Masters Theses

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Browsing Masters Theses by Department "Chemistry"
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    A COBALT OXIDE CARBON NANOTUBE COMPOSITE FOR DOPAMINE DETECTION
    (Middle Tennessee State University, 2018) Kader, Mohammad Salauddin ; Chemistry
    Dopamine (DA) is a catecholamine and performs as a neurotransmitter in the human body. Dopamine plays an important role in the process of many biological networks. Research showed that unusual amounts of DA can cause several neurological diseases such as Parkinson’s disease, schizophrenia, and other mental disorder. Cobalt oxide (CoO