Physical Sciences and Mathematics Commons^™

A Ring-Closing Strategy For The Synthesis Of Β,Γ-Unsaturated Δ-Lactones, Erbing Hua

Masters Theses

Spiro β,γ-unsaturated δ-lactones and fused β,γ-unsaturated δ-lactones are integral to a large number of naturally occurring compounds exhibiting a diverse range of biological activity. A new synthetic route to β,γ-unsaturated δ-lactones, consisting of a three-step sequence, has been investigated for the synthesis of these kinds of pharmacological intermediates. Ring closure of a β-hydroxy acid by dehydration, providing a 4-vinyl substituted β-lactone, and its ring expansion/rearrangement are the two key steps in this protocol. The results have proved that this new method is efficient and quite expeditious. One spiro and four fused β,γ-unsaturated δ-lactones were synthesized through this protocol albeit in …

Computational Studies Of Constant Bond Dissociation Enthalpy Ratios And Novel Structures For [H3, B, C, F]+, Le Li

Masters Theses

This thesis describes two separate computational chemistry projects. The first project is a study of constant bond dissociation enthalpy ratios, and the second project is a study of the rearrangement and fragmentation processes on the singlet potential energy surface of the [H₃, B, C, F]⁺ system.

G2 and G2(MP2) enthalpies have been calculated for isoelectronic AB₂ systems with singlet-linear, singlet-nonlinear, triplet-linear, and triplet-nonlinear electronic states and geometries, and for isoelectronic AB systems with singlet and triplet electronic states. For these systems, A = B^-, Al^-, Ga^-, C, Si, Ge, N …

Linkage Isomers Of Tungsten Carbonyl Complexes Of Ph₂Pch₂Pphch₂Pph₂, Chaminda P. Gamage

Masters Theses

The linkage isomers (CO)₅W[η¹-PPh₂CH₂PPhCH₂PPh₂], 1, and (CO)₅ W[η¹-PPh(CH₂PPh₂)₂], 2, have been synthesized from the reaction of (OC)₅W(NH₂Ph) and Ph₂PCH₂PPhCH₂PPh₂. In addition, linkage isomers (CO)₅W[μ-PPh₂CH₂PPhCH₂PPh₂]-W(CO)₅, 3, and (CO)₅W{μ-PPh₂CH₂PPh[W(CO)₅] CH₂PPh₂}, 4, have been prepared. Attempts to obtain (OC)₅WPPh₂CH …

Order-Disorder Phase Transitions In Kno2 , Csno2, And Tlno2 Crystals: A Molecular Dynamics Study, Chun-Gang Duan, Wai-Ning Mei, Robert W. Smith, Jianjun Liu, M. M. Ossowski, John R. Hardy

Physics Faculty Publications

The order-disorder phase transitions of KNO2 , CsNO2, and TlNO2 have been studied using parameter-free molecular dynamics simulation. It is found that the phase transitions in nitrites investigated are driven by the rotations of the NO2 2 ions about different axes together with displacements of cations and anions. We successfully reproduce the high-temperature phases of these nitrites, i.e., the NaCl-like structure for KNO2 and CsCl-like structure for Cs(Tl)NO2. Based on the investigation of the radial distribution function of the cations and anions, we explain why KNO2 and Cs(Tl)NO2 form quite different low-temperature phases.

Observations Of Apan During Texaqs 2000, James M. Roberts, Frank Flocke, Andrew Weinheimer, Hiroshi Tanimoto, Bertram T. Jobson, Daniel Riemer, Eric Apel, Elliot Atlas, Stephen G. Donnelly Ph.D., Verity Stroud, Kristen Johnson, Rachel Weaver, Fredrick C. Fehsenfeld

Chemistry Faculty Publications

Measurements of peroxycarboxylic nitric anhydrides (PANs) made in Houston, Texas during TexAQS (Texas Air Quality Study) 2000 showed a relatively abundant PAN compound that had not been identified in previous studies in North America [cf. Williams et al., 2000]. This compound was hypothesized to be peroxyacrylic nitric anhydride { CH2=CHC(O)OONO2, APAN} based on the work of Tanimoto and Akimoto, [2001]. APAN was synthesized and characterized on one of the two GC systems used to make those measurements, subsequent to the TexAQS 2000 field study, confirming that APAN was observed during TexAQS 2000, both on the ground and in airborne measurements. …

Synthesis Of A Ruthenium-Tetra(Tht)Dichloride Compound And The Molecular Structure Of The Partially Oxidized Compound Rucl2(Tht)2.2(Tht-O)1.8, L. A. Thornton, Mark Draganjac, Andres Meza, A. W. Cordes

Journal of the Arkansas Academy of Science

No abstract provided.

