Chemistry Commons^™

Measurement, Characterization, And Source Apportionment Of The Major Chemical Components Of Fine Particulate Material, Including Semi-Volatile Species, Brett D. Grover

Theses and Dissertations

The promulgation of revised standards for atmospheric fine particles (PM2.5) by the US EPA has sparked renewed interest in the ability to accurately measure and characterize suspended atmospheric particulate matter. Semi-volatile material (SVM), consisting of ammonium nitrate and semi-volatile organic material (SVOM), is not accurately measured by EPA accepted methods such as the Federal reference method (FRM) or Tapered Element Oscillating Microbalance (TEOM). However, SVM is often a major fraction of urban aerosols. Recent advances in atmospheric sampling instrumentation allowed for the semi-continuous characterization of urban PM2.5, including SVM. The Filter Dynamic Measurement System (FDMS) was shown to measure total …

Characterization, Functionalization And Applications Of Alkyl Monolayers On Silicon Surfaces, Guilin Jiang

Theses and Dissertations

Investigations were performed on the stability, mechanism of formation and an application of alkyl monolayers chemomechanically prepared on silicon surfaces. A new method of surface modification, laser-activation modification of surfaces (LAMS), and multivariate analyses of time-of-flight secondary ion mass spectrometry (ToF-SIMS) images of LAMS spots were also reported. X-ray photoelectron spectroscopy (XPS) and other data show that alkyl monolayers prepared by scribing silicon under 1-iodoalkanes and 1-alkenes were stable over extended periods of time to air, water, a boiling acid and Al Ka X-rays. The stability is attributed to direct Si-C bonding in the monolayers. The observation that the oxygen …

Quantitative Model For The Prediction Of Hydrodynamic Size Of Nonionic Reverse Micelles, Melissa A. Michaels

Theses and Dissertations

The sizes of nonionic reverse micelles were investigated as a function of the molecular structure of the surfactant, the type of oil, the total concentration of surfactant [NP], the ratio of NP4 to total surfactant (r), the water to surfactant molar ratio (ω), temperature, salt concentration, and polar phase. The basis of our investigation was nonylphenol polyethoxylates - NP4 and NP7. Micelle sizes were determined using dynamic light scattering (DLS). A central composite experimental design was used to quantitatively model reverse micelle size as a function of ω, [NP], and r. The model has demonstrated the capability of predicting the …

Enhancing The Third-Order Nonlinear Optical Properties Of Porphyrins And Molecular Wires, Jonathan L. Humphrey

Theses and Dissertations

The third-order nonlinear optical (NLO) properties of indium tin oxide (ITO) thin films, Fe3+, Mn3+, Co2+ 5,10,15,20-tetrakis-4hydroxytetraphenyl)porphyrin (TPP) films, and a series of ethynyl-linked azobenzene oligomers were investigated using degenerate four wave mixing (DFWM) with 100 fs laser pulses. To measure the NLO of ITO thin films, A DFWM method for measuring thin films on thick substrates was refined for the characterization of films less than 100 nm thick and applied to ITO films ~25 nm thick. It was found that the third-order nonlinear susceptibility of ITO, χ(3)ITO, is purely electronic at 900 - 1300 nm (11000 - 7700 cm-1) …

Chemometric Analysis Of Multivariate Liquid Chromatography Data: Applications In Pharmacokinetics, Metabolomics, And Toxicology, Sarah Elizabeth Graham Porter

Theses and Dissertations

In the first part of this work, LC-MS data were used to calculate the in-vitro intrinsic clearances (CLint) for the metabolism of p-methoxyrnethamphetamine (PMMA) and fluoxetine by the CYP2D6 enzyme using a steady-state (SS) approach and a new general enzyme (GE) screening method. For PMMA, the SS experiment resulted in a CLint of 2.7 ± 0.2 µL pmol 2D6-1min-1 and the GE experiment resulted in a CLint of 3.0 ± 0.6 µL pmol 2D6-1min-1. For fluoxetine, the SS experiment resulted in a CLint of 0.33 ± 0.17 µL pmol 2D6-1min-1 and the GE experiment resulted in a CLint of 0.188 …

Photochemical Applications To The Study Of Complexity Phospholipid Bilayer Environments, Christopher John Wohl Jr.

