Chemistry Commons^™

Monitoring Photocatalytic Degradation Of X-Ray Contrast Media With Raman Spectroscopy, Sabina Salkic

Masters Theses & Specialist Projects

X-ray contrast media such as diatrizoate and iohexol have been found in wastewater and drinking water and are difficult to remove because they are resistant to water treatment processes. A removal process can be started with ultraviolet photocatalytic degradation of X-ray contrast media in the presence of titanium dioxide or other catalysts. Raman spectra of diatrizoate and iohexol were taken in an aqueous solution in the presence and absence of titanium dioxide during exposure to ultraviolet radiation. Raman intensity is directly proportional to concentration; therefore, we can measure the rate of the reaction based on changes in the Raman spectrum. …

Lipid Peroxides And Glutathione Status In Human Progenitor Mononuclear (U937) Cells Following Exposure To Low Doses Of Nickel And Copper, William Y. Boadi, Shalandus Harris, Justin B. Anderson, Samuel E. Adunyah

Chemistry Faculty Research

Effects of Cu2+, Ni2+ or Cu2+ + Ni2+ on lipid peroxide and glutathione (GSH) levels in U937 cells were investigated. Cells were treated with 0, 5, 10, and 20 µM of Cu2+ and/or Ni2+ and H2O2 (0.01 mM) and incubated for 24 hours at 37°C. Lipid peroxides were measured by the thiobarbituric acid assay (TBA). GSH intracellular levels were assayed by the GSH assay kit from EMD/Calbiochem (San Diego, California, USA). Cu2+ or Ni2+ significantly (P < 0.01) increased lipid peroxides in a dose-dependent manner, compared to controls. The effect was more pronounced for Cu2+, compared to the Ni2+-treated samples. Cu2+ + Ni2+ increased lipid peroxides in a significant (P < 0.001), dose-dependent manner, compared to Cu2+ or Ni2+ alone (i.e., ratio of 2.5:1-fold for combined versus single treatments, respectively). Cu2+ or Ni2+ significantly decreased GSH levels in U937 cells, with the effect being pronounced for Cu2+. Cu2+ + Ni2+ metal ions significantly (P < 0.001) depleted cells of GSH in a dose-dependent manner. Ethylene diamine tetraacetic acid (EDTA) at 50 or 100 µM moderately reduced the Cu2+- or Ni2+-induced effects on GSH levels. Interestingly, GSH levels generally decreased to half (except for the combined metal dose of 20 µM at 100 µM EDTA) of its level at the highest metal concentration tested for both the single or combined treatments. In conclusion, multiple exposures of cells to metal ions may be lethal to cells, compared to their single treatments.

High Resolution Spectroscopy: The Study Of Isobutylene, Tabetha Lynn Osborn

Student Theses and Dissertations

The explosive bouquet theory suggests that canines trigger on volatile organic species within an explosive and not the pure explosive. Modeling an explosive detection scheme after this theory, an experimental design using mid infrared sources was established at the ArCLAS facility. A calibration program, documented within this thesis, was created in a Visual Basic platform as an Excel Add-In. The calibration program converts time based spectra collected with a germanium etalon into frequency spaced scans and then to known frequencies to allow spectral assignments to rovibrational transitions of molecules of interest. Additionally, the analysis of isobutylene, a volatile organic bouquet …

Patent: Methods Of Treating Fgf21-Associated Disorders, Brian R. Boettcher, Shari L. Caplan, Douglas S. Daniels, Bernhard Hubert Geierstanger, Norio Hamamatsu, Stuart Licht, Andreas Loew, Stephen Craig Weldon

Chemistry Faculty Publications

The invention relates to the identification of new polypeptide and protein variants of fibroblast growth factor 21 (FGF21) that have improved pharmaceutical properties. Also disclosed are methods for treating FGF21-associated disorders, includ ing metabolic conditions.

Magnetic Ordering And Structural Phase Transition In Strained Ultrathin Srruo3/Srtio3 Superlattice, Mingquiang Gu, Xiaoshan Wu, Guoping Zhang

Symposium 2012

No abstract provided.