Design Of Peptides With, Α,Β-Dehydro-Residues: A Dipeptide With A Branched Β-Carbon Dehydro-Residue At The (I+1) Position, Methyl N-(Benzyloxycarbonyl)-Α,Β-Didehydrovalyl-L-Tryptophanate, Vijayaraghavan Rangachari, Pravindra Kumar, Sharmistha Dey, Tej P. Singh

Faculty Publications

The structure of the title peptide, C₂₅H₂₇N₃O₅, has been determined and its conformation analysed. Values of the standard peptide torsion angles are φ(1) = -44.2 (3)°, ψ(1) = 135.9 (2)°, φ(2) = -141.6 (2)° and ψ(T/2) = 168.0 (2)°. The crystal structure is stabilized by an intermolecular hydrogen bond, with an N···O distance of 2.919 (3)Å, which is formed between screw-axis-related NH and CO groups of dehydrovaline residues.

Study Of The Effects Of Co2(G) On The Fe(Ii)-Luminol Chemiluminescence System: Application To Ultra-Trace Analysis Of Fe(Ii), Sara Beth Lovitz

Honors Theses

The Fe(II)-catalyzed oxidation of luminol has been a well-accepted chemiluminescence method for the trace and ultra-trace analysis of Fe(II) and Fe(III) in natural waters. Investigation into this chemiluminescence system has shown that COlg) is essential to Fe-catalyzed luminol chemiluminescence. In absence of CO2(g) there is no chemiluminescent signal. These reactions worked well in the past because CO2 is present in most laboratory H20 supplies. Intentional saturation of CO2 results in a 5-fold increase for this conventional system. We propose a mechanism for CO 2(g) enhancement that includes formation of a CO2-superoxide intermediate, which serves as the oxidant of luminol to …

Probing The Capabilities Of Copper Complexes With Nitrogen And Sulfur Containing Macrocyclic Ligands As Aziridination Catalysts, Jonathan Natkin

Honors Theses

Aziridines are three-membered rings containing one nitrogen atom. They are useful as synthetic intermediates in many organic reactions. Much work has been devoted to synthesizing their analogs, cyclopropanes and epoxides, but little work has been done on the aziridination reaction. This study endeavored to probe the efficiencies of novel copper aziridination catalysts with N3 and S3 macrocyclic ligands compared to an NS2 analog for the reaction with the nitrene precursor (N-(paratosylsulfonyl) imino)phenyliodinane, PhINTs, and the olefin styrene. The nitrogen containing catalyst complex gave higher yields than the sulfur containing catalyst complex. Both ligands were found to decrease the yield of …

Synthetic Approach To Hexaoxa[6]Peristylanes. A Novel Ddq-Induced Oxidative Rearrangement, Douglas Arthur Otte

Honors Theses

The structural beauty and interesting bonding properties of polycyclic cage compounds have been a source of fascination to many chemists. In this work, progress toward the synthesis of large oxabowl systems, such as hexaoxa[6]peristylane and its derivative dipbenylhexaoxa[6)peristylane, is described. Thus, the adduct obtained from the cycloaddition of maleic anhydride and cyc!ooctatetraene is converted into key dicarbonyl intermediates. Subsequently, the ozonolysis of these intermediates is carried out in order to generate hexaoxa(6)peristylane as well as diphenylhexaoxa[6]peristylane. Molecular modeling studies, performed at the semi-empirical level, are also described.

Exploratory Chemistry In Route To Aromatic Natural Products, Nicholas P. Bizier

Honors Theses

The focus of this research was the synthesis of two natural products, 1-methyl-s-(1,2,2-trimethy1cyclopentyl)-benzene (formally cuparene), and 3-(1,2dimethylcyclopenty1)-5-methylbenzene-l,2-diol (formally herbertene diol). Cuparene possesses anti-fungal and anti-arthritic properties. This molecule has been the target of a number of syntheses. Herbertene diol, a natural product itself, represents one retrosynthetic step back from mastigophorane; a compound isolated form the liverwort Mastigophora diaclolades. Mastigophorane has been shown to have neural network forming capabilities and has warranted complete synthetic efforts. Through the same chemistry involve in the formation of cuparene, we sought a route to herbertene diol in two steps. We report a successful route to …

Isolation And Characterization Of Chromium- And Cobalt-Binding Peptides, Michael J. Jose