Theses and Dissertations

The physical and biophysical properties of a biological membrane model, phosphatidylcholine bilayers, were investigated using novel spiropyran/merocyanine molecular probes. The femtosecond to second dynamics of this system's photochemistry enabled bilayer viscosity and free volume to be studied over a broad time scale. Spiropyrans/merocyanines with different polarity were synthesized by changing the substitution of the indole moiety enabling determination of the trans-membrane properties of the bilayer. In addition, transient grating spectroscopy was used to study thermal energy transfer in phospholipid bilayers on a picosecond time scale.Femtosecond transient absorption spectroscopy was used to study the photo-induced spiropyran ring-opening and isomerization reactions that …

A Prelude To A Third Dimension Of The Periodic Table: Superatoms Of Aluminum Iodide Clusters, Naiche Owen Jones

Theses and Dissertations

Calculations have been carried out to investigate the stability and electronic structure of aluminum iodide clusters using first principles gradient-corrected density functional theory. Analysis of A113Ix-, A114Ix-, and A17I- clusters reveals that their stability is governed by the geometrically unperturbed A113-, A1142+, and A17+ units, respectively, that are demonstrated to constitute the compact cores of the clusters upon significant iodine content. The compact, icosahedral A113, icosahedral-like A1 14, and capped square bi-pyramid A17 superatom structures of the stable aluminum cores have an analogous electronic configuration to that of halogen, alkaline-earth, and alkaline atoms, respectively. Novel chemistry is demonstrated in superatoms, …

Synthesis Of Novel Antimycobacterials And A Fluorescent Sensor For Simple Carbohydrates, Brian Thomas Walker

Theses and Dissertations

Cell surface carbohydrates play an important role in a wide variety of biological processes such as inflammation, tumor metastasis, and viral and bacterial infection. The goal of our research has been two-fold. The first objective was the synthesis of antimycobacterial compounds. A mannose containing tetrasaccharide from the mannan core of lipoarabinomannan (LAM) of Mycobacterium tuberculosis has been synthesized using α-D-methylmannopyranoside as starting material and Koeings-Knorr reactions to couple saccharides. The synthesis was completed in nine steps and in 14% total yield. This compound should be useful in competitive inhibition studies with macrophages or as an immunological marker. We have successfully …

The Role Of Phosducin-Like Protein And The Cytosolic Chaperonin Cct In G Beta Gamma Dimer Assembly, Ting Hu

Theses and Dissertations

Phosducin-like protein (PhLP), a G protein beta gamma subunit dimer binder and G protein signaling regulator, was suggested to regulate the activity of cytosolic chaperonin CCT by their high affinity interaction. In the present study, the three-dimensional structure of PhLP:CCT complex has been solved by cryoelectron microscopy. PhLP was found to bind only one of the chaperonin rings with both N- and C-terminal domains. It spans the central folding cavity of CCT and interacts with two opposite sides of the top apical region, inducing the constraining of the entry of the folding cavity. These findings support a putative role of …

Palladium-Imidazolium Carbene Catalyzed Heck Coupling Reactions And Synthesis Of A Novel Class Of Fluoroanthracenylmethyl Ptc Catalysts, Jiuqing Zhang

Theses and Dissertations

Palladium catalyzed Heck coupling with aryl and alkenyl halides has become a powerful means of carbon-carbon bond formation. This standard synthetic method has been developed to a high level of utility using various catalysts, conditions and substrates. Yet significant drawbacks remain, including poor reactivity, the need for high temperatures and base, limited substrate generality, and selectivity. Mixed products often suffer from olefin migration following insertion. N-Heterocyclic carbenes (NHC) have proven to be electron-rich donors which provide higher stability and reactivity than phosphines. In a previous paper reported by our research group the imidazolium-palladium carbene has proven to be highly efficient …

Total Syntheses Of (+)-Geldanamycin, (-)-Ragaglitazar, And (+)-Kurasoin A And Phase-Transfer-Catalyzed Asymmetric Alkylation, Erik J. Hicken

Theses and Dissertations

Geldanamycin possesses various biological activities as seen in the NCI 60 cell line panel (13 nM avg., 70 nM SKBr-3 cells). The predominant mode of action providing these unique results arises from the ability of geldanamycin (GA) to bind to the chaperone heat shock protein 90 (Hsp90). Despite its complicated functionality, the first total synthesis of GA was accomplished, which included two new reactions developed specifically to address the stereochemical features. The final step in the synthesis of GA was a demethylation-oxidation sequence to generate the desired para-quinone. This step could only be accomplished with HNO3/AcOH, producing GA in …

