Chemistry Commons^™

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

Separations Campaign (TRP)

The objectives of this project are to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solution, and to use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborator, 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. Phase 3 has been partially completed. The tasks have been expanded …

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 Pu are …

F-Element Electrochemistry In Room Temperature Ionic Liquids, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This proposal focuses on f-element electrochemistry in room temperature ionic liquids (RTILs). The ultimate goal is to fully characterize the oxidation/reduction of elements in RTILs to establish the baseline thermodynamic and kinetic data for these systems. The data will be used to critically evaluate the ability to use electrochemical methods for controlled, potential mediated, separation off-elements by electroplating on electrodes surfaces. Factors that will influence the ability to measure the redox processes in f-elements in RTIL solutions and electroplating on electrode surfaces include the structure, solubility, and stability of the target species in these solutions. These factors will be addressed …

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 UREX separation scheme, providing data useful to modeling. The areas to be examined include the speciation of U and Pu with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK system. The complexation constants of U and Pu with tributylphosphate will be evaluated. In the TALSPEAK system, …

Evaluation Of Cs/Sr Waste Form For Long Term Storage And Disposal, Gary Cerefice, Longzhou Ma

Waste Forms Campaign (TRP)

The goal of this project is to examine two potential concerns regarding the long-term performance of a proposed cesium/ strontium waste form. To facilitate long-term storage, up to 300 years, the disposal containers will need to be able to survive for the entire storage interval. The first aspect of the project will explore the potential interaction of the aluminosilicate waste form with the storage canister materials to determine if there is any corrosion or chemical interaction concerns for the storage of the materials.

At the end of the storage interval, most of the 137Cs in the waste form will have …

A Novel Tio2 / Pvc Layer For Use In A Photoelectrochemical Cell, Faiza Touati, John Cassidy, Kevin Mcguigan

Articles

A novel method of coating titanium dioxide on a glassy carbon electrode as a polyvinylchloride composite , is described. On illumination , there is an enhanced voltammetric current at this TiO2/PVC composite in aqueous formic acid solution. This electrode is used as the basis of a formic acid fuel cell where oxygen is reduced at a platinum cathode. The system yields 100 cm-2 for 0.01 mol dm-3 HCOOH in 0.1 mol dm-3 NaOH under illumination from a 150 W xenon lamp. The current without illumination is 0.5 cm-2.

Supramolecular Usefulness Of Hexamethylenetetramine, Philias Daka

Masters Theses

Because non-covalent contacts are important to the design and construction of materials with functional applications, efforts that seek to uncover chemical features responsible for the assembly of multimolecular arrays hold current interest. The building-block approach is one strategy that has been successfully employed for the construction of molecular assemblies. By designing molecular components with complementary functional groups, the construction of predictable supramolecular motifs is possible. Although various modes of molecular alignment have been generated using this strategy, the extension of low dimensional motifs (discrete and 1-D patterns) to 2- and 3-D patterns remain a current challenge.

Identification And Characterization Of A New Tubulin-Binding, Susan L. Mooberry, Kimberly N. Weiderhold, Sivanesan Dakshanamurthy, Ernest Hamel, Edith J. Banner, Anastasia Kharlamova, Jonathan Hempel, John T. Gupton, Milton L. Brown

Chemistry Faculty Publications

We studied the mechanism of action of 3,5-dibromo-4-(3,4-dimethoxyphenyl)-1H-pyrrole-2-carboxylic acid ethyl ester (JG-03-14) and found that it is a potent microtubule depolymerizer. JG-03-14 caused a dose-dependent loss of cellular microtubules, formation of aberrant mitotic spindles, accumulation of cells in the G₂/M phase of the cell cycle, and Bcl-2 phosphorylation. These events culminated in the initiation of apoptosis, as evidenced by the caspase 3-dependent cleavage of poly(ADP-ribose) polymerase (PARP). JG-03-14 has antiproliferative activity against a wide range of cancer cell lines, with an average IC₅₀ value of 62 nM, and it is a poor substrate for transport …

