Physical Sciences and Mathematics Commons^™

Phosphorus Bearing Substrates In Ring Expansion Reactions, Bradley K. Norwood

Theses and Dissertations

A variety of substituted phosphonium salts, phosphorus ylides and phosphonates were studied to assess their utility in ring expansion reactions. The strategy involved formation of fused ring systems whose ring strain could be exploited to accomplish ring expansion to medium sized rings. β-Alkoxy vinylphosphonium salts were found to be unreactive with species such as the dimethylsulfoxonium methylide anion, Simmons-Smith type reagents. and carbenes in attempts to produce cyclopropyl phosphonium salts.

C-Alkylation of β-keto phosphorus ylides using haloalkanes bearing terminal groups that could be converted and reacted with the B-carbonyl, was also examined as a method for accessing strained rings bearing …

Cis-(Diethyldithiocarbamato)Diiodo(Phenyl)Tellurium(Iv), Phte(S2Cnet2)I2, And Its Methoxy-Substituted Mixed Br/1 Analogue Cis-Bis(0.4-Bromo/0.6-Iodo)-(Diethyldithiocarbamato)(4-Methoxyphenyl) Tellurium(Iv), P-Meoc6H4Te(S2 Cnet2)(Br0.4I0.6)2, Steinar Husebye, Steffen Kudis, Sergey V. Lindeman, Peter Strauch

Chemistry Faculty Research and Publications

The Te^IV complexes PhTe(S₂CNEt2)I₂, (1), and p-MeOC₆H₄Te(S₂CNEt₂)Br_0.4/I_0.6) ₂, (2), have been synthesized by reacting PhTeI₃ with NaS₂CNEt₂, and p-MeOC₆H₄Te(S₂CNEt₂)₂I with Br₂, respectively. In (2), both I atoms are partially replaced by Br atoms in a 3:2 ratio. The structures display distorted octahedral Te coordination with two symmetrically coordinated S atoms [Te—S 2.550 (2)—2.569 (2) Å in three independent molecules of (1) and 2.523 …

A Spectroscopic Study Of A Rationally Designed Zinc Binding Protein, Jill Funk

Honors Theses, 1963-2015

Recently, biomedical science has turned its drug research endeavors towards a philosophy known as rational drug design. Its goal is to avoid the guesswork and instead design and create the exact proteins that are needed. In order for rational drug design to be feasible, a better understanding of protein structure and function needs to be obtained. This research analyses the structure and function of a "rationally" designed mutation of the calcium binding protein parvalbumin. Parvalbumin was chosen because certain aspects of its composition facilitate analysis and in addition, there is extensive data already known about the protein. The mutation involved …

Determination Of Hydroxyl Radical Production Rates In Natural Waters Using The Fluorometric Reagent P-Hydroxyphenylacetic Acid, Jason D. Hosmer

Honors Theses

A means of determining hydroxyl radical production rates in natural waters through the formation of a directly detectable fluorescent product has been developed. A method similar to the enzyme mediated oxidation of phydroxyphenylacetic acid by hydrogen peroxide is used (Miller and Kester, 1988). Due to the high reactivity of hydroxyl radicals, and subsequently low steady state concentrations, direct detection is very difficult. In the past detection was achieved through the introduction of a probe, usually a substituted aromatic or alcohol, that decays away at an observable rate upon reaction with hydroxyl radicals. Detection limits and accuracy of such difference based …

Detection Of Dityrosine In Apoferritin, Stephen E. Bialkowski

Stephen E. Bialkowski

Laser-excited fluorescence spectroscopy was adopted for dityrosine detection in horse spleen apoferritin. Dityrosine was identified in horse spleen apoferritin. Fractionation of acid-hydrolyzed horse spleen apoferritin showed fluorescence attributed to dityrosine, and other compounds, excited by 325-nm laser radiation. The other fluorescent compounds resulted in a broad fluorescence emission spectrum of horse spleen apoferritin. The broad emission band overlapped with the fluorescence emission spectrum of pure dityrosine. Fractionation of horse spleen apoferritin acid hydrolysate prior to laser-excited fluorescence detection was necessary for dityrosine quantitative analysis. The concentration of dityrosine in horse spleen apoferritin was 2.5% (mol/mol), estimated from the method of …