Specific Heat And Thermodynamic Properties Of Metallic Systems: Instrumentation And Analysis, Brian E. Lang

Theses and Dissertations

A small-scale adiabatic calorimeter has been constructed as part of a larger project to study nano-particles and to facilitate specific heat measurements on samples where it is difficult to obtain enough material to run on the current large-scale adiabatic apparatus. This calorimeter is designed to measure sample sizes of less than 0.8 cc over a temperature range from 13 K to 350 K. Specific heat results on copper, sapphire, and benzoic acid show the accuracy of the measurements to be better than ±0.4% for temperatures higher than 50 K. The reproducibility of these measurements is generally better than ±0.25%. Experimental …

Polymer Microchips For Capillary Electrophoresis And Electric Field Gradient Focusing Of Biomolecules, Ryan Thomas Kelly

Theses and Dissertations

Polymeric materials have seen increasing use as microfluidic device substrates due to their low cost and the simplicity of templated fabrication procedures. I showed that poly(methyl methacrylate) (PMMA) microdevices could be enclosed in a boiling water bath, which allowed the seal to form more quickly than in conventional approaches, and enabled microchannels to remain hydrated throughout the bonding process. Microchip capillary electrophoresis (µ-CE) devices were fabricated using water-based enclosure, and a mixture of fluorescently labeled amino acids was separated in 30 s in these microchips. To create more robust capillary electrophoresis (CE) microdevices with improved separation performance, phase-changing sacrificial materials …

Structure Elucidation Of Bioactive Compounds Isolated From Endophytes Of Alstonia Scholaris And Acmena Graveolens, Nicholas James Hundley

Theses and Dissertations

Alstonia scholaris is an evergreen tree native to Southeast Asia and Australia. It is commonly used as a medicinal plant throughout these regions. In the present study, an endophyte of the genus Xylaria was isolated from a stem of Alstonia scholaris, its mycelia and exudate extracted, and the extract assayed for growth inhibition of HeLa cancer cells in vitro. Several known compounds were isolated and identified based on NMR, infrared, and mass spectral data. The compounds identified are 19,20-epoxycytochalasin C; 19,20epoxycytochalasin D; and xylobovide. Two other compounds, fusaric acid and dehydrofusaric acid, were discovered in an endophyte of the Hypocreales …

An Acyl Radical Cascade Model For The Total Synthesis Of Lyconadin A, Seth W. Grant

Theses and Dissertations

Lyconadin A (1) is a structurally unique Lycopodium alkaloid with antitumor properties, isolated from the club moss Lycopodium complanatum. We are developing a synthetic route to 1 based on a novel 7-exo-trig/6-exo-trig acyl radical cascade cyclization. The synthesis of model acyl radical cascade precursor 23 will be presented. Key features of this synthesis include the suppression of competing elimination during the alkylation of a hindered phenethyl bromide and the use of a lactone as a precursor to a compound bearing two differentially protected primary alcohols. An account of our studies on the model acyl radical cascade cyclization (23 to 24 …

Effect Of Melatonin And Dopamine In Site Specific Phosphorylation Of Phosducin In Intact Retina, Arinzechukwu Okere Nkemdirim

Theses and Dissertations

Phosducin (Pdc) is a 28 kDa binding partner for the G protein beta gamma subunit dimer (G-beta-gamma) found abundantly in the photoreceptor cells of the retina and pineal gland. In the retina, light-dependent changes in cAMP and Ca2+ control the phosphorylation of Pdc at serine 73 and 54, respectively, which in turn controls the binding of Pdc to G protein beta gamma subunit dimer . G protein beta gamma subunit dimer binding has been proposed to facilitate light-driven transport of G protein beta gamma subunit dimer from the site of phototransduction in the outer segment of the photoreceptor cell to …

Angiotensin Ii-Mediated Regulation Of The Human Angiotensin Ii Type 1 Receptor Gene, Xylophone Vijai Aasee Victor

Theses and Dissertations

The physiological responses of angiotensin II (Ang II) are mediated across the cell membrane through the angiotensin II type 1 receptor (AT1R), a heptahelical membrane protein coupled to trimeric G-proteins on the cytosolic side. AT1R on binding its ligand, Ang II, leads to downregulation of cell-surface receptor and also its mRNA. We have investigated whether the 3'- and 5'-untranslated regions of the human AT1R mRNA mediate the degradation of hAT1R mRNA by post-transcriptional mechanisms in human adrenocortical carcinoma cell line (H295R cells). Protein kinase C (PKC) activator, phorbol-12-myristate-13-acetate (PMA), showed that the downregulation of hAT1R mRNA is mediated by the …

