Physical Sciences and Mathematics Commons^™

Capillary Liquid Chromatography Using Micro Size Particles, Yanqiao Xiang

Theses and Dissertations

High speed and/or high efficiency separations can be realized using small particles (~ 1 µm) in liquid chromatography (LC). However, due to the large pressure drop caused by small particles, conventional LC pumping systems cannot satisfy the pressure requirements needed to drive the mobile phase through the column. Use of ultrahigh pressure, elevated temperature, or both can overcome these pressure limitations and allow the use of very small particles for high speed and/or high efficiency separations.

In this dissertation, the use of ultrahigh pressures with and without elevated temperatures in capillary LC is described. Very fast separations of various samples …

Velocity And Temperature Characterization Of The First Vacuum Stage Expansion In An Inductively Coupled Plasma - Mass Spectrometer, William Neil Radicic

Theses and Dissertations

The inductively coupled plasma - mass spectrometer (ICP-MS) is the analytical instrument of choice for trace element detection and quantification. Despite the popularity of ICP-MS, significant degradation in sensitivity and precision occurs as the result of matrix and instrument-induced effects. The sources of these effects are not well understood, characterized, or correlated to particular plasma operating condition settings or matrix compositions and involve both neutral and charged species. The purpose of this study is to characterize the behavior of metastable Ar (I) atom and Ca (II) ion through the measurement of Doppler velocities and fluorescence line width "temperatures."

For the …

N9 Alkylation And Glycosylation Of Purines; A Practical Synthesis Of 2-Chloro-2'-Deoxyadenosine, Minghong Zhong

Theses and Dissertations

(a) The Robins reagent [2-acetamido-6-O-(diphenylcarbamoyl)purine] was utilized for glycosylation under Lewis acid conditions. Regioselectivity of glycosylation depends on the glycosyl donor and its 2-O- or 2-N-protecting group. Regioselective N9 glycosylation of 2-acetamido-6-O-(diphenylcarbamoyl)purine with problematic glucosamine has been accomplished by protecting the amino function as a phthalimido group with consequent stabilization of the oxocarbenium cation, and lowering the activation energy by introduction of trichloroacetimidate at the anomeric carbon.

(b) 6-Heteroaryl functions [6-(1,2,4-triazol-4-yl) and 6-(imidazol-1-yl)] were introduced into purine derivatives for regioselective N9 alkylation. The regiospecificity of alkylation mainly results from steric effects due to the coplanar conformation of the two linked …

Fluorescence Detectors For Proteins And Toxic Heavy Metals, Uchenna Prince Paul

Theses and Dissertations

An inexpensive detector for proteins is described. The detection technique was based on two-photon excitation intrinsic protein fluorescence using a visible 532 nm diode-pumped nano laser as the excitation source. Proteins that exhibit intrinsic fluorescence must contain at least one tryptophan, tyrosine, or phenylalanine residue in their amino acid sequences. The detector was characterized and was found to have a detection limit of 4 micro-molar for tryptophan, 22 micro-molar for tyrosine and 500 micro-molar for phenylalanine. Bovine serum albumin, a serum protein with 3 tryptophan residues in its amino acid sequence was also used to characterize the detector. It was …

Analysis Of Clinically Important Compounds Using Electrophoretic Separation Techniques Coupled To Time-Of-Flight Mass Spectrometry, Zlatuse Durda Peterson

Theses and Dissertations

Capillary electrophoretic (CE) separations were successfully coupled to time-of-flight mass spectrometric (TOFMS) detection for the analysis of three families of biological compounds that act as mediators and/or indicators of disease, namely, catecholamines (dopamine, epinephrine, norepinephrine) and their O-methoxylated metabolites (3-methoxytyramine, norepinephrine, and normetanephrine), indolamines (serotonin, tryptophan, and 5-hydroxytryptophan), and angiotensin peptides. While electrophoretic separation techniques provided high separation efficiency, mass spectrometric detection afforded specificity unsurpassed by other types of detectors.

