Chemistry Commons^™

Explosive Vapor Generation And Sampling In Conjunction With Ion Mobility Spectrometry, Saeed H. Almeer

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research is to develop an inexpensive and reliable method to generate vapor pulses of explosives using 2,4,6-trinitrotoluene TNTl for proof of concept. A secondary objective is to demonstrate the use of the vapor generator in various applications keeping in mind potential field scenarios involving explosives. A vapor generator/collector system was developed which gives reproducible pulses of TNT vapors at nanogram levels. The use of this technology was demonstrated in evaluating different surfaces for vapor adsorption of TNT in conjunction with ion mobility spectrometry as the primary analytical tool. Of the materials examined, Teflon was by …

Generation Of Intense Excimer Radiation From High-Pressure Hollow Cathode Discharges, Ahmed El-Habachi, Karl H. Schoenbach

Bioelectrics Publications

By reducing the diameter of the cathode opening in a hollow cathode discharge geometry to values on the order of 100 μm, we were able to operate these discharges in noble gases in a direct current mode up to atmospheric pressure. High-pressure discharges in xenon were found to be strong sources of excimer radiation. Highest intensities at a wavelength of 172 nm were obtained at a pressure of 400 Torr. At this pressure, the vacuum ultraviolet (VUV) radiant power of a single discharge operating at a forward voltage of 220 V and currents exceeding 2 mA reaches values between 6% …

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 …

Comparison Of The Dichlorination Of Organic N-Chloramines By Caroate And By Bisulfite: A Kinetic Study, Said H. Lubbad

Chemistry & Biochemistry Theses & Dissertations

Bisulfite is commonly used to dechlorinate chlorinated municipal wastewater. However, several studies suggest that bisulfite is not effective in dechlorinating N-chlorinated amino components of wastewater. The purpose of this study was to investigate the effectiveness of an alternate dechlorinating agent, caroate (peroxysulfate), and to compare its rate of dechlorination of three different types of chloramines with that of bisulfite.

Four N-chlorinated amino compounds were investigated: N-chlorodiethylamine, N­ chloroalanylphenylalanine, N-chloroglycylphenylalanine, and N-[2-(N'-chloroimino)­ propanoyl]phenylalanine. These compounds were selected from different families of N­ chloramines to study the effect of structure on dechlorination by both caroate and bisulfite. At pH …

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 …

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 …

Development Of Solid Phase Microextraction Methods For Contraband Drugs, Vangielynn Cruz Tersol

Chemistry & Biochemistry Theses & Dissertations

The objective of this study is to develop analytical methods for studying contraband drugs at nanogram levels and to demonstrate the utility of the methods. A method which combines solid phase microextraction with ion mobility spectrometry (SPME-IMS) was developed. The SPME-IMS method was used as a rapid screening tool in studying the chemistry of cocaine HCI, heroin HCI, and heroin freebase on surfaces. The total time for sample preparation, reaction, and analysis is approximately seven minutes. Another method that was developed is one that combines solid phase microextraction with gas chromatography (SPME-GC) for the quantitative analysis of cocaine freebase and …

Development Of A Fluorescent Indicator For Inorganic Monochloramine, Xiaojun Dong Zou

Chemistry & Biochemistry Theses & Dissertations

Current methods used to determine combined residual chlorine cannot distinguish between inorganic monochloramine (NH₂Cl) and organic chloramines. Studies described in this thesis were carried out to develop a novel method of determining the concentration of inorganic monochloramine in aqueous solutions. Based on the observation that the reaction of 3-formyl-1-methylpyridinium chloride (3FMPCl) with NH₂Cl produces a solution which is fluorescent, experiments were conducted to characterize the reaction and optimize the experimental conditions. Using the finalized protocol, NH₂Cl measurements were made in the presence and absence of organic amines and compared with a commonly used N, …

Microwave Plasma Chemical Vapor Deposited Diamond Tips For Scanning Tunneling Microscopy, Sacharia Albin, Jianli Zheng, John B. Cooper, Weihai Fu, Arnel C. Lavarias

Electrical & Computer Engineering Faculty Publications

Diamond microparticles were grown on etched tungsten wires using a microwave plasma-assisted chemical vapor deposition process. The apexes on cubo-octahedral particles bound by {100} and {111} facets were effectively used as tunneling tips for scanning tunneling microscopy. The atomically resolved surface image of highly oriented pyrolytic graphite was acquired. Tunneling characteristics revealed a higher electron emission from the diamond tips than that from the platinum–iridium tips. The same diamond tips were used to produce surface indentation and its image. © 1997 American Institute of Physics.