Laser Excited Fluorescence Of Dityrosine, Sahar F. Mahmoud, Stephen E. Bialkowski

Stephen E. Bialkowski

In this research, laser-excited fluorescence was examined for sensitive detection of aqueous dityrosine. Samples were excited with a 6.3-mW, 325-nm helium-cadmium laser focused into a small volume-fluorescence cell with a 10-cm lens. The resulting fluorescence emission was collected perpendicular to the excitation and detected with two different schemes. An optical bandpass filter was used with a photomultiplier tube for sensitive quantitative measurement, while a photodiode array detector was used in conjunction with a spectrograph for qualitative characterization of fluorescence emission spectra. Dityrosine detection on the order of 2 × 10^-11 M was obtained with the use of the photomultiplier …

The Selective Synthesis Of 3-Alkylidenetetrahydrofurans, Robin Elaine Southward

Dissertations, Theses, and Masters Projects

No abstract provided.

New Optical Cell Design For Laser Flash Photolysis Studies In Supercritical Fluids, Steven R. Goates, Milton L. Lee, Qin Ji, Edward M. Eyring, Rudi Van Eldik, Kedika Bal Reddy

Faculty Publications

A high-pressure optical cell has been designed that achieves an effective separation between the chemical sample and the pressurizing medium and system. This design limits possible sample contamination and catalytic effects under supercritical fluid sample conditions. Laser flash photolysis experiments were carried out on molybdenum hexacarbonyl dissolved in supercritical CO2. The thermal ring closure reaction of the species Mo(CO)5L, where L is 2,2- bipyridine was found to proceed at rates comparable to those measured previously in liquid benzene or toluene. Much larger activation volumes were found for the reaction in supercritical CO2 than in liquid toluene.

Volatilization Of Contaminants From Wastewater, Shaoyan Wu

Theses

Emission of volatile organic compounds (VOCs) from many industrial wastewater treatment facilities are a major source of air pollution, and getting much attention from EPA. In order to determine "Best Available Control Technology" and "Lowest Achievable Emission Rate" for controlling emissions of VOCs from industrial wastewater, the accurate estimation of VOCs emission rate and realistic modeling of contaminant volatilization are required.

In this research, the volatilization of three compounds (Toluene, Xylene, and Aniline) were studied under varying aeration, stirring, and quiescent scenarios. The concentrations of contaminant were analyzed by HPLC. Experimental rate constants were obtained by using the first order …

Preparations Of Polycarbynes, Reuben D. Rieke

Chemistry Department: Faculty Publications

Polycarbynes prepared from a soluble source of electrons and an organic monomer or co-monomer containing at least one carbyne group in an ethereal, polyethereal, or hydrocarbon solvent are presented. A wide variety of arylcarbyne and/or alkylcarbyne monomers and co-monomers can be combined with a source of electrons soluble in an ethereal, polyethereal, or hydro-carbon solvent to form novel polycarbyne polymers. These polycarbyne polymers can be used to form synthetic diamond materials, fibers, and other materials that can withstand extreme conditions.

Cis-6-Methoxycarbonyl-2,10-Dioxa-1-Phosphabicyclo[4.4.0]Decane 1-Oxide, Thomas M. Lane, Oscar P Rodriguez, Anthony Gerard Sommese, Sheldon E. Cremer, Dennis W. Bennett

Chemistry Faculty Research and Publications

The crystal structure of the title compound, C₉H1505P, is described. The molecule consists of two cis-fused six-membered rings, both in the chair conformation..

Ignition And Environmental Effects Of Wildfires As Related To Giant Impacts, Gregory S. Kufner

Honors Projects

Soot has been discovered by Wolbach et al. at the Cretaceous-Tertiary boundary in various geographic locations, supporting the theory that worldwide wildfires were ignited by the impact of a giant meteorite which caused the mass extinction 65 million years ago. This project examines a deep sea core sample from the North Central Pacific Ocean for evidence of soot. Soot discovery at this site, the only deep ocean site to be studied, supports the theory that soot distribution from the fires was worldwide. In another project, samples from the suevite breccia of the Kara Ust-Kara craters in Russia (unrelated to the …