Studies Directed Toward The Diastereocontrolled Synthesis Of Heritol, Prashanth K. Padakanti

Masters Theses

3,3-Dichloro-4-indanyloxetan-2-one was synthesized and its double ring expansion in the presence of the Lewis acid magnesium bromide was investigated, which resulted only in a trans-fused butyrolactone in 25% yield. Of the natural products containing butyrolactones fused to 6-membered rings, trans is more common. This method of double ring expansion can be applied to the synthesis of the natural product heritol, whose core structure contains the butenolide moiety. A model study of the double ring expansion was performed with 3-chloro-4-indanyl-3-methyloxetane-2-one B6, but this study was not completed.

In order to apply the double ring expansion methodology to synthesize heritol, the preparation …

Intramolecular Chemistry Of Ss-Acetoxyethylidene And Photochemical Generation Of Vinylidenes, Jennifer M. Nguyen

Honors Theses

The parent carbene ß-acetoxyethylidene has been previously generated by the photolysis of its precursor, acetic acid 1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-yl methyl ester. Mechanistic studies on ß-acetoxyethylidene have indicated the possibilities of three rearrangement pathways to the formation of vinyl acetate: a proton shift, an acyl shift, and a cyclic rearrangement (see Figure 8). A deuterium labeling study involving the replacement of the hydrogens on the methylene carbon has indicated that the simple 1,2-H shift was the primary manner of rearrangement, with an 82% yield of product. However, a primary kinetic isotope effect may have occurred due to the greater strength of a C-D …

Computational Models To Predict The Inhibition Of Cytochrome P450 3a4 By Selected Natural Compounds, Sushma Thotakura

Theses and Dissertations

Cytochrome P450 3A4 (CYP3A4) plays a pivotal role in the metabolism of xenobiotics. Methylenedioxobenzene containing natural products have been shown to inhibit CYP3A4. Given that these compounds are widely distributed in nature there is a strong potential for drug interaction with many plants used for dietary or medicinal purposes. In this research we have developed two different computational models (Comparative Molecular Field Model and Artificial Neural Network Model) to assist in the identification of potentially strong inhibitors that could be further studied for potential inhibitory effects. These models were used to screen for the CYP3A4 inhibitory effects of 100 naturally …

Evaluation And Characterization Of Some Biologically Active Coumarin Derived Sulfonamides, Harish Gosike

Theses and Dissertations

Sulfonamide drugs discovered in the 1930's were the first effective chemotherapeutic agents to be employed for the prevention and cure of bacterial infections in humans. Bacterial resistance to these drugs over the years has led to the development of new variety of sulfonamide derivatives. Recently Chohan et al. synthesized a series of coumarin derived sulfonamides and their chemical structures have been established. In this report, we present some microbiological studies to establish the antibacterial characters of these compounds. In order to establish their chemical structure-biological activity relationship, electrochemical and spectroscopic studies have been conducted. Antibacterial studies conducted on these compounds …

Identification Of Potential Organic Contributors In Carbonaceous Aerosols: Enhanced Uv Absorption Spectra, Anand Mangu

Theses and Dissertations

Direct aerosol climate effects include light scattering and absorption that present the largest uncertainties in the assessment of radiative forcing. To estimate the overall effect of aerosols on climate the relative amounts of scattering and absorption must be known. Determination of aerosol UV-absorption spectra is the primary focus of this thesis research. Aerosol samples were collected in Mexico City in 2003 and 2006 as a part of Mexico City Metropolitan Area field study and also at Little Rock. UV-visible absorption spectra of these aerosol samples have been obtained by using an integrating sphere coupled to a UV-visible spectrometer and compared …

Synthesis And Characterization Of Highly Conductive Polypyrrole And Polypyrrole/Lignosulfonate/Graphite Composites, Aopeau Imvittaya