Characterization Of Iron Oxides And Atmospheric Corrosion Of Steel, Sei Jin Oh

Physics Theses & Dissertations

The study of corrosion behavior was performed using three different analytical techniques, which provided information on the formation, development and layering of iron oxides on the corrosion products as a function of atmospheric conditions, exposure time and type of steel. In particular, the protective layer formed on weathering steel was investigated as a function of different amounts of alloying elements in the steel, atmospheric conditions and exposure times. Combined together, the results provided a better understanding of the atmospheric corrosion behavior of steel, and formed a part of database of the atmospheric corrosion characteristics.

Accurate characterization of the iron oxides …

Concentrations, Complexation And Speciation Of Total Dissolved Zinc In The Chesapeake Bay, Charles William Henry Iii

Chemistry & Biochemistry Theses & Dissertations

This is the first research to examine the horizontal, vertical, and temporal variability of total dissolved zinc, organic complexation of zinc, and zinc speciation in the Chesapeake Bay. Filtered (0.45μm) surface and bottom water samples were taken along the salinity gradient of the Chesapeake Bay in October 1993, March 1995, July 1995, and October 1995. Analysis by Differential Pulse Anodic Stripping Voltammetry (DP ASV) indicated that total dissolved zinc concentrations in the Bay ranged from 2.9 ± 0.7nM to 38.8 ± 2nM. Total zinc was highest at the northern end of the Bay (low salinity), approximately 10 times lower at …

Comparison Of Positive Screening And Confimatory Results From Federally Mandated Drug Testing Of Urine, Mary M. Stuck

Community & Environmental Health Theses & Dissertations

The purpose of this study was to analyze the accuracy of FDA approved immunoassays for the detection of drug positive urine samples.

Federal civilian employees are tested under the strict protocol of the Department of Health and Human Services mandatory guidelines for federal workplace drug testing programs. The guidelines provide for a two instrument testing protocol for the analysis of urine samples. The first is an FDA approved immunoassay. Samples which test positive on this screening immunoassay are then submitted for confirmatory testing with the "gold standard" gas chromatography/mass spectrometry.

Agency monthly drug testing summaries, required under the DHHS guidelines …

Reactions Of Aqueous Chlorine With Alanylphenylalanine In Model Solutions And In A Wastewater, Thomas C. Fox

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the dipeptide alanylphenylalanine were chlorinated to four different chlorine-to-amino nitrogen (Cl₂/Ala-Phe) mole ratios and analyzed by high performance liquid chromatography. At mole ratios ≤ 1, N-chloroalanylphenylalanine was the only major product. As the Cl₂/Ala-Phe mole ratio was increased to ≥ 2, N,N-dichloroalanylphenylalanine was the only major product. In model solutions (pH 7.0) the dichlorinated dipeptide decomposed (t_1/2= 4.1 hr) to form a stable N-chloroketimine, which has a half-life of 125 hours. This N-chloroketimine then decomposed to form phenylalanine.

To follow these reactions in a wastewater, alanyl-p-[ …

Petrochemical Analysis By Remote Fiber-Optic Raman Spectroscopy And Partial Least Squares Regression Analysis, Philip Edmund Flecher Jr.

Chemistry & Biochemistry Theses & Dissertations

A dispersive Raman system with charge coupled device (CCD) detection, distributed Bragg reflector (DBR) diode laser excitation, and a fiber optic probe has been developed for the rapid analysis of petrochemicals and fuels. Initially, mock petroleum fuels with analyte concentrations from 1.S - 16% were prepared and analyzed with the system. The inability of the original index guided diode laser to maintain a constant frequency during the mock petroleum analysis was a recurrent problem. The DBR laser was subsequently shown to have stability superior to index guided lasers, and was used in the remainder of the research.

