Chemistry Commons^™

The Study Of Carbon Acylation Of Highly Delocalized Enolates Using Catalytic Dmap On 3-Phenyl Benzofuranone Derivatives, Xiguang Zhao

Masters Theses

Benzofuranones along with their derivatives compose a diverse array of natural products and drugs, and show a wide variety of biological effects. Several synthetic methods have been published that describe the preparation of 2-(3H)-benzofuranones having mono alkyl or aryl substituents attached to the fused furanone ring with moderate to high yields. To date, reports describing the preparation of disubstituted 2-(3H)-benzofuranones, especially with one acyl group, are rare. Early approaches are limited by low yields, economical expenditure and environmental risk.

Direct acylation of benzofuranones consistently provides O-acylated isomers rather than C-acylated isomers, which are desired products in the great majority of …

Pressure Induced Octahedral Tilting Distortion In Ba2ytao6, Michael W. Lufaso, René B. Macquart, Yongjae Lee, Thomas Vogt, Hans-Conrad Zur Loye

Chemistry Faculty Research and Scholarship

Herein we communicate the first example of a pressure induced octahedral tilting distortion in a double perovskite phase, which was observed during the structural characterization of Ba2YTaO6 using high-pressure synchrotron X-ray powder diffraction.

Measurement Of Ammonium By Ion Chromatography In High Sodium Concentration, Sharon Klein

The Journal of Undergraduate Research

Chemical analysis of Antarctic ice cores provides valuable information on the history and dynamics of the atmosphere environment. The ice core samples contain trace amounts of ammonium, sodium, and other ionic chemical species, which are usually, measured using ion chromatography. High concentrations of sodium may interfere with the accurate and precise measurement of ammonium, due to insufficient resolution of their chromatographic peaks. The extent of the interference is investigated in this project by quantitative determination of the ammonium concentration in solutions of various ammonium and sodium concentrations. A criterion of 20% relative error of measured ammonium concentration is used to …

University Of Nevada, Las Vegas Transmutation Research Program Annual Report Academic Year 2005-2006, Anthony Hechanova, Rebecca Arbour

Transmutation Research Program Reports (TRP)

It is my pleasure to present the UNLV Transmutation Research Program’s fifth annual report that highlights the academic year 2005 – 2006. Supporting this document are the many technical reports and scientific papers that have been generated over the past five years.

In the fifth year of our program, we saw amazing growth in the Radiochemistry Ph.D. program with a total of 12 students in the second year of the program (twice the number we anticipated in the program proposal). In the back of this issue, under Infrastructure Augmentation, you will find some news about the new academic programs sponsored …

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 …

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 …

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 a national laboratory collaborators, electrochemical methods and materials will be 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 is in its third year and has successfully completed Phases 1 and 2.

The following were specific goals for this year:

• To develop a fundamental …

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, …

Isothermal Titration Calorimetry And Transmission Electron Microscopy Of Main-Chain Viologen Polymer Containing Bromide As Counerions, Pradip K. Bhowmik, Marcos A. Cheney, Haesook Han, Longzhou Ma

Transmission Electron Microscope

Polyelectrolytes are an important class of macromolecules that contain dissociable ionic groups. When introduced into polar solvent, usually the universal solvent water, dissociation takes place so that electrically charged macromolecule is suspended in solution. The electrostatic interaction is operative between ionized groups inside the macromolecule, between the macromolecules, between the counterions, and between the macromolecule and counterion. Since this interaction is characterized by its long-range nature, the solution exhibits various interesting properties including the polyelectrolyte behavior very different from solutions of neutral polymers.

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 1st Quarterly Report, 2006, Clemens Heske

Fuels Campaign (TRP)

This project is devoted to an in-depth study of the chemical and electronic impact of metal fission products on the coating layers in TRISO nuclear fuel. In particular, there is a focus on the investigation of Pd, Cs, and Ag and their interface formation with SiC and carbon-based substrates. A variety of surface and near-surface bulk sensitive probes that investigate the occupied and unoccupied electronic states of the substrate and the metal overlayer have been utilized. By a controlled and stepwise deposition of the metal overlayer, it is possible to gain substantial insight into the formation of interfaces and their …

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

Fuels Campaign (TRP)

