Physical Sciences and Mathematics Commons^™

The Determination Of The Crystal Structure Of 2-Methyl-2methylacrylyl-Cyclohexanone- (1,5)-Diaxaspiro Mononeopentyl By X-Ray Christallography, Joann Stevenson

McCabe Thesis Collection

Cyclohexanone, the central component of the compound 2-methyl-2-methylacrylylcyclohexanone-( l,5)-diaxaspiro mononeopentyl (see figure on page 2), serves as a solvent for oil in piston type aircraft and in natural and vinyl resins. It is used in the production of crude rubber, waxes, fats, shellac and DDT and other pesticides. Cyclohexanone also is a part of the production of adipic acid, which is used to prepare nylon and is used to prepare cyclohexanone resins via condensation to enhance the adhesive properties of products like floor paints.

Cyclohexanones are among the most accessible hydroaromatic derivatives and serve as the initial materials for the …

Pan, Ppn And Mpan Measurements And The Systematic Relationship Between Mpan And Macr At A Semi-Rural Site In Tennessee, George Nouaime

Masters Theses

Simultaneous measurements of peroxymethacryloyl nitrate (MPAN) and its primary and secondary precursors, methacarolein (MACR) and isoprene, were carried out for the first time in July 1995 at a semi-rural site southeast of Nashville. In addition to these compounds, peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), other volatile organic compounds (VOCs) and supporting measurements were also collected in collaboration with other research groups. The mean concentrations of PAN, PPN, MPAN and MACR were found to be 485 pptv, 50 pptv, 30 pptv and 0.290 ppbv respectively. MP AN levels, which closely tracked those of MACR during the day, peaked and dropped earlier …

Elucidation Of The Pathway Required For The Stimulation Of G6pdh Gene Expression By Insulin And Its Mimetics, Asavari Wagle

Masters Theses

Insulin, an anabolic hormone, exquisitely controls cellular physiology and metabolism by modulating the activity of key proteins which regulate metabolic and mitogenic events. Insulin activates several cytosolic proteins via a phosphorylation cascade, but only some of these proteins are required for its specific action. We have elucidated the insulin signal transduction cascade in primary rat hepatocytes, and outlined some of the events that are required for the insulin induced stimulation of glucose-6-phosphate dehydrogenase (G6PDH) gene expression. Using well-characterized and structurally different inhibitors, we show that insulin stimulation of the gene requires the IRS-1/P13K pathway and not the RAS/RAF/MAPK pathway. Gene …

Evaluation Of The Natural Biodegradation Of Aircraft Deicing Fluid Components In Soils, Laura M. Johnson

Theses and Dissertations

This research effort was conducted to analyze the biodegradation of propylene glycol (PG) and tolyltriazole in two different soil types; a sandy soil and a high clay soil. Both an automated respirometer and a high performance liquid chromatograph (H PLO) were used in the analysis. Two separate experiments were conducted. In the first experiment, one level of tolyltriazole was added to the soils to determine whether or not there was a difference in the biodegradation rates of tolyltriazole in the two soils. The respirometer results indicated that there was a significant difference between the respiration rates of the microorganisms in …

Modeling The Uptake And Transpiration Of Tce Using Phreatophytic Trees, Douglas P. Wise

Theses and Dissertations

Phytoremediation is a recent addition to the numerous methods used today to remediate ground water contaminants. It is proving more effective and efficient compared to existing remediation techniques. The use of phreatophytes, or water seeking trees, has great potential for phytoremediation. These trees are fast growing, long lived, grow their roots down to the ground water table, transpire large amounts of water, and are proven to actively remove contaminants from the soil horizon. The purpose of this research is to develop quantitative concepts for understanding the dynamics of TCE uptake and transpiration by phreatophytic trees over a short rotation woody …

A Modeling Study For The Implementation Of In Situ Cometabolic Bioremediation Of Trichloroethylene-Contaminated Groundwater., John A. Christ

Theses and Dissertations

The limitations of conventional groundwater remediation technologies have led to the development of innovative technologies which may achieve national hazardous waste site remediation goals. Before an innovative technology can be implemented in the field, remedial project managers, regulators and other stakeholders require adequate modeling tools to help assess the applicability of the technology at a particular site. This modeling study investigates how an innovative technology, in situ cometabolic bioremediation, might be implemented to remediate a TCE-contaminated site, under different site conditions. A steady-state model is developed which couples an analytical expression to simulate the effect of flow between multiple pumping …

Hybrid Quantum And Molecular Mechanics Embedded Cluster Models For Chemistry On Silicon And Silicon Carbide Surfaces, James R. Shoemaker

Theses and Dissertations

Fabrication of silicon carbide SiC semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO₂ layer on SiC is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics QM, do not exist because of the huge computational cost of solving Schroedingers equation for a molecular cluster large enough to represent a surface. Molecular mechanics MM, which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, …

