers were b-lactam antibiotics: methicillin, oxacillin, benzylpenicillin, penicillin F, penicillin dihydro F, propicillin, carbenicillin, penicillin K, penicillin X, and ampicillin. An oxymethyl (-O-CH2-) group is inserted as the linker between the antibiotic and the carrier group. Structure Property Correlations and multivariate methods such as regression analysis, cluster analysis, principal component analysis, discriminate analysis, self-organizing tree algorithm, and factor analysis clearly showed that nicotinic acid performs as an effective carrier …