Photochemistry Of The Nitrite Ion, Laura J. Wilson '95

Honors Projects

Nitrogen containing compounds contribute to many environmental problems such as acid rain, air pollution, groundwater contamination, and smog formation. For example, when the atmosphere is heavily polluted with nitrites and aromatic hydrocarbons, nitrogen compounds can undergo photochemical reactions to produce harmful compounds that can adversely affect the environment. This project studied the photochemistry of the nitrite ion in aqueous basic solution. Both ·OH and NO· radicals are produced during photolysis, but the two radicals recombine in the presence of pure water causing no net reaction. Aromatic compounds present in the solution being photolyzed can act as scavengers reacting with either …

Calculations Of The Interactions Of Energetic Ions With Materials For Protection Of Computer Memory And Biological Systems, Myung-Hee Y. Kim

Dissertations, Theses, and Masters Projects

Theoretical calculations were performed for the propagation and interactions of particles having high atomic numbers and energy through diverse shield materials including polymeric materials and epoxy-bound lunar regolith by using transport codes for laboratory ion beams and the cosmic ray spectrum. Heavy ions fragment and lose energy upon interactions with shielding materials of specified elemental composition, density, and thickness. A fragmenting heavy iron ion produces hundreds of isotopes during nuclear reactions, which are treated in the solution of the transport problem used here. A reduced set of 80 isotopes is sufficient to represent the charge distribution, but a minimum of …

First Principles Linear Response Calculations Of Lattice Dynamics, Cheng-Zhang Wang

Dissertations, Theses, and Masters Projects

First principles calculations, using the density-functional theory and particularly the local density approximation (LDA), have achieved remarkable success in studying the properties of solid state systems. Although the basic results of these calculations are the electronic structures (eigenvalues, eigenfunctions, etc.) and the total energy of ground state, many other related physical properties can be deduced from them by investigating their response under external perturbations. Using the linear response method with linearized-augmented-plane-wave (LAPW) basis, we have calculated lattice dynamical properties of important semiconductors CuCl, SiC and ferroelectric KNbO{dollar}\sb3.{dollar} CuCl is known to exhibit large anharmonic effects and possibly a complicated multi-well …

The Synthesis, Characterization, And Application Of Ether-Containing Polymides, Catharine Croall Fay

Dissertations, Theses, and Masters Projects

Polyimides are a family of heterocyclic polymers that have received extensive evaluation as adhesives, fibers, films, moldings, composite matrices, insulators, coatings, membranes, and resists. their outstanding thermal stability, excellent mechanical and electrical properties, and chemical resistance make them attractive for many applications.;This research developed ether-containing polyimides for three applications: liquid crystalline polyimides as processing aids, polyimides for microelectronic applications, and polyimides for harsh environments. The approach consisted of three primary activities: (1) developed novel diether dianhydrides for polyimide fabrication, (2) designed, characterized, and evaluated polyimide architectures based on the material application requirements, and (3) provided extensive structure-property relationships utilizing a …

Dynamic Phenomena In Layer Superconducting Cuprate And Organic Metals, Juana Acrivos, Lei Chen, C. Burch

Faculty Publications, Chemistry

Dynamic electron spin resonance (ESR) and extended x-ray absorption edge fine structure (XAFS) measurements suggest that layered organic metals and cuprate superconductors behave similarly. The response to microwave radiation in a modulated external magnetic field indicates that: (i) triplet state, T * ESR is observed below Tc for both; (ii) the condensation of free spin doublet D to T* occurs above the transition temperature to superconductivity Tc (10 ± 1 K for the organic metal (BEDT-TTF)3Ta2F11 and 92 to 12 K for YBa2Cu3O7-δ and its rare earth derivatives); (iii) antiferomagnetic (AF) resonance is detected above Tc for the organic metal. …

Neutron Diffraction Studies Of Erni₅₋ₓcoₓ (X=0.68, 1.68, 2.26) Alloys, Z. Zu, William B. Yelon, G. K. Marasinghe, William Joseph James

Physics Faculty Research & Creative Works

ErNi_5-xCo_x alloys were prepared by RF induction melting and analyzed using neutron powder diffraction. Rietveld analysis neutron diffraction data indicates the unit cell volume increases with Co content while the a and c lattice parameters show different dependencies on the composition. the Co atoms show higher affinity for the 3g sites than for the 2c sites. the Co sublattice tends to couple antiferromagnetically to the Er sublattice. the easy magnetization direction is along the c axis.