Extraction Of Premafloxacin Radiolabeled With Carbon Fourteen From Loam Soil, Steven Gregory Staskiewicz

Masters Theses

Premafloxacin is a fluoroquinolone antibiotic being developed by Pharmacia & Upjohn for veterinary indications. Since the parent drug and possibly metabolites will be applied to soil through the deposition of animal excreta, many regulatory agencies will require environmental assessment testing. In order to determine if ¹⁴C-premafloxacin would biodegrade in the soil, loam soil was extracted with solvents and C18 solid phase columns were used to isolate the compound after three weeks of incubation. In addition to extracting the soil, production of ¹⁴CO₂ was monitored by trapping the degradation by-product in 2 N NaOH. Liquid scintillation counting of …

Speciation Of Selenium In Serum, Alice Tsapayi-Musapatike

Chemistry & Biochemistry Theses & Dissertations

We investigated the separation of selenoprotein P and extracellular (serum) glutathione peroxidase using a concanavalin A affinity column. We were able to show that the method does not adequately separate serum glutathione peroxidase from selenoprotein P because human glutathione peroxidase binds strongly to the column. We also found that albumin can interfere with measurement serum of glutathione peroxidase activity when hydrogen peroxide is used as the substrate. When t-butyl hydroperoxide was used as the substrate, less than 10% of the measured activity was due to the presence of albumin. We also found that the pH of the elution buffer plays …

Evaluation Of Solid Phase Extraction Followed By Supercritical Fluid Elution Of Semi-Volatile Organic Compounds In Toxicity Characteristic Leachates, William Edward Corl Iii

Chemistry & Biochemistry Theses & Dissertations

The Environmental Protection Agency (EPA) developed the toxicity characteristic leaching procedure (TCLP) to determine the potential for unknown wastes to leach haz.ardous constituents into the environment. Methods currently being used for the extraction of semi-volatile organic compounds from aqueous TCLP leachates involve acid/base partitioning into methylene chloride. The concentrated extract is then analyzed by gas chromatography/mass spectrometry (GC/MS). The methods are either timeconsuming or labor intensive and they generate significant volumes of haz.ardous wastes themselves. Considering the haz.ards and disposal costs of methylene chloride wastes, great interest has been elicited by the EPA in other extraction techniques which would reduce …

Fabrication And Evaluation Of Boron-Doped Cvd Diamond Microelectrodes, Song Pang

Chemistry & Biochemistry Theses & Dissertations

The electrochemical behavior of boron-doped diamond microelectrodes has been studied in acetonitrile solutions containing two redox couples using cyclic voltammetry. One test system is 1-2.5 mM ferrocene, containing 0.1 M Tetrabutyl ammonium hexafluorophosphate (TBAH). This well-known reversible redox system involves only one electron transfer with little or no change in the solvation sphere and no breakage/formation of chemical bonds. Another test system is a 1 mM S₂Mo₁₈0₆₄^4- solution containing 0.1 M HCIO₄. This is one of the most complicated redox systems. In the presence of acid, electrons are usually transferred consecutively and …

Synthesis Of Biologically Active Substituted Chalcones, Kiel Steven Hoff

Masters Theses

Two different synthetic routes to poly-hydroxylated chalcones are investigated. The wittig synthesis and protection of the hydroxyl functionalities by forming the methyl ether followed by the base catalyzed Claissen-schmidt reaction and then deprotection were investigated. It was demonstrated that the protection-condensation- deprotection route was more efficient. The antiviral activity of 2,2', 4' - trihydroxychalcone against the HIV virus is also presented.

The Effect Of Protein Environment And Ring Substitution On The Electrostatic Charges, Dipole Moment, And Ultraviolet Spectra Of Flavin, Jared Berger

Honors Theses

Old Yellow Enzyme is an interesting protein clue to its involvement in many biochemical systems, such as bioluminescence and degradation of variety of substrates. The flavin mononucleotide (FMN) is the active site of the protein. The FMN is an isoalloxazine ring with a phospholipid tail, which attaches to the protein through a phosphate group and hydrogen bonding in the hydrophilic section of the ring system. My research is a theoretical, computational calculation, which uses Spartan, a quantum mechanical calculation program, to determine how the dipole moment and electrostatic charges change upon the substitution of the FMN and within the protein …

Molecular Recognition Of Blunt-Ended Dna, Michael D. Farwell

Honors Theses

Many important enzymatic and physical processes occur specifically at the ends of DNA molecules. The goal of this project was to develop a molecule that would be an effective probe of the chemistry a. the ends of DNA. To do this, ethidium bromide, a well-known intercalation (a molecule that binds between DNA base pairs), was blocked to intercalation with bulky t-butyl groups. We proposed that this new molecule would preferentially bind to blunt-ended DNA, where there is much less steric hindrance. The synthesized molecule was characterized by NMR, Fluorescence, UV/Vis, and Mass Spectroscopy. Supporting data were acquired through fluorescence lifetime …