Honors Theses

Metal substitution has been proposed as an aid in the characterization of the structure of Low-Molecular-Weight Chromium-binding substance (LMWCr), which appears to be the biologically active chromium species. Preparations of bovine liver were diced and suspended in an isolation solution containing either a cobalt or a chromium salt. Peptide samples from these preparations were isolated by precipitation and centrifugation and purified by liquid chromatography. Several methods were used to analyze these samples, which may contain LMWCr or the cobalt-substituted form (LMWCo), in order to determine their purity, molecular weight (MW), and metal-to-peptide ratio. Methods used to determine MW included sodium …

An Xps Investigation Of Thermal Degradation And Charring Of Cross-Linked Polyisoprene And Polychloroprene, Jianwei Hao, Charles A. Wilkie, Jiangqi Wang

Chemistry Faculty Research and Publications

Our interest in butadiene-containing polymers had led to an investigation of the thermal degradation of polyisoprene, PIP, and polychloroprene, PCP. The connection between cross-linking and thermal stability through an examination of PIP and PCP has been reported. Like the course of thermogravimetric analysis (TGA) the cross-linking and charring of polymers subjected to heat can also be experimentally observed as function of temperatures by the pseudo-in-situ XPS (X-ray Photoelectron Spectroscopy). Data acquisition of C1s spectra as function of temperature permits us to explore: (1) the extent of cross-linking and/or carbon accumulation of systems of PCP and PIP with/without initiators, BPO and …

Fire Properties Of Polystyrene-Clay Nanocomposites, Jin Zhu, Alexander B. Morgan, Frank K. Lamelas, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polystyrene−clay nanocomposites have been prepared using a bulk polymerization technique. Three new “onium” salts have been used to prepare the nanocomposites, two are functionalized ammonium salts while the third is a phosphonium salt. By TGA/FTIR, both ammonium and phosphonium treatments have been shown to degrade by a Hofmann elimination mechanism at elevated temperatures. TGA/FTIR showed that the phosphonium treatment is the most thermally stable treatment when compared to the two ammonium salts. The nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, strength and elongation at break, as a measure of the mechanical properties, thermogravimetric analysis, and cone calorimetry. The …

Electron Redistribution Of Aromatic Ligands In (Arene)Cr(Co)3 Complexes. Structural (Bond-Length) Changes As Quantitative Measures, P. Le Maguères, Sergey V. Lindeman, Jay K. Kochi

Chemistry Faculty Research and Publications

Arene ligands experience significant ring expansion upon coordination with chromium tricarbonyl, as established by precise X-ray crystallographic analyses of various (η⁶-arene)Cr(CO)₃ complexes. Such changes in ligand structures result from the charge (electron) redistribution, Ar⁺−Cr^-, upon arene coordination, since they are closely related to those found in the intermolecular 1:1 complexes of the corresponding series of arenes with nitrosonium cation (NO⁺). The latter are prototypical examples of charge-transfer complexes as described by Mulliken. As such, they show enhanced degrees of charge (electron) transfer that approach unity, which is confirmed by quantitative comparison …

Synthesis Of Cyclopropanes Via Organoiron Methodology: Preparation Of 2-(2′-Carboxy-3′-Ethylcyclopropyl)Glycine, Kamil Godula, William Donaldson

Chemistry Faculty Research and Publications

A route to 1,2,3-trisubstituted cyclopropanes has been developed. The relative stereochemistry at the three cyclopropane centers is established by nucleophilic attack on the pentadienyl ligand on the face opposite to iron and subsequent oxidatively induced reductive elimination with retention of configuration. This methodology was applied to the synthesis of 2-(2′-carboxy-3′-ethylcyclopropyl)glycines. The diastereomeric glycine dimethyl esters are separable as their diphenylmethylene imines.

The conformationally restricted glutamate analogs (2S,1′S,2′S,3′R)- and (2R,1′S,2′S,3′R)-ECCG's 5a and5b were prepared in five steps (17 and 15% yield, respectively) from (pentadienyl)Fe(CO) …

Photooxidation Of Polymeric-Inorganic Nanocomposites: Chemical, Thermal Stability And Fire Retardancy Investigations, Adams Tidjani, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of polypropylene-graft-maleic anhydride/clay and polypropylene/clay were prepared by melt blending using two different approaches. X-Ray diffraction results showed an intercalated structure. Samples of nanocomposites were exposed to UV light under atmospheric oxygen and their photo-oxidative stability was studied using FTIR and UV spectroscopy. The consequences of this photo-oxidation on the thermal stability and fire retardant performance of the nanocomposites were also addressed from thermogravimetry analysis and Cone calorimetry.