Cs2ga2o(Bo3)2, Robert W. Smith

Chemistry Faculty Publications

The structure of dicaesium digallium diorthoborate oxide constitutes a new type of oxide borate. It consists of a three-dimensional gallium-oxide-orthoborate lattice with Cs atoms occupying large cavities in the lattice. This lattice is made from pairs of Ga atoms connected through a shared O atom along the [001] direction; these Ga dimers are interconnected through shared O vertices to trigonal BO3 groups along the [010], [110] and [i10] directions, completing the tetrahedral coordination environment of each Ga atom.

The Analysis And Isolation Of Diarrhetic Shellfish Poisoning Toxins, Seán S. Kelly

Theses

This research was initiated to examine the Diarrhetic Shellfish Poisoning (DSP) toxin profiles in mussels (Mytilus edulis) in south-west Ireland. Extensive sampling and testing of shellfish was conducted during the toxic periods of 1991 to 1994. This was the most comprehensive study ever undertaken of toxin profiles in shellfish from a single cultivation area.

A new toxin named dinophysistoxin-2 (DTX-2), which is an isomer of okadaic acid (OA), was the major toxin during prolonged DSP episodes. This toxicity in shellfish occuired soon after high cell counts of Dinophysis acuta were observed. As well as seasonal variability in toxin levels, substantial …

Remote Sensing: A Simpler Way To Reduce Air Pollution, Donald H. Stedman, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Mechanisms Of Poly(Vinyl Chloride) Pyrolysis In The Presence Of Transition Metals, William Stephen Bryant

Dissertations, Theses, and Masters Projects

No abstract provided.

Benz[4,5]Isoquino[1,2-B]Quinazoline-7,9-Dione And A Rearrangement Product Of Its Hydrolysis, 2-(1,8-Naphthalenedicarboximido)Benzamide, Sergey V. Lindeman, Igor I. Ponomarev, Alexandr L. Rusanov

Chemistry Faculty Research and Publications

No abstract provided.

Tris(Diethyldithiocarbamato)(4-Methoxyphenyl)Tellurium(Iv), P-Meoc6H4Te(S2Cnet2)3, And The Triclinic Modification Of Tris(Diethyldithiocarbamato)Phenyltellurium(Iv), Phte(S2Cnet2)3, Steinar Husebye, Sergey V. Lindeman

Chemistry Faculty Research and Publications

No abstract provided.

Studies On The Cyclization Of Cis-1,4-Dichloro-2-Butene With Sodium Dialkylmalonates, Hovis M. E. Imade

Master's Theses

No abstract provided.

Electrochemical, Chromatographic, And Spectrometric Studies Of An Osmium Containing Polymer, Lawrence John Rhodes

Master's Theses

No abstract provided.

Mechanisms Of Poly(Vinyl Chloride) Fire Retardance And Smoke Suppression Induced By Copper Additives, Jong Paul Jeng

Dissertations, Theses, and Masters Projects

The purpose of this study was to elucidate the mechanisms of PVC fire retardance and smoke suppression induced by copper additives.;The experimental approaches involved: (1) the use of activated copper (Cu{dollar}\sp0{dollar}) to study PVC model-compound reactions and the crosslinking of PVC and (2) the pyrolysis of PVC model compounds in the presence of several copper additives in order to examine all of the possible chemical reactions involved in the formation of heavy products.;The results obtained from experiments with activated copper and allylic chloride model compounds suggest that the reductive coupling mechanism is a viable process in PVC. The Cu{dollar}\sp0{dollar} that …

Blends Of Reactive Diluents With Phenylethynyl-Terminated Arylene Ether Oligomers, Rachel Louise Knudsen

Dissertations, Theses, and Masters Projects

No abstract provided.

Characterization Of Nylon-11 Degradation, Leslie Christian Mccullough

Dissertations, Theses, and Masters Projects

No abstract provided.

Characterization Of Pr500 For Use In Resin Transfer Molding, Rhonda Michelle Barksdale

Dissertations, Theses, and Masters Projects

No abstract provided.