Cloning And Characterization Of Sas0754, A Hypothetical Protein From Community Associated Staphylococcus Aureus, Unknown Unknown

Symposium 2012

Community associated Staphylococcus aureus (strain MSSA476) is a gram positive cocci capable of infecting many different parts of the body and known to cause serious infections that can be fatal, such as bacterial arthritis and acute endocarditis. To find effective ways of fighting against CA-MRSA strains we must learn more about their ability to infect. The focus of this study was cloning and characterization of a protein referred to as SAS0754. The size of SAS0754 is 340 amino acids and the gene sequence is 1023 nucleotides. The hypothetical function of this protein is that it is an extracellular matrix binding …

A Convenient Synthesis Of 2,6-Dichlorohomonicotinic Acid, Chase Buchanan, Richard W. Fitch

Symposium 2012

In our synthetic efforts toward the alkaloid phantasmidine, we required a convenient source of the title compound. Herein, we describe a short synthesis of 2,6-dichlorohomonicotinic acid by direct allylation of 2,6-dichloropyridine with LDA/allyl chloride, followed by permanganate oxidation of the side chain [figure1]. Yields for the allylation are high, while permanganate oxidation required more adjustment. Successful conditions require the modest acidification of the mixture with acetic acid and cleanup by acid base workup. No chromatography is needed.

Convenient Parallel Synthesis Of Alkyl- And Aryl-S-Tert-Butyl Thiothers, Rebecca Norcross, Jessica Stanfield, Richard W. Fitch

Symposium 2012

While preparing novel cysteine derivatives as oxidation catalysts, we needed S-tert-butylcysteine. We also examined acid-promoted tert-butylation of thiols using tert-butanol as reagent and solvent. While cysteine and aminoethanethiol work well using tBuOH in 4M HCl, other thiols fail in the aqueous environment and aerobic conditions. We examined a variety of aliphatic and aromatic thiols in tBuOH with H2SO4 catalysis and found that argon sparging and the use of 1 eq of acid led to good yields in a parallel format.

Electronic Properties Of Memantine (Alzheimer's Disease) And Amantadine (Anti-Flu) Drugs, Kirsten Middleton, Guo-Ping Zhang, Thomas F. George

Symposium 2012

Alzheimer’s Disease is the 5th leading cause of death for Americans 65 and older Treatment The U.S. Food and Drug Administration Only five drugs approved that “temporarily slow worsening of symptoms for about six to 12 months.” Effective for only about half of all patients.

Synthesis Of S-Ribosyl-L-Homocysteine And Analogs Modified At The Homocysteine-C3 Position, Ruoyi Liu

Master's Theses

Quorum sensing (QS) is a process of bacterial cell-to-cell communication that conveys population density information in order to coordinate gene expression to produce synchronized behaviors. QS regulates the expression of virulence genes in many species of bacteria; hence, the manipulation of QS pathways may lead to treatment options against many bacterial diseases. The LuxS enzyme converts S-ribosyl-L-homocysteine (SRH) into homocysteine (HCys) and 4(S),5-dihydroxypentane-2,3-dione (DPD), which is the precursor of autoinducer-2 (AI-2). Thus, inhibitors of LuxS could prevent QS by halting the conversion of SRH to AI-2 rendering the cell “uncommunicative”. This work shows the successful chemical synthesis …

Synthesis And Biological Evaluation Of Rigid Analogues Of Methamphetamines, Andrea N. Forsyth

LSU New Orleans Theses and Dissertations

A series of rigid azetidenyl-based methamphetamine analogs were synthesized from commercially available N-Boc-azetidinone. The benzylideneazetidine analogs were prepared via a Wittig olefination via the ylides generated from the corresponding triphenylphosphonium benzylhalide salts. The substituted benzylazetidine analogs were synthesized from the corresponding benzylideneazetidienes via hydrogention over palladium and platinum catalysts. The benzylideneazetidine and benzyliazetidine analogs were evaluated at monoamine transporters as a part of preliminary structure-activity study for the development of novel monoamine transporter ligands. The binding affinities of the azetidine analogs were determined at dopamine (DAT) and serotonin (SERT) transporters in rat brain tissue preparations. The preliminary in vitro …

Enhancement In Degradation Of Environmental Pollutants: Fenton Degradation Of 2,4,6-Trinitrotoluene And Photodegradation Of Deepwater Horizon Crude Oil, Sarah M. King

LSU New Orleans Theses and Dissertations

Pollution poses serious threats to both the environmental and the organisms that depend on their environment for survival. Due to the toxicity of most contaminants, there is a dire need for remediation of polluted sites. Remediation studies were conducted on two high priority pollutants: 2,4,6-trinitrotoluene (TNT) and crude oil.