Methylene Blue Doped Sol-Gels Preparation And Application As Fiber-Optic Fluorescence Sensors, Dawn M. Landry

Honors Theses

The goal of this thesis project was to create a Methylene Blue (MB) doped sol-gel fiber-optic fluorescence sensor. Ideally this sensor would be capable of detecting changes in sulfite concentration in solution continuously and reversibly. In aqueous solution, MB, a redox indicator, is converted from a bright blue color to the colorless leuco-MB species upon exposure to sulfite or other reducing agents. This reaction is reversible in the presence of an oxidizing agent Therefore, if MB can be immobilized properly, it would make a suitable reversible indicator for the sulfite anion in solution. The method of MB immobilization employed in …

A Binding Investigation Of Fluorescence\Probes And Cyclodextrin Derivatives, Sara L. Mcintosh

Honors Theses

Cyclodextrins (CDs) are cyclical carbohydrates composed of repeating glucopyranose units. The three most common CDs, α-, β-, or y-, contain 6, 7 and 8 glucopyranose units, respectively, and have hydrophilic exteriors, which makes them water soluble. CD polymers (CDPs) have been synthesized, containing glyceryl link, between CD units. These polymers are more water soluble than their monomer counterparts. CDs and CDPs, because of their hydrophobic interior cavities, form inclusion complexes with various molecules, including aromatics. This latter property is one we have investigated using fluorophores, including naphthalenes and pyrene. We have shown, through absorption spectral and fluorescence lifetime data, that …

Comparison Of Outgassing And Surface Reactivity Of Graphic Substrates, Philip Ross Tavernier

Honors Theses

Materials constructed of carbon are widely used in applications requiring high emissivity at temperatures above 1300°C. The ability to transmit heat efficiently makes these materials an excellent choice for use with x-ray tubes. However, heating carbon substrates to high temperatures also leads to thermal desorption of surface bound species. The release of these species increases the total vapor pressure inside sealed x-ray tubes. Our present study considers the outgassing of these carbon substrates as a function of temperature, as a result of their reactivity towards oxygen, carbon monoxide, carbon dioxide, and water vapor. By modeling the factors that influence outgassing …

A Computational Study Of The Inclusion Processes Of Cyclodextrins And Cyclodextrin Polymers, James A. Best

Honors Theses

Cyclodextrins (CDs) are molecules that are composed of glucopyranose rings. Cyclodextrins can be formed from either 6, 7, or 8 glucopyranose units yielding, α-, β-, or y-Cyclodextrins respectively. Cyclodextrin polymers (COPs) can occur when glyceryl linkers are added to the previously mentioned cyclodextrins. CDs and COPs are hydrophilic, yet contain a hydrophobic cavity. This cavity allows for the binding of numerous guest molecules. Some practical purposes resulting from the host-guest interactions can be seen in cosmetology, food science, and pharmacy. Using the MacroModel Interactive Molecular Modeling System Version 5.0 we studied the binding of guest molecules to α-, β-, and …

Design, Synthesis, And Characterization Of Short Salt And Non-Salt Bridged Peptides, Clark K.N. Choi

Honors Theses

Peptides with secondary characteristics such as α-helices are among the most important structures in nature. Previous studies from Baldwin and coworkers have shown that short alanine-based peptides with specific salt spacing adopt helical conformations. In the study of helix formation, we have synthesized our versions of alanine- and glutamine-based peptides with (i, i + 4) and (i, i + 5) salt spacing. The design of the salt bridge is most suitable when it contains (i, i + 4) salt spacing. The rational is that the (i, i + 4) salt spacing yields a value close to 3.6, the number of …

Kinetics And Mechanism Of Chromium Hexacarbonyl Photochemistry Using Flash By Photolysis, Marina Zaydman

Honors Theses

Chromium hexacarbonyl, Cr(CO)6, has been shown to be a very effective photochemical catalyst for many reactions, such as the 1,4- hydrogenation and 1 ,4-hydrosilation of conjugated 1 ,3-dienes resulting in the formation of a cis alkene product in greater than 99% yield. Although much research has been done on the reactions which Cr(CO)6 catalyzes, not much data exists on the reactions of photochemically created fragments of Cr(CO)6 , such as Cr(CO)6. This study focuses on the reactivity of organotransition metal intermediates with the goal of contributing to the growing database of the reactions involving the photochemistry of Cr(CO)6. Particular emphasis …

The Crystallation Of Estrogen-Binding Protein From Candida Albicans, Chia-En Chen