In this project the chemical bonding and interface formation of metal fission products with the coating materials used in TRISO fuel particles is investigated. The interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon is studied in detail. Using the SiC single crystals and TRISO coating materials as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied with a photoelectron spectroscopy, Auger electron spectroscopy, Inverse Photoemission, X-ray emission spectroscopy, and X-ray absorption spectroscopy. Recent additions to the experimental approach include microscopic techniques (Transmission Electron Microscopy, Scanning Tunneling Microscopy, Atomic Force Microscopy) …

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

Fuels Campaign (TRP)

This project examines 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 are 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 are synthesized and characterized based on the reactor physics results. The solubility of the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, are investigated in a manner to provide thermodynamic data necessary for …

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Thomas Hartmann

Fuels Campaign (TRP)

A wide variety of fuel concepts are considered for advanced reactor technology including metals, metal oxides or metal nitrides as solid solutions or composite materials. Nitride fuels have appropriate properties for advanced fuels including high thermal conductivity, thermal stability, solid-state solubility of actinides, fissile metal density, and suitable neutronic properties. A drawback of nitride fuels involves their synthesis. A key parameter for preparing oxide fuels is the precipitation step in the sol-gel process. For nitride fuels, the current synthetic route is carbothermic reduction from the oxide to the nitride. This process step is based on solid phase reactions and for …

A Chloride Selective Calix[4]Arene Optical Sensor Combining Urea Functionality With Pyrene Excimer Transduction, Benjamin Schazmann, Dermot Diamond

Articles

A neutral 2-site chloride selective compound has been developed (3), based on a 1,3- alternate tetrasubstituted calix[4]arene providing a preorganised supramolecular scaffold. The resultant supramolecular cavity is amongst the first to combine urea functional groups bridged with single methylene spacers to pyrene moieties. It combines a naturally and synthetically proven H-bonding system with the elegant ratiometric fluorescent signalling properties of an intramolecular pyrene excimer system, triggered by conformational changes upon anion coordination. The excimer emission of 3 is quenched, with a simultaneous rise in the monomer emission solely by the chloride anion amongst a wide variety of anions tested. 3 …

Development Of A Calix[4]Arene Sensor For Soft Metals Based On Nitrile Functionality, Benjamin Schazmann, Dermot Diamond

Articles

The current work is amongst the first to examine the potential usefulness of the nitrile functional group in potentiometric analytical sensors for soft metals. Nitrile functionality has hereby been incorporated into a calix[4]arene skeleton to give a series of new cation selective hosts. The analytical sensing behaviour of these hosts was examined by Ion Selective Electrode (ISE) based potentiometry. In all cases a preference for soft metals was observed, explained primarily in terms of soft–soft compatibility between calix[4]arene nitrile hosts and metal guests in combination with a classical ‘lock and key’ best fit mechanism. Hosts 2, 3 and 4 showed …

Trans-Atlantic Correlation Of Upper Cretaceous Marine Sediments, Marcus R. Ross, David E. Fastovsky

Faculty Publications and Presentations

Upper Cretaceous marine deposits from the Mid-Atlantic region of North America (Delaware, Maryland, and New Jersey) and the Maastricht area (southern Netherlands, and nearby Belgium and Gennany) are correlated across the Atlantic using a variety of macro invertebrates, nannofossils, and sequence stratigraphy. Four late Cretaceous Mid-Atlantic sequences, the Marshalltown, Englishtown, Merchantville, and Navesink, span the upper Santonian to lowennost Danian, and have direct correlatives in the Maastricht area. Correlations between the Mid-Atlantic and the Maastricht regions (respectively) are as follows: the upper Santonian to lower Campanian Merchantville and Matawan formations with the Achen and lower Vaals fonnations; the middle Campanian …

A Taxonomy Of Teleology: Phillip Johnson, The Intelligent Design Community, And Young-Earth Creationism, Marcus R. Ross, P. A. Nelson

Faculty Publications and Presentations

No abstract provided.

The Mechanism Of Potential Shifts Of Activated Carbon Due To Adsorption Of Organic Compounds, Mikhail M. Goldin, Vladimir Avramenko, Alexander G. Volkov, Mark Goldin

Faculty Publications and Presentations

No abstract provided.