Real gasoline samples …

Microhollow Cathode Discharges, K. H. Schoenbach, R. Verhappen, R. Tessnow, F. E. Peterkin, W. W. Byszewski

Bioelectrics Publications

The current–voltage characteristics of hollow cathode discharges and their predischarges in argon under dc and pulsed conditions were found to have a positive slope at pressures up to approximately 50 Torr, and currents up to 20 mA, at a hole diameter of 0.7 mm. In this range of pressure and current, parallel operation of hollow cathode discharges, without ballast, was demonstrated. Scaling to higher pressure is possible by reducing the hole diameter. Pulsed experiments with an array of cathode rings of 75 μm diameter allowed us to obtain parallel operation of more than 50 discharges at a pressure of 350 …

Structural Characterization Of A Novel Inhibitor Of Hiv Reverse Transcriptase (Hiv Rt), Greggory Jon Woitte

Chemistry & Biochemistry Theses & Dissertations

Human immunodeficiency virus (HIV) infections have become a leading cause of death among young people in the United States today. As the number of HIV infections increases, so too does the cost of treatment. Together, these numbers have prompted an increase in the development of pharmaceutical interventions. HIV reverse transcriptase (HIV RT) has become a suitable target for drug therapy because it is the sole enzyme responsible for HIV replication.

Fucoidan, a sulfated polysaccharide isolated from the brown algae Fucus vesiculosus, has been shown to block a variety of cell adhesion related events including metastasis. In addition, fucoidan has also …

A Diamond Thin Film Flow Sensor, Sacharia Albin, John C. Hagwood, John B. Cooper, David L. Gray, Scott D. Martinson, Michael A. Scott

Electrical & Computer Engineering Faculty Publications

We present the results of theoretical modeling and experimental testing of a diamond thin film sensor for flow studies. It is shown that the high thermal conductivity of a diamond film can enhance the frequency response of the flow sensor. One-dimensional heat diffusion equation was solved using the finite difference method for determining the frequency response. Two different sensor structures were analyzed: a Ni film on a quartz substrate (Ni/Q) and an intermediate layer of diamond film between the Ni film and quartz substrate (Ni/D/Q). The theoretical model predicts a frequency response for the Ni/D/Q sensor higher than that of …

Determination Of Pancreatic And Salivary Amylase By Enzyme Immunoassay And Their Prevalence In Hyperamylasemic Patients, Sabdra Borgens Ward

Theses and Dissertations in Biomedical Sciences

Currently, amylase determinations are nonspecific for the organ source and are based entirely on the enzymatic properties of amylase to produce a measurable product or byproduct. The determination of pancreatic amylase is important in the diagnosis of acute pancreatitis. Most commercially available tests for amylase employ the measurement of the change in NADH absorbance at 280 nm or of the p-nitrophenol released from a maltotetrose substrate. These are nonspecific measurements of pancreatic amylase and often necessitate other tests to be run such as a serum lipase.

The two predominant isoenzymes of amylase are pancreatic (p-amylase) and salivary (s-amylase); the most …

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Investigation Of The Oxidation Of Co On Platinum/Tin(Iv) Oxide-Based Catalysts, Julie Christi Stiltner Patrick

Chemistry & Biochemistry Theses & Dissertations

Platinum/tin(IV) oxide-based catalysts have been developed for the oxidation of carbon monoxide at 55 °C and 1 atmosphere pressure. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) investigation of this oxidation has been performed. Four catalyst samples have been subjected to a 5% carbon monoxide pretreatment at 125 °C, helium exposure at 55 °C, bottled air (20% oxygen) exposure at 55 °c, and exposure to a 2:1 stoichiometric mixture of carbon monoxide and oxygen at 55 °C. During the course of these exposures, evidence for the development of two different surface carbon monoxide configurations has been found: one that is …