Both catecholamines and indolamines are present in body fluids at concentrations that make it possible for them to be determined by capillary zone electrophoresis coupled to TOFMS without employing any …

An Evaluation Of Formate As An Electron Donor To Facilitate Palladium (Pd) - Catalyzed Destruction Of Chlorinated Aliphatic Hydrocarbons, Matthew D. Welling

Theses and Dissertations

Chlorinated aliphatic hydrocarbons (CAHs) such as trichloroethylene (TCE), tetrachloroethylene (PCE), and trichloroethane (TCA) are probable human carcinogens that have been used widely within the DoD, primarily as solvents for cleaning and metal degreasing. These compounds are frequently found to be groundwater contaminants. In fact, TCE and PCE are the first and third most commonly detected groundwater contaminants nationwide. The focus of this study was to determine the effectiveness of using a palladium (Pd) catalyst with formate as a reductant to treat CAH-contaminated groundwater. TCE was used as a model CAH. Other investigators have focused on hydrogen gas (H₂) …

Aerobic Biodegradation Of Alternative Fuel Oxygenates In Unsaturated Soil Columns, Kevin A. Mares

Theses and Dissertations

Groundwater contamination problems caused by methyl-tertiary butyl ether (MTBE) in subsurface waters have prompted the search for a gasoline oxygenate replacement. In order to avoid the problems encountered with MTBE, it is prudent to evaluate the fate and transport in the subsurface of proposed replacements, such as ethanol. In this study, ethanol transport and degradation in unsaturated soil was investigated using a series of eight soil columns. This preliminary study was to see if the soil column system components functioned properly, how similarly the eight soil columns performed, and if soil oxygen concentration affected degradation of ethanol. Tracer tests, using …

Characterization Of Chlorinated Solvent Degradation Profile Due To Microbial And Chemical Processes In A Constructed Wetland, Teresa A. Sobolewski

Theses and Dissertations

Perchloroethene (PCE) and its degradation products are among the most common organic groundwater contaminants in the United States. Constructed wetlands are a relatively new approach to dealing with this contamination problem. With their upward flow capability it is possible to introduce an aerobic and anaerobic environment with a consortium of microorganisms available to degrade the contaminants to within acceptable levels established by the Environmental Protection Agency (EPA). This study is a follow-up to the previous two years of research on PCE degradation in cell 1 at Wright-Patterson Air Force Base. This thesis was conducted in order to study the wetland …

An Evaluation Of Formic Acid As An Electron Donor For Palladium (Pd) Catalyzed Destruction Of Nitroaromatic Compounds, Mark R. Stevens

Theses and Dissertations

The Department of Defense is responsible for over 2,000 hazardous waste sites containing nitroaromatic compounds (NACs) such as 2,4,6-TNT, 2,4- and 2,6-DNT that resulted from the production and use of munitions throughout the nation and world, NACs are typically persistent in natural environments, though they can be oxidized or reduced under engineered conditions, NACs and their reduction products are toxic chemicals and suspected human carcinogens, Both TNT and 2,4-DNT are listed as priority pollutants by the U,S EPA, This study investigates the effectiveness of using a palladium (Pd) catalyst in concert with formic acid as an electron donor to reduce …

Experimental Studies On Nucleation, Nanoparticle's Formation And Polymerization From The Vapor Phase, Victor Maher Abdelsayed

Theses and Dissertations

This research is divided into three major parts. In part I, the critical supersaturations required for the homogeneous nucleation of 2,2,2-trifluorothanol (TFE) vapor have been measured over a temperature range (266-296 K) using an upward thermal diffusion cloud chamber (DCC). The measured supersaturations are in agreement with the predictions of both the classical and the scaled theory of nucleation. Moreover, the condensation of supersaturated TFE vapor on laser-vaporized magnesium nanoparticles has been studied under different experimental conditions, such as the supersaturation, the pressure and the electric field. In part II, the laser vaporization controlled condensation (LVCC) technique was used to …

Gas Phase Studies Of Molecular Clusters Containing Metal Cations, And The Ion Mobility Of Styrene Oligomers, Edreese Housni Alsharaeh

Theses and Dissertations

This study is divided into three parts. Part I deals with the mechanism of the self-initiated polymerization (or thermal polymerization) of styrene in the gas phase. In this work, we present the first direct evidence for the thermally self-initiated polymerization of styrene in the gas phase. Our approach is based on on-line analysis of the gas phase Oligomers by mass-selected ion mobility. The mobility measurements provide structural information on the ionized oligomers based on their collision cross-sections (Ω) which depend on the geometric shapes of the ions. Theoretical calculations of possible structural candidates of the Oligomers ions are then used …