Theses and Dissertations

Polypyrrole (PPy) is one of the conductive polymers frequently used in commercial applications, mainly due to its long-term stability and the possibility of forming homopolymers or composites with optimal properties. Polypyrroles were prepared by the chemical polymerization of pyrrole using various methods. The effects of several parameters such as oxidant, dopant type, additives and reaction conditions on the properties of PPy were investigated. In addition, PPy/graphite composites were prepared because graphite is highly conductive and effectively incorporated into the polymer matrix during the polymerization. The amount of graphite in the composite was varied to determine the maximimum conductivity achievable in …

Modular Polyketide Synthases And Cis Double Bond Formation:  Establishment Of Activated Cis-3-Cyclohexylpropenoic Acid As The Diketide Intermediate In Phoslactomycin Biosynthesis, Mamoun M. Alhamadsheh, Nadaraj Palaniappan, Suparna Daschouduri, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The majority of modular polyketide synthase (PKS) systems which generate unsaturated products do so with trans double bonds. Phoslactomycin B (PLM B) presents a class of antitumor and antiviral natural polyketide products that have unique structural features, including a linear unsaturated backbone with one trans and three cis double bonds. There is substantial evidence that trans double bonds are established by ketoreductase-dehydratase (KR-DH) didomains within a PKS module. In cases where modules containing these didomains appear to generate product containing a cis double bond there is no experimental evidence to determine if they do so directly, or if they also …

Antibacterial Targets In Fatty Acid Biosynthesis, H. Tonie Wright, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The fatty acid biosynthesis pathway is an attractive but still largely unexploited target for development of new anti-bacterial agents. The extended use of the anti-tuberculosis drug isoniazid and the antiseptic triclosan, which are inhibitors of fatty acid biosynthesis, validates this pathway as a target for anti-bacterial development. Differences in subcellular organization of the bacterial and eukaryotic multi-enzyme fatty acid synthase systems offer the prospect of inhibitors with host vs. target specificity. Platensimycin, platencin, and phomallenic acids, newly discovered natural product inhibitors of the condensation steps in fatty acid biosynthesis, represent new classes of compounds with antibiotic potential. An almost complete …

Probing Reactivity And Substrate Specificity Of Both Subunits Of The Dimeric Mycobacterium Tuberculosis Fabh Using Alkyl-Coa Disulfide Inhibitors And Acyl-Coa Substrates, Sarbjot Sachdeva, Faik Musayev, Mamoun M. Alhamadsheh, J. Neel Scarsdale, H. Tonie Wright, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The dimeric Mycobacterium tuberculosis FabH (mtFabH) catalyses a Claisen-type condensation between an acyl-CoA and malonyl-acyl carrier protein (ACP) to initiate the Type II fatty acid synthase cycle. To analyze the initial covalent acylation of mtFabH with acyl-CoA, we challenged it with mixture of C6-C20 acyl-CoAs and the ESI-MS analysis showed reaction at both subunits and a strict specificity for C12 acyl CoA. Crystallographic and ESI-MS studies of mtFabH with a decyl-CoA disulfide inhibitor revealed a decyl chain bound in acyl-binding channels of both subunits through disulfide linkage to the active site cysteine. These data provide the first unequivocal evidence that …

Singlet Oxygen Generation Using New Fluorene-Based Photosensitizers Under One- And Two-Photon Excitation, Stephen James Andrasik

Electronic Theses and Dissertations

Molecular oxygen in its lowest electronically excited state plays an important roll in the field of chemistry. This excited state is often referred to as singlet oxygen and can be generated in a photosensitized process under one- or two-photon excitation of a photosensitizer. It is particularly useful in the field of photodynamic cancer therapy (PDT) where singlet oxygen formation can be used to destroy cancerous tumors. The use of two-photon activated photosensitizers possesses great potential in the field of PDT since near-IR light is used to activate the sensitizer, resulting in deeper penetration of light into biological tissue, less photobleaching …

Discrimination Of Forensic Trace Evidence Using Laser Induced Breakdown Spectroscopy, Candice Bridge