Honors Theses

In the past decade scientists have discovered that the pathogenic fungus Candida albicans contains a highly specific estrogen-binding protein (EBP). Since it is known that the use of estrogen-containing compounds causes one to be more prone to infection by this organism, it is hypothesized that this estrogen system may have a role in infection. Understanding the structure and function of EBP would be helpful in developing treatments for infection by C. albicans. One way to approach the structure and function question of any protein is to crystallize the protein and solve its structure using X-ray diffraction. In the past few …

Syntheses And Characterizations Of Unsymmetrical Porphyrins As Photosensitizers For A Solid-State Solar Cell, Yinping Zhao

Dissertations and Theses

Solar light is the most important source of regenerative energy and represents mankind's only inexhaustible energy source. One of today's most promising tools to make use of solar energy is its direct conversion into electrical energy in a photovoltaic cell. The practical use of these solar cells depends on the price of the devices and therefore of the obtained energy. The conventional silicon cells, although efficient, are expensive for common consumer applications. The Grätzel cell is a photovoltaic system for harvesting the sun's energy that operates at about 10-15% overall efficiency, like a conventional solar cell, but does it at …

Signal Transduction Pathways In Volvox Carteri, Heide Girardin

Honors Theses

The green alga Volvox carteri exhibits a virtual absence of protein synthesis in the dark, but begins synthesizing proteins necessary for growth and development almost immediately after exposure to the light. The regulation of protein synthesis in this system is known to be translational since extracts prepared in the dark have identical pools and quantities of mRNA as extracts prepared in the light (Kirk and Kirk, 1983). Exploration of the mechanism of translational regulation has led us to consider the importance of signal transduction pathways. By using a variety of commercially available drugs that affect specific components of known signaling …

Celluloid Blackness : Race, Modernity, And The Conflicted Roots Of American Cinema (1915-1939), Lincoln Farr

Honors Theses

Introduction: "The Problem of the Twentieth Century" In a full page interview in the New York Times on May 29, 1912, the Swiss psychiatrist Dr. Carl G. Jung told the American people, "It seems to me that you are about to discover yourselves. You have discovered everything else-all the land of this continent; all the resources, all the hidden things of nature."Jung used the interview to address the American people, at a moment which he somehow recognized as crucial in the development of human civilization. America, the "tragic" country which he struggled to comprehend, would soon become the harbinger of …

Computer Modeling Of Molecular Vibration Frequencies And Its Application To The Modeling Of Silane Compounds, Ryan T. Merrell

Honors Capstone Projects and Theses

No abstract provided.

Synthesis And Protection Of Nitrogen Containing Heterocycles, Timothy I. Elwell

Undergraduate Honors Capstone Projects

The pyrrolo[2,3-d] pyrimidine ring systems are present in a variety of antibacterial/anticancer compounds. A scarcity of natural sources has made necessary the need for researchers to find more efficient methodologies to synthesize such compounds.1 The Edstrom research group is currently exploring new routes to these compounds, varying the protecting groups and the precursors used to make them.

Binding Of Cobalt (Iii) To Nucleic Acids Via Reaction With [Co(Nh3)5(Oh2)]3+, David M. Calderone

Seton Hall University Dissertations and Theses (ETDs)

No abstract provided.

Synthesis Of 1-Alloc-Piperidine-4-Fmoc-Amino-4-Carboxylic Acid: A Novel, Protected ?,?- Disubstituted Amino Acid, Muna K. Thalji

Honors Theses

No abstract provided.

Thermal Studies Of Complex Formations Of First Row Transition Metals With Phenolic Compounds In Aqueous Solution, Nabil Adnan Amro

Masters Theses

The coordination chemistry of protocatechuic acid and catechols with the first row of transition metals was studied as a model for the more complicated natural humic substance.

The reaction between Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and the phenols, catechol and protocatechuic acid in aqueous solution was studied by the spectrophotometric method. The composition of the complexes formed was determined by continuous variation, iso-molar series and molar ratio methods. The presence of complexes with metal:ligand ratio of 1:1, 1:2 and 1:3 was established in the pH range 3 to …

Analysis Of Organic Nitrates In Artic Outflow, Deanna Elyea-Piper

Masters Theses

The Arctic Outflow Study (AOS) was a project funded by the National Science Foundation to assess the impact of tropospheric ozone concentrations by the measurement of oxidized nitrogen. Measurements of arctic outflow were made to assess the seasonal cycle of compounds in arctic air and the partitioning of NOy during transport to the North Atlantic region. These photochemically active compounds are elevated in the arctic during the winter and spring because of the lack of photochemical processes to destroy them.

Measurements of PAN, Alkyl nitrates, NOy, NO, NO₂, CO, HNO₃, O₃, and particulate nitrate …