TNT was the most common explosive used in the 20^th century. Continuous contamination has resulted in an urgent need for remediation. Fenton reagent provides an advanced oxidation process that is capable of remediating recalcitrant explosives, such as TNT. One drawback of Fenton chemistry is that the reaction requires acidic pH …

Investigating The Electron Transport And Light Scattering Enhancement In Radial Core-Shell Metal-Metal Oxide Novel 3d Nanoarchitectures For Dye Sensitized Solar Cells, Gayatri Sahu

LSU New Orleans Theses and Dissertations

Dye-sensitized solar cells (DSSCs) have attained considerable attention during the last decade because of the potential of becoming a low cost alternative to silicon based solar cells. Electron transport is one of the prominent processes in the cell and it is further a complex process because the transport medium is a mesoporous film. The gaps in the pores are completely filled by an electrolyte with high ionic strength, resulting in electron-ion interactions. Therefore, the electron transport in these so called state-of-the-art systems has a practical limit because of the low electron diffusion coefficient (D_n) in this mesoporous film …

Synthesis And Development Of Potential Cb1 Receptor Neutral Antagonists, Kimari Slaughter

LSU New Orleans Theses and Dissertations

Cannabis and its derivatives have been used for both medicinal and recreational purposes. The study of this plant led to the discovery of over 60 cannabinoids, found exclusively in cannabis, that contribute to the behavioral effects of cannabis use, the most common is delta-9-tetrahydrocannabinol. Cannabinoid receptors function to increase activity in the mesolimbic dopamine reward system. Dopamine is a neurotransmitter that plays a major role in addition and its regulation plays a crucial role in mental and physical well-being. There is evidence that CB₁ receptors are important to the reinforcing effects and the development of physical dependence on opiate …

Synthesis And Characterization Of Sugar Based Low Molecular Weight Gelators, Hao Yang

LSU New Orleans Theses and Dissertations

Low molecular weight gelators (LMWGs) have gained great attention over the past two decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and form gel. LMWGs are interesting compounds with many potential applications in material and biomedical sciences.

Many different structures have been found to be good LMWGs. Our interests focus on the carbohydrate based LMWGs. Previously, we have found that several ester derivatives of methyl 4, 6-O-benzylidene-α-D-glucopyranoside are good gelators for organic solvents and aqueous solutions. In this study, in order to understand the …

Controlled Attachment Of Nanoparticles To Layered Oxides, Yuan Yao

LSU New Orleans Theses and Dissertations

A series of oxide materials were modified with different nanoparticles (NPs). Novel cobalt@H₄Nb₆O₁₇ nanopeapod structures were fabricated and magnetic NPs modified oxide nanosheets and nanoscrolls were prepared. Both aqueous method and two-phase method were applied to prepare gold NPs onto oxide nanosheets, nanoscrolls and other nanocrystals.

The combination of H₄Nb₆O₁₇ nanoscrolls and cobalt NPs generate a novel method to fabricate nanopeapod structures. Cobalt NPs were synthesized in the presence of exfoliated H₄Nb₆O₁₇ nanosheets and the resulting magnetic chain structures, formed due to the dipole-dipole interaction, …

Active Response Of Polymer Materials From External Stimuli – Solvents And Light; Grafting Reactions On Perovskite Layers, Jianxia Zhang

LSU New Orleans Theses and Dissertations

The active response of a series of polymeric materials was investigated. Both solvent activated and light activated thin films and wire systems show dynamic behaviors when exposed to different stimuli.

Solvent mediated fluxional behavior of polymer thin films involved extensive, rapid curling both on infusion and evaporation of good solvents. These films can be either lab-fabricated ones or commercial ones, and the curling behavior can be as fast as seconds. Conditions including polymer materials, chosen solvents, and film geometry can affect the behavior.