Xps Characterization Of Friedel-Crafts Cross-Linked Polystyrene, Jiangqi Wang, Jianxin Du, Hongyang Yao, Charles A. Wilkie

Chemistry Faculty Research and Publications

The combination of a difunctional alkylating agent, either hydroxymethylbenzyl chloride or α,α′-dichloroxylene with polystyrene or high-impact polystyrene together with a Friedel-Crafts catalyst, 2-ethylhexyldiphenylphosphate, and an amine to react with hydrogen chloride has been studied by X-ray photoelectron spectroscopy. The results confirm what had been suggested from previous investigations using thermogravimetric analysis; cross-linking of the polymer occurs as the temperature is raised and the alcohol-containing alkylating agent gives a greater amount of cross-linking than does the dichloro compound.

Thermal Degradation Of Pvc In The Presence Of Polystyrene, Qiang Yao, Charles A. Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of poly(vinyl chloride) (PVC) and blends of PVC with polystyrene has been studied using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. The degradation of PVC commences at weak links by an ionic pathway, but there is evidence to suggest the presence of a radical pathway at high temperatures. While there is some chemical interaction between PVC and polystyrene, the principal mode of stabilization is a physical process.

Identification Of The Domains Of Urer, An Arac-Like Transcriptional Regulator Of The Urease Gene Cluster In Proteus Mirabilis, Carrie A. Poore, Christopher Coker, Jonathan D. Dattelbaum, Harry L.T. Mobley

Chemistry Faculty Publications

Proteus mirabilis urease catalyzes the hydrolysis of urea to CO₂ and NH₃, resulting in urinary stone formation in individuals with complicated urinary tract infections. UreR, a member of the AraC family, activates transcription of the genes encoding urease enzyme subunits and accessory proteins, ureDABCEFG, as well as its own transcription in the presence of urea. Based on sequence homology with AraC, we hypothesized that UreR contains both a dimerization domain and a DNA-binding domain. A translational fusion of the leucine zipper dimerization domain (amino acids 302 to 350) of C/EBP and the C-terminal half of UreR …

Photoelectron Spectroscopy And The Dipole Approximation, Oliver Hemmers, Dennis W. Lindle

Environmental Studies Faculty Publications

Over the past three decades, the dipole approximation has facilitated a basic understanding of the photoionization process in atoms and molecules. Advances in gas-phase photoemission experiments using synchrotron radiation have recently highlighted nondipole effects at relatively low photon energies while probing the limits of the dipole approximation. Breakdowns in this approximation are manifested primarily as deviations from dipolar angular distributions of photoelectrons. Detailed new results demonstrate nondipolar angular-distribution effects are easily observable in atomic gases at energies well below 1 keV, and, in molecules, a previously unexpected phenomenon greatly enhances the breakdown of the dipole approximation just above the core-level …

Photochemical Degradation Of 2,4-D And Atrazine In Well-Defined Media, Asher D. Ghertner

Honors Theses

Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.

Optical Bleaching In Continuous Laser Excited Photothermal Lens Spectrometry, Agnes Chartier, Stephen E. Bialkowski

Stephen E. Bialkowski

This paper presents methods for measuring and modeling optical bleaching that occurs, by using continuous laser sources for solution-phase organic dye molecule spectrometry. Photothermal lens experiments are used to measure the nonlinear optical absorption coefficients of eosin Y, erythrosin B, and pseudo-isocyanine iodide dyes in ethanol as a function of excitation irradiance. Excitation irradiance-dependent photothermal lens data are subsequently interpreted in terms of the photophysics and excited-state relaxation dynamics of the condensed-phase dye molecules under study. The model uses first-order kinetics for excitation and subsequent metastable-state relaxation back to the ground state and accounts for both ground- and metastable-state absorption. …

The Functionalization Of Thermally Stable Third-Order Nlo Chromophores, James Richard Sawyer

Browse all Theses and Dissertations

There is a need to functionalize NLO chromophore systems to incorporate them into polymeric matricies by covalent attachment. The functionalization of a series of NLO chromophores based on the N,N-diphenyl-N-[7-(2-benzothiazolyl)-9,9-diethyl-2- fluorenyl ]amine structure has been investigated. All the chromophores were synthesized from the intermediate chromophore N-phenyl-N-[4-(4-bromophenyl)phenyl ]-N-[7-(2- benzothiazolyl)-9,9-diethyl-2-fluorenyl ]amine which was prepared by a six-step process. Bromination of fluorene yielded 2,7-dibromo-fluorene which could be converted to 2,7- dibromo-9,9-diethylfluorene by alkylation with ethyl iodide in DMSO.Reaction of 2,7- dibromo-9,9-diethylfluorene with one equivalent of butyl lithium followed by reaction with DMF provides 2-bromo-7-formyl-9,9-diethylfluorene.Condensation of 2-bromo-7- formyl-9,9-diethylfluorene and 2-aminobenzenethiol in DMSO results in …