Diamond Thin Film Sensors For Hypersonic Flow Studies, Bhaskar Kumar Bulusu

Electrical & Computer Engineering Theses & Dissertations

Conventional metal film sensors can measure flow instabilities of the order of 60 kHz. The turbulence fluctuations in the hypersonic regime are of the order of 200- 400 kHz. To measure these fluctuations, sensors with an enhanced frequency response are required. Therefore, it is required to identify the parameters to enhance the frequency response. These include parameters such as the temperature sensitivity, the resistivity, the thermal conductivity, the diffusivity, specific heat capacity and the geometric size and shape of the film and the substrate. A selection of materials was then carried out to maximize the frequency response. Diamond was identified …

Surface Flow Structure Of The Gulf Stream From Composite Imagery And Satellite-Tracked Drifters, C. P. Mullen, A. D. Kirwan Jr.

CCPO Publications

A unique set of coutemporaneous satellite-tracked drifters and five-day composite Advanced Very High Resolution Radionmeter (AVHRR) satellite imagery of the North Atlantic has been analyzed to examine the surface flow structure of the Gulf Stream. The study region was divided into two sections, greater than 37 degrees N and less than 37 degrees N, in order to answer the question of geographic variability. Fractal and spectral analyses methods were applied to the data. Fractal analysis of the Lagrangian trajectories showed a fractal dimension of 1.21 +/- 0.02 with a scaling range of 83 - 343 km. The fractal dimension of …

Identification And Quantitation Of Volatile Amines In Chesapeake Bay Sediments, Neeraja Y. Krishna

Chemistry & Biochemistry Theses & Dissertations

Sediments from different parts of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A HF-HCl extraction method was used to extract both exchangeable and fixed amines from the sediments and a purge-and-trap technique was used to concentrate the amines. Following derivatization with heptafluorobutyric anhydride (HFBA), the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One primary amine, i-amylamine with a concentration ranging from 0. 78 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty seven samples collected on three different dates in 1993. Another primary amine, 2-methylbutylamine with a concentration ranging from 0.18 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty three samples collected on three different dates in 1993. A secondary amine, diethylamine was detected but could not be quantified in a total of seven samples collected in September 1993. The concentrations of these amines varied with location in the Bay, depth in the sediment, and time of year the sediments were collected. The origin of i-amylamine and 2-methylbutylamine might be from the biological decarboxylation of amino acids leucine and isoleucine, respectively. The origin of diethylamine is unknown.

A Study Of The Chlorination Products Of Methionine In Model Solutions And In Wastewater, D. Scott Winters

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid methionine were chlorinated to seven chlorine-to-nitrogen (Cl₂/N) molar ratios. After 30 minutes, the solutions were analyzed by high performance liquid chromatography (HPLC). At a Cl₂/N molar ratio of 1, methionine sulfoxide was found to be the main product. At Cl₂/N molar ratios ≥ 2, a mixture of methionine sulfoxide, methionine sulfone, an unidentified sulfoxide (product 1), and N-chloro-3-(methylsulfonyl) propionaldimine are formed. These products were identified by comparison to synthesized standards which were characterized by ¹H-NMR and ¹³C-NMR nuclear magnetic resonance spectroscopy, ion trap mass spectroscopy, …

The Isolation And Identification Of Polyphenolics From Grape Seeds And Their Activity Towards Specific Cell Lines, Joseph A. Reddy

Chemistry & Biochemistry Theses & Dissertations

Grape seed extract is being marketed in France for cardiovascular use and skin care. The active constituents of both these drugs are certain polyphenols called procyanidins. A similar seed extract has now been obtained from Virginia Chardonnay grape seeds. Ten of the major components in this extract have been isolated in their pure form by the semi-preparative HPLC separation on a YMC ODS-AQ (Octadecylsilane-AQ) column. The ODS-Aq column has been shown to have a better resolving capacity compared to the Spherisorb ODS (Octadecylsilane) column previously described in the literature. This has been attributed to the ODSAQ support which has both …

Chlorination Products Of Glycylphenylalanine In Model Solutions And A Wastewater, Daniel J. Keefe