Methods that allowed for the creation and retention of distorted wire structures were also developed; the asymmetric …

Analysis Of Biodiesel Quality Using Reversed Phase High-Performance Liquid Chromatography, Kellyann M. Murphy

Pomona Senior Theses

The alternative fuel biodiesel is produced from the transesterification of vegetable oils or animal fat to fatty acid methyl esters. Pomona has a reactor on campus that can be used to run this reaction and produce biodiesel. The use of biodiesel has been found to lower air pollutant and greenhouse gas emissions, but can be potentially harmful to the engines if it contains impurities. This paper proposes a method using high-performance liquid chromatography to test the quality of biodiesel. This method utilizes instrumentation and materials that are available in Pomona College's Chemistry Department, requires very little sample preparation, and is …

Synthesis Of Fluorogenic Substrates For The Enzymatic Characterization Of Rv0045c From M. Tuberculosis, Kelly Jo Mckenna

Undergraduate Honors Thesis Collection

Mycobacterium tuberculosis is the pathogenic bacterial agent commonly responsible for tuberculosis, or TB. Although treatment exists for the active form of tuberculosis, no method has been developed for eliminating M tuberculosis in its dormant state. One hypothesized method for the elimination of dormant TB is to develop an inhibitor specific for M tuberculosis esterases and lipases, as these esterases and lipases are essential to the survival of dormant TB infection. In this research, the substrate specificity of the Rv0045c esterase from M tuberculosis was studied due to the essential role of Rv0045c in TB metabolism and its dissimilarity to other …

Chiral Recognition In Amino Acid And Peptide Based Chiral Ionic Liquids, Daniel Mccray Kroupa

Undergraduate Honors Thesis Collection

In this study, amino acid and peptide based chiral ionic liquids (ILs) were prepared and their chiral recognition ability probed using circularly polarized luminescence (CPL) spectroscopy. Potential applications of amino acid and peptide based chiral ILs include asymmetric synthesis and chiral resolution. The amino acid based chiral ILs under study were prepared from amino acid methyl ester cations and bis(trifluoromethane)sulfonamide ([TF2ND anions, specifically L-alanine methyl ester, D-alanine methyl ester, L-Ieucine methyl ester, and L-proline methyl ester. Cationic peptide ILs were prepared from L-alanyl glycine methyl ester cations and [TF2Nr anions and anionic peptide based ILs were prepared from tetrabutylammonium ([TBAt) …

Unconventional Superhalogens: Design And Applications, Devleena Samanta

Theses and Dissertations

Electron affinity is one of the most important parameters that guide chemical reactivity. Halogens have the highest electron affinities among all elements. A class of molecules called superhalogens has electron affinities even greater than that of Cl, the element with the largest electron affinity (3.62 eV). Traditionally, these are metal-halogen complexes which need one electron to close their electronic shell. Superhalogens have been known to chemistry for the past 30 years and all superhalogens investigated in this period are either based on the 8-electron rule or the 18-electron rule. In this work, we have studied two classes of unconventional superhalogens: …

Refining Vibrationally-Resonant Sum Frequency Generation Spectroscopy For Studies Of Interfacial Interactions, Alexander D. Curtis

Theses and Dissertations

Many phenomena of interest to science and engineering occur at interfaces; however, access to, or discrimination of, interfacial interactions has been challenging, especially at buried interfaces. Vibrationally resonant sum-frequency generation (VR-SFG) spectroscopy is a powerful tool for investigating the molecular structure of free or buried interfaces, but spectral analysis has relied on many assumptions. To claim accurate new insights, practitioners must be able to make unique determinations from the data without experimental artifacts affecting the final results. For example, two independent and overlapping studies for the polystyrene/air interface were carried out, but reported different surface structures. Initially, this difference was …

Hydrocarbon/Water Interactions: Encouraging Energetics And Structures From Dft But Disconcerting Discrepancies For Hessian Indices, Kari L. Copeland, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

In this work, ab initio electronic structure computations have been used to systematically examine the structures and energetics of nine small hydrocarbon molecules interacting with water. Full geometry optimizations and harmonic vibrational frequency calculations were performed on 30 unique dimer configurations with the MP2 method and a triple-ζ correlation consistent basis set (cc-pVTZ for H and aug-cc-pVTZ for C and O, denoted haTZ). Three different estimates of the CCSD(T) complete basis set (CBS) limit interaction energies were determined for all 30 MP2 optimized hydrocarbon/water structures, and they never deviate from their mean by more than 0.07 kcal mol -1. MP2 …

Mechanistic Studies And Optimization Of Microwave-Assisted Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions And An Academic Prospective On “Quality By Design”, Neha K. Grewal

Honors Scholar Theses

This compilation of work includes four aspects: (1) an academic review on the significance and implementation of Quality by Design (QbD), (2) mechanistic studies on the palladium-catalyzed synthesis of diarylmethanes, (3) the optimization of microwave-assisted click reactions and Suzuki couplings for use in an undergraduate organic chemistry laboratory manual, and (4) monitoring the progress of organic transformations using Raman spectroscopy.