Impedance Feedback Control For Scanning Electrochemical Microscopy, David O. Wipf, Mario A. Apuche-Avlles

College of Arts and Sciences Publications and Scholarship

A new constant-distance imaging method based on the relationship between tip impedance and tip-substrate separation has been developed for the scanning electrochemical microscope (SECM). The tip impedance is monitored by application of a high frequency ac voltage bias between the tip and auxiliary electrode. The high frequency ac current is easily separated from the dc level faradaic electrochemistry with a simple RC filter, which allows impedance measurements during feedback or generation/collection experiments. By employing a piezo-based feedback controller we are able to maintain the impedance at a constant value and, thus, maintain a constant tip-substrate separation. Application of the method …

Moisture Determination By Thermal Titrimetry Using The Enthalpy Of Reaction Of 2,2-Dimethoxypropane With Water, Edmond W. Wilson Jr., Reagan Baber

Journal of the Arkansas Academy of Science

Assays for water content can be readily and simply carried out using the technique of thermal titrations. The method is based on measuring the endothermic heat of reaction exhibited when 2,2-dimethoxypropane is brought into contact with water in the presence of an acid catalyst. The apparatus is simple, requiring a constant delivery rate buret, a recording thermistor thermometer, and a stirred, thermally insulated reaction container. The 2,2-dimethoxypropane reagent used for the water assays is environmentally friendly ("green"). It is stable, pleasant smelling and economical. Working curves in three solvents, acetonitrile, tetrahydrofuran and 1,4-dioxane, show excellent precision and linearity with increasing …

Meso-1, 2-Bis (Methylazo)-1, 2-Diphenylethane, Craig A. Bayse, Barry K. Carpenter, Rudy L. Luck

Chemistry & Biochemistry Faculty Publications

The title compound, meso-1,2-bis(methyldiazenyl)-1,2-diphenylethane, C16H18N4, is arranged in a disordered manner around an inversion point. The N—N atom distances in the azo group of 1.192 (8) and 1.195 (8) Å, and the C—C atom distances in the ethylene moiety at 1.512 (8) and 1.503 (8) Å in the two models [refined to 51.7 (6) and 48.3 (6)% occupancies] were not significantly different.

Chemically Accurate Conformational Energies For Aziridine-2-Carbonitrile, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

The energy of trans-aziridine-2-carbonitrile relative to cis-aziridine-2-carbonitrile was determined by carrying out extensive ab initio computations. The coupled cluster technique was used to determine the higher order computations, that includes perturbative estimate of the triple excitations. The electronic energy of the transition structure connecting the two conformers was determined to be 77.15 kJ/mol higher than the cis-isomer.

The Synthesis Of Deuterated Arylamine Dna Adducts For Use In The Development Of An Isotope Dilution Lc/Ms/Ms Method, Philip Dmitri Olsen

LSU Doctoral Dissertations

Polycyclic aromatic amines (arylamines) are a class of chemical carcinogens that are prevalent in environmental and industrial settings. In order to study the mechanism of their toxicity a quantitative and qualitative detection method was developed to measure the C8-adenine adducts of benzidine and 2-aminofluorene in DNA samples. To do this a novel synthetic method using a palladium catalyst was developed to prepare authentic and deuterated arylamine adducts to serve as standards. These standards were then used to develop a high performance liquid chromatography, electrospray, tandem mass spectrometry, isotope dilution, detection method. To demonstrate the validity of this method two spike …

Preliminary X-Ray Diffraction Studies Of The Transcriptional Inhibitory Antibody Fab41.4, Johanna Mazlo, Robyn L. Stanfield, Ian A. Wilson, Steven H. Hinrichs, John J. Stezowski

Chemistry Department: Faculty Publications

The binding of transcription factor ATF-1 to DNA contributes to gene expression and regulation of cell growth. Antibody Mab41.4, raised against ATF-1, and its derivatives Fab41.4 and scFv41.4 inhibit specific DNA binding in vitro and induce apoptotic death of tumor cells in vivo. Structural studies of Fab41.4 were performed to gain insight into the mechanism of action of this potentially therapeutic antibody. The optimal conditions for crystallization of Fab41.4 were determined. Crystals were needle-like in appearance, displayed C2 space-group symmetry and diffracted to a resolution of 1.6 Å. The unit-cell parameters were determined to be a = 186.64, b = …