Electronic Theses and Dissertations

Elemental analysis in forensic laboratories can be tedious and many trace evidence items are not analyzed to determine their elemental composition. Presently, scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) is the primary analytical tool for determining the elemental composition of trace evidence items. However, due to the time it takes to obtain the required vacuum and the limited number of samples that can be analyzed at any one time, SEM-EDS can be impractical for a high volume of evidence items. An alternative instrument that can be used for this type of analysis is laser ablation inductively coupled plasma mass spectrometry …

Two-Photon 3d Optical Data Storage Via Fluorescence Modulation Of Fluorene Dyes By Photochromic Diarylethenes, Claudia Corredor

Electronic Theses and Dissertations

Three-dimensional (3D) optical data storage based on two-photon processes provides highly confined excitation in a recording medium and a mechanism for writing and reading data with less cross talk between multiple memory layers, due to the quadratic dependence of two photon absorption (2PA) on the incident light intensity. The capacity for highly confined excitation and intrinsic 3D resolution affords immense information storage capacity (up to 1012 bits/cm3). Recently, the use of photochromic materials for 3D memory has received intense interest because of several major advantages over current optical systems, including their erasable/rewritable capability, high resolution, and high sensitivity. This work …

Analytical Potential Of Polymerized Liposomes Bound To Lanthanide Ions For Qualitative And Quantitative Analysis Of Proteins, Marina Santos

Electronic Theses and Dissertations

One of the intriguing features of biological systems is the prevalence of highly selective and often very strong interactions among different cellular components. Such interactions play a variety of organizational, mechanical, and physiological roles at the cellular and organism levels. Antigen-antibody complexes are representative examples of highly selective and potent interactions involving proteins. The marked specificity of protein-antibody complexes have led to a wide range of applications in cellular and molecular biology related research. They have become an integral research tool in the present genomic and proteomic era. Unfortunately, the production of selective tools based on antigen-antibody interactions requires cumbersome …

Advances In Fire Debris Analysis, Mary Williams

Electronic Theses and Dissertations

Fire incidents are a major contributor to the number of deaths and property losses within the United States each year. Fire investigations determine the cause of the fire resulting in an assignment of responsibility. Current methods of fire debris analysis are reviewed including the preservation, extraction, detection and characterization of ignitable liquids from fire debris. Leak rates were calculated for the three most common types of fire debris evidence containers. The consequences of leaking containers on the recovery and characterization of ignitable liquids were demonstrated. The interactions of hydrocarbons with activated carbon during the extraction of ignitable liquids from the …

The Application Of Controlled Radical Polymerization Processes On The Graft Copolymerization Of Hydrophobic Substituents Onto Guar Gum And Guar Gum Derivatives, Veronica Holmes

LSU Doctoral Dissertations

Guar gum is a naturally occurring polysaccharide; guar gum and its derivatives, such as carboxymethyl guar gum (CMG) are widely used in the oil and gas industry. A hydraulic fracturing fluid for rock formations to enhance oil recovery (EOR) is comprised of viscosifier, gelled CMG, and sand particles (proppants). The gel is mixed with proppant (sand) and pumped at high rate and high pressure into an oil/gas well to the hydrocarbon-producing zone. The applied pressure will force the rock formation to fracture allowing entry of the guar gel/sand mixture. The mixture then fills the resultant fracture. The viscosity of the …

Synthetic Methods For Biologically Relevant Organofluorine Compounds, Meher Perambuduru

Doctoral Dissertations

"This thesis describes novel synthetic methodologies for the synthesis of biologically relevant organofluorine compounds"--Abstract, page iii.