Development Of A Model For The Kinetics And Mechanism Of Nitrogenase, Phillip E. Wilson

Theses and Dissertations

Nitrogenase has a central role in the global nitrogen cycle as the enzyme that catalyzes the reduction of atmospheric N2 to NH3. Fixed nitrogen is generally limiting in the environment and in agriculture, so nitrogenase has received much attention as an alternative to nitrogen fertilizers. Characterizing the mechanism of nitrogenase is the goal of this work. The molybdenum nitrogenase enzyme system is comprised of the MoFe protein and the Fe protein. Interactions between these proteins and nucleotides are crucial to catalysis. An important approach to characterize these interactions is to correlate the kinetics of nitrogenase catalysis to a mechanism based …

Alterations In Uterine And Placental Sodium Pump Abundance May Contribute To The Onset Of Mouse Labor, Carlos Jacob Vance

Theses and Dissertations

Objective: Reductions in sodium pump (SP) abundance can give rise to increases in contractile force in uterine and vascular smooth muscle as well as an increased secretion in secretory cells, including potentially those of the placenta. To determine whether the mouse might serve as a model for human pregnancy in terms of the SP and to determine whether changes in SP abundance anticipate or follow labor, we studied pregnant mice over the final trimester of their pregnancy.

Study Design: C57Bl6 dams (n=46) were bred and studied during their pregnancy. Animals (n=4) were sacrificed at specific gestational time points. Other mice …

Ion Transmission In The First Vacuum Stage Of An Inductively Coupled Plasma Mass Spectrometer, Jeffrey Harris Macedone

Theses and Dissertations

The inductively coupled plasma mass spectrometer (ICP-MS) is the instrument of choice for trace and ultra-trace elemental analysis. However, the ICP-MS suffers from matrix effects. Matrix effects occur when instrument response varies as the composition of the sample matrix is changed. Matrix effects, or non-spectroscopic interferences, limit the accuracy of routine analysis. Identification of the sources of matrix effects provide a basis for reducing or eliminating them. As inaccuracies in the ICP-MS are more severe than those in the ICP atomic emission spectrometer, the problem may be due, at least in part, to the vacuum interface used to couple the …

An Investigation Into Palladium-Catalyzed Reduction Of Perchlorate In Water, Eric G. Barney

Theses and Dissertations

In this study, application of a catalytic reactor to facilitate chemical reduction of perchlorate was investigated. Palladium-coated pellets were used as the catalyst, and formic acid was used as the reductant. Reactor performance was evaluated under a variety of operating conditions (influent pH, reductant concentration, residence time). Very little perchlorate reduction was observed under any operating condition. At best, approximately 8% perchlorate reduction was observed. This small reduction efficiency is clearly not sufficient for environmental treatment applications. Perchlorate strongly adsorbed to the catalyst at low pH (3 - 3.3). At higher pH (4 - 10), little adsorption was observed. This …

Optimal Sampling Of A Chemical Hazard Area, Jennifer R. Plourde

Theses and Dissertations

This thesis proposes a methodology for optimally sampling a chemical hazard area subsequent to a chemical weapons attack. The objective is to identify the maximum number of areas that no longer require protective gear for safe operations. We model the area as an undirected graph and employ network analysis techniques to provide a methodological framework for identifying an optimal sampling sequence within a fixed time limit. We propose four models that characterize the secondary vapor concentrations: i) static and deterministic, ii) static and stochastic, iii) dynamic and deterministic, and iv) dynamic and stochastic. Comparisons of the static cases and their …

Non-Adiabatic Energy Surfaces Of The B+H2 Systems, Lachlan T. Belcher

Theses and Dissertations

In order to solve the dynamics of a system, the kinetic energy operator of the Hamiltonian must be diagonalized. Diagonalization requires rotation of the system into a non-adiabatic representation. This rotation is a coupling angle determined by the derivative coupling terms. Derivative coupling terms are calculated using Columbus and Brooklyn, software packages. Separation of internal dynamics characterized by Jacobi coordinates, and external dynamics characterized by a set of Euler angles and the center of mass position, requires a transformation from Cartesian coordinates to Jacobi coordinates required for subsequent dynamical calculations. Previous attempts to solve for non-adiabatic energy surfaces in this …

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 …

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 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) …