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the dipeptide glycylphenylalanine were chlorinated to five different chlorine-to-amino nitrogen (Cl/N) mole ratios and analyzed after 30 min by high performance liquid chromatography. At mole ratios of ≤ 1, N-chloroglycylphenylalanine (I) appeared to be the only major product. At a mole ratio ≤ 2, N, N-dichloroglycylphenylalanine (II) was the only product. Compound II decomposes in model solutions (t_1/2= 6.4 hr) at pH 7.0 to form a compound tentatively identified as an H-chloroaldimine (III). Compound III in turn decomposes (t_1/2= 36 hr) in model solutions at pH 7. o to (IV) . From ^{13 …}

Absolute-Convective Instabilities And Their Associated Wave Packets In A Compressible Reacting Mixing Layer, F. Q. Hu, T. L. Jackson, D. G. Lasseigne, C. E. Grosch

Mathematics & Statistics Faculty Publications

In this paper the transition from convective to absolute instability in a reacting compressible mixing layer with finite rate chemistry is examined. The reaction is assumed to be one step, irreversible, and of Arrhenius type. It is shown that absolute instability can exist for moderate heat release without backflow. The effects of the temperature ratio, heat release parameter, Zeldovich number, equivalence ratio, direction of propagation of the disturbances, and the Mach number on the transition value of the velocity ratio are given. The present results are compared to those obtained from the flame sheet model for the temperature using the …

Interferences Of N-Chloroorganic Compounds In Free Chlorine Determination, Sushma H. Gandhi

Chemistry & Biochemistry Theses & Dissertations

Various N-chlorinated organic compounds give positive responses to the analytical methods used to determine free chlorine. The present work quantifies interferences due to N-chloroisoleucine, N-chloropiperidine and N-chloro-2-methylbutyraldiminein the free chlorine determination by amperometry. These N-chloroorganic compounds were also studied for the recovery in response by the indicator electrode in amperometric titrimetry. The total chlorine content of the chloroaldimines derived from the chlorination of the amino acids, alanine, glutamic acid, glycine, isoleucine, leucine, phenylalanine, serine, valine, and those of dipeptides, alanylvaline and glycylleucine, was determined by amperometry and DPD-FAS titrimetry. The two methods were compared and evaluated with respect to recovery …

Investigation Of Alignment Dynamics In Mg-Ne And Mg-Ar Two-Photon Fractional Collisions, David Allen Olsgaard

Physics Theses & Dissertations

A new technique is used to observe the dynamics of electronic alignment in a dissociating collision complex. The technique requires the absorption of two optical photons during a single binary collision. Two exciting light fields are tuned into the wings of the 3s¹s₀-3p₁ and 3p¹p₁-5s¹s₀ resonances of Mg where strong collisions with rare gas atoms induce transitions between corresponding molecular states. The alignment produced in the intermediate state by the first excitation is probed by the second laser as a function of relative linear laser polarization and laser …

Biodegradation Of Crude Oil By Marine Higher Fungi, Brian J. Dyer

Biological Sciences Theses & Dissertations

Four experiments were performed to determine the ability of marine higher fungi to grow in and degrade crude oil. Eight species, previously determined to be hydrocarbonoclastic, were grown in artificial sea water medium (ASM) and southern Louisiana crude oil. The dry mycelial weights were measured and consumption of crude oil was measured gravimetrically. The two species with the best growth, Corollospora maritima and Zalerion maritimum, were grown in ASM containing crude oil spiked with three known hydrocarbons. To this was added glucose (0.15%) and incubated 49 days to test for possible cometabolism of hydrocarbons. Hydrocarbons remaining in the growth …

Thermal Characterization Of Carbon Monoxide Oxidation Catalysts Using Thermogravimetric Analysts And Differential Scanning Calorimetry, Rene A. Bartgis

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin (IV) oxide supports, with and without silica gel, as well as catalysts composed of gold on manganese oxide, have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A thermogravimetric method and a differential scanning calorimetric method have been developed for the thermal characterization of these catalysts. The mass loss data and the enthalpy changes determined as the catalysts lost water were then related to existing activity data for these catalysts. No relationship was found between the thermal data and the …