Controlling Charge Injection In Organic Field-Effect Transistors Using Self-Assembled Monolayers, B H. Hamadani, D A. Corley, Jacob W. Ciszek, J M. Tour, D Natelson

Chemistry: Faculty Publications and Other Works

We have studied charge injection across the metal/organic semiconductor interface in bottom-contact poly(3-hexylthiophene) (P3HT) field-effect transistors, with Au source and drain electrodes modified by self-assembled monolayers (SAMs) prior to active polymer deposition. By using the SAM to engineer the effective Au work function, we markedly affect the charge injection process. We systematically examine the contact resistivity and intrinsic channel mobility and show that chemically increasing the injecting electrode work function significantly improves hole injection relative to untreated Au electrodes.

Synthesis And Analysis Of An Α-Amylase Inhibitor And An Antimicrobial Peptide, Brahmlin Kaur Sethi

Senior Honors Theses and Projects

Abstract 1: α-Amylase is an important enzyme in the body responsible for hydrolyzing many polysaccharides such as dietary starch. Inhibition of this enzyme could be extremely beneficial in diabetic patients because it could lower the glucose levels in the blood. Our objective is to synthesize a small analog of a natural α-amylase inhibitor, Tendamistat. This molecule has 15-22 residue segment that are critical for its activity. The peptide was synthesized, cleaved, purified, analyzed, and an enzyme assay was run. Michaelis Menton and Lineweaver-Burk plots were constructed to determine the V_max, K_m, and K_i for each …

Limited Proteolysis Of Human Histone Deacetylase 1, Nayana Kamath, Paulina Karwowska-Desaulniers, Mary Kay H. Pflum

Wayne State University Associated BioMed Central Scholarship

Abstract

Background

Histone deacetylase (HDAC) proteins are associated with cell proliferation, differentiation, apoptosis, and cancer. Specifically, HDAC1 is linked with cell growth, a hallmark of cancer formation. HDAC1 is a phosphoprotein and phosphorylation at S421 and S423 promotes HDAC1 enzymatic activity and protein association. While single and double point mutants of HDAC1 at S421 and S423 appear functionally similar, the evidence suggests that HDAC1 is phosphorylated simultaneously at both S421 and S423 in vivo. Additional experiments are necessary to probe the role of double phosphorylation of HDAC1 at S421 and S423.

Results

To characterize HDAC1 phosphorylation at S421 and S423, …

Simultaneous Ejection Of Six Electrons At A Constant Potential By Hexakis(4-Ferrocenylphenyl)Benzene, Vincent J. Chebny, Dwairath Dhar, Sergey V. Lindeman, Rajendra Rathore

Chemistry Faculty Research and Publications

A simple synthesis of a dendritic hexaferrocenyl electron donor (5) is described in which six ferrocene moieties are connected at the vertices of the propeller of the hexaphenylbenzene core. The molecular structure of 5 is confirmed by X-ray crystallography. An electrochemical analysis along with redox titrations (which are tantamount to coulometry) confirmed that it ejects six electrons at a single potential.

Ligand-Promoted Solvent-Dependent Ionization And Conformational Equilibria Of Re(Co)3Br[Ch2(S-Tim)2] (Tim = 1-Methylthioimidazolyl). Crystal Structures Of Re(Co)3Br[Ch2(S-Tim)2] And {Re(Co)3(Ch3Cn)[Ch2(S-Tim)2]}(Pf6), Rosalice M. Silva, Brendan J. Liddle, Sergey V. Lindeman, Mark D. Smith, James R. Gardinier

Chemistry Faculty Research and Publications

The compounds Re(CO)₃Br[CH₂(S-tim)₂] (1) and {Re(CO)₃(CH₃CN)[CH₂(S-tim)₂]}(PF₆) (2), where tim is 1-methylthioimidazolyl, were prepared in high yields and characterized both in the solid state and in solution. The solid-state structures show that the ligand acts in a chelating binding mode where the eight-member chelate ring adopts twist-boat conformations in both compounds. A comparison of both solid-state IR data for CO stretching frequencies and the solution-phase voltammetric measurements for the Re^1+/2+ couples between 1, 2, …

Polystyrene Nanocomposites Based On An Oligomerically-Modified Clay Containing Maleic Anhydride, Xiaoxia Zheng, David D. Jiang, Charles A. Wilkie

Chemistry Faculty Research and Publications

An oligomerically-modified clay containing maleic anhydride was used to prepare polystyrene-clay nanocomposites by melt blending and the effect of this modified clay on the thermal stability and fire performance was studied. These nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis and cone calorimetry. The results show a mixed immiscible/intercalated/delaminated morphology. The maleic anhydride modified clay improved the compatibility between the clay and the polystyrene.

The Redox Couple Of The Cytochrome C Cyanide Complex: The Contribution Of Heme Iron Ligation To The Structural Stability, Chemical Reactivity, And Physiological Behavior Of Horse Cytochrome C, Abel Schejter, Michael D. Ryan, Erica R. Blizzard, Chongyao Zhang, Emanuel Margoliash, Benjamin A. Feinberg

Chemistry Faculty Research and Publications

Contrary to most heme proteins, ferrous cytochrome c does not bind ligands such as cyanide and CO. In order to quantify this observation, the redox potential of the ferric/ferrous cytochrome c–cyanide redox couple was determined for the first time by cyclic voltammetry. Its E⁰′ was −240 mV versus SHE, equivalent to −23.2 kJ/mol. The entropy of reaction for the reduction of the cyanide complex was also determined. From a thermodynamic cycle that included this new value for the cyt c cyanide complex E⁰′, the binding constant of cyanide to the reduced protein was estimated to …

Magnetic Order In The Quasi-One-Dimensional Spin-1/2 Molecular Chain Compound Copper Pyrazine Dinitrate, T Lancaster, S J. Blundell, M L. Brooks, P J. Baker, F L. Pratt, Jamie L. Manson, C P. Landee, C Baines

Chemistry and Biochemistry Faculty Publications

We present evidence of magnetic order in the quasi-one-dimensional spin-1/2 molecular chain compound, copper pyrazine dinitrate Cu(C4H4N2)(NO3)(2). Zero field muon-spin relaxation measurements made at dilution refrigerator temperatures show oscillations in the measured asymmetry characteristic of a quasistatic magnetic field at the muon sites. Our measurements provide convincing evidence for long-range magnetic order below a temperature T-N=107(1) mK. This leads to an estimate of the interchain coupling constant of vertical bar J'vertical bar/k(B)=0.046 K and to a ratio of vertical bar J'/J vertical bar=4.4x10(-3).

Open-Ocean Carbon Monoxide Photoproduction, Aron Stubbins, Günther Uher, Cliff S. Law, Kenneth Mopper, Carol Robinson, Robert C. Upstill-Goddard

Chemistry & Biochemistry Faculty Publications

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQY_CO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQY_CO and the CDOM spectra collected. …

Effects Of Salinity Changes On The Photodegradation And Ultraviolet-Visible Absorbance Of Terrestrial Dissolved Organic Matter, E. C. Minor, J. Pothen, B. J. Dalzell, H. Abdulla, K. Mopper

Chemistry & Biochemistry Faculty Publications

We performed laboratory studies to determine the effects of salinity on the photodegradation of dissolved organic matter (DOM) from the Great Dismal Swamp, Virginia, an important source of terrestrial DOM to the lower Chesapeake Bay. Samples were created by mixing Great Dismal Swamp water (ionic strength approximate to 0 mol L^-1) with modified artificial seawater solutions of differing salinities while keeping the final dissolved organic carbon (DOC) concentration constant. These samples were then irradiated for 24 h in a light box providing ultraviolet (UV) light similar to that of natural sunlight. Light absorbance and DOC concentrations decreased after …

New Developments On High-Resolution Luminescence Spectroscopy And Their Application To The Direct Analysis Of Organic Pollutants, Shenjiang Yu

Electronic Theses and Dissertations

Polycyclic aromatic compounds (PACs), which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion of pyrolisis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air, soil, and water. Chemical analysis of PACs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Because PACs carcinogenic properties strongly depend on molecular …

Structural And Thermodynamic Parameters Associated With The Interaction Of Cobalt (Iii) Complexes And Duplex Dna, Jaime M. Ferreira

Seton Hall University Dissertations and Theses (ETDs)

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