The Application Of Electrospray Ionization Coupled To Ultrahigh Resolution Mass Spectrometry For The Molecular Characterization Of Natural Organic Matter, Rachel L. Sleighter, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (> 3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (> 200000) techniques such as electrospray ionization (ESI) coupled …

An Evaluation Of Supercritical Drying And Peg/Freeze Drying Of Waterlogged Archaeological Wood, Eric Schindelholz, Robert Blanchette, Desmond C. Cook, Michael Drews, Steve Hand, Benjamin Held, Joel Jurgens, Betty Seifert

Physics Faculty Publications

This study was undertaken to evaluate the physical effects of drying waterlogged archaeological wood using supercritical carbon dioxide as compared to air drying and the popular polyethylene glycol (PEG)/freeze drying method. Previous studies have shown supercritical drying to be a potentially advantageous alternative to current methods of drying waterlogged wood through reduced processing time, minimal shrinkage, and increased success for reversibility. Samples in the form of blocks and planks of a few centimeters in size were prepared from two archaeological waterlogged wood sources and grouped into three treatment sets: one for air drying, one for PEG/freeze drying, and the other …

Effects Of Combined Exposure To Ethanol And Ionizing Radiation On The Antioxidant Status Of In Vitro And In Vivo Models, Joshua Ogony

Doctoral Dissertations

"Ethanol and ionizing radiation exposure are independently known to cause tissue damage through various mechanisms. Non-enzymatic and enzymatic metabolism of ethanol, the latter via the cytochrome P₄₅₀2E1-dependent pathway, produces free radicals which deplete cellular glutathione (GSH). Ionizing radiation exposure has been shown to induce lipid peroxidation, DNA damage, protein oxidation, and GSH depletion, as well. It was postulated that initial exposure to ethanol, followed by ionizing radiation, would result in heightened oxidative stress. The in vitro model used in this investigation was HepG2 cells (human hepatocellular liver carcinoma cell line), while the in vivo model was Cd-1 mice"--Abstract, page iii.

Exploring The Binding Of Amine And Sulfonamide Ligands In Rhenium(I) Tricarbonyl And Platinum(Ii) Complexes, Anna Maria Christoforou

LSU Doctoral Dissertations

Platinum is the metal present in various classes of inorganic medicinal agents directed at important diseases such as cancer or viral infections. Several new Pt(II) complexes of polyamine ligands bearing a dansyl moiety linked by a sulfonamide group were prepared; in some cases the sulfonamide nitrogen formed a bond to Pt. The sulfonamido group donates strongly to Pt and places the dansyl group close to a vacant coordination position, allowing it to stack with bound guanine base (G) when G binds. The emission of the fluorophore decreases with decreasing distance to Pt. Metal nuclide radiopharmaceuticals contain a metal core and …

Synthesis And Properties Of Isoporphyrins And Related Derivatives For Application In Photodynamic Therapy, Sandra Celinah Mwakwari

LSU Doctoral Dissertations

Isoporphyrins are tautomers of porphyrins with an interrupted macrocyclic conjugation owing to the presence of a sp3 hybridized meso-carbon. Due to their absorption at long wavelengths (~800nm), isoporphyrins are potential candidates as photosensitizers in photodynamic therapy (PDT), a ternary modality of cancer treatment. They are also of biological interest due to their unique redox properties among porphyrin derivatives and could be a new class of near-IR dyes. Isoporphyrins are known to be unstable with respect to transformation back to the fully conjugated porphyrin chromophore except when the meso-carbon is geminally substituted and for this reason a detailed study of this …

Copper(Ii) Oxide Mediated Formation And Stabilization Of Combustion Generated Persistent Free Radicals, Hieu Truong

LSU Doctoral Dissertations

Biologically damaging semiquinone-type radicals have been reported in cigarette smoke, their likely origin being hydroquinone (HQ) and catechol (CT) molecular precursors contained by the tobacco. Since other biomass contains HQ and CT-type species, it is likely that combustion of other biomass will also form semiquinone-type radicals. All hydrocarbon fuels will form phenol and substituted phenol that can form substituted phenoxyl radicals. Because each of these radicals has the potential to be environmentally persistent and biologically active, their formation and stabilization from various molecular precursors was studied with the focus on surface-bound radicals formed in association with combustion-generated fly-ash particles. Comprehensive …