Synthesis, Characterization, And Photocatalytic Testing Of Titania-Based Aerogels For The Degradation Of Volatile Organic Compounds, Dayton Thomas Horvath

Honors Scholar Theses

The need to degrade volatile organic compounds (VOC’s) has grown with recent economic and environmental concerns. Advanced oxidation processes governing breakdown of VOC’s have received significant attention due to environmentally conscious practices and objectives. Photocatalysis is a logical approach for VOC removal in air because of minimal energy requirements and ease of implementation. Titania with high pore volume and surface area are synthesized using a modified sol-gel method in conjunction with carbon dioxide supercritical drying. Vanadium doping increases the visible absorption of titania aerogels. Solvent removal is achieved using a custom-built high pressure chamber designed for carbon dioxide supercritical drying. …

Nuclear Translocation Of Foxo3a Transcription Factor During Prelamin A Induced Cell Cycle Arrest In 3t3 Cells., Jessica B. Keasler

Undergraduate Honors Theses

As the so-called “Mothership of the Human Genome,” the cell nucleus must keep all vital genetic information safe, but accessible, inside a strong protective envelope. The inner membrane of the nuclear envelope is lined by tough but adaptable proteins called lamins. While lamins polymerize into fibrous structures that hold up the “walls” of the nucleus, they also serve as an internal scaffold for the complex machinery involved in DNA replication and gene expression. It is in this later role that we have been looking for clues to premature and possibly to normal aging. One type of lamins, Lamin A is …

Studies On The Preparation, Immobilization, And Luminescence Properties Of Zinc Oxide (Zno)Quantum Dots, Yasemin Hakat

Electronic Theses and Dissertations

Quantum dots are a part of very important our technological future because of their intriguing and useful properties. These properties are different in character from those of the corresponding bulk material. Quantum dots are inorganic artificial semiconductor nanocrystal whose electrons influence their physical and chemical properties. Zinc oxide quantum dots were synthesized through an ethanol based precipitation via colloidal synthesis method at various pH values. Various emission colors were obtained because the excited quantum dots of various sizes emitted specific wavelengths of light. The emission spectra indicated that the pH dependent quantum dots were successfully synthesized. Zinc oxide quantum dots …

The Analysis Of Protein-Bound Thiocyanate In Plasma Of Smokers And Non-Smokers As A Marker Of Cyanide Exposure, Stephanie L. Youso, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

When cyanide is introduced into the body, it quickly transforms through a variety of chemical reactions, normally involving sulfur donors, to form more stable chemical species. Depending on the nature of the sulfur donor, cyanide may be transformed into free thiocyanate, the major metabolite of cyanide transformation, 2-amino-2-thiazoline-4-carboxylic acid or protein-bound thiocyanate (PB-SCN) adducts. Because protein adducts are generally stable in biological systems, it has been suggested that PB-SCN may have distinct advantages as a marker of cyanide exposure. In this study, plasma was analyzed from 25 smokers (chronic low-level cyanide exposure group) and 25 non-smokers for PB-SCN. The amount …

Synthesis And Structural Studies Of Calcium And Magnesium Phosphinate And Phosphonate Compounds, Victoria Naa Kwale Bampoh

Chemistry - Dissertations

The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, …

Design And Synthesis Of Solid State Materials Constructed From Polyoxomolybdate Clusters, Stephanie Jones

Chemistry - Dissertations

This work encompasses detailed investigations of the synthesis and structures of polyoxomolybdate materials. The design and synthesis of hybrid organic-inorganic materials constructed from various anionic polyoxomolybdate units and cationic secondary metal-ligand units, and the synthesis and ligand-exchange capacity of the giant polyoxomolybdate cluster Mo-132 are described. These studies aim to increase our understanding of the formation and physiochemical properties of these materials, and thereby aid in the ability to control and predict their structural chemistry.

The analysis of a number of structural determinants in the oxomolybdenum-organodiphosphonate system aims to expand the current knowledge of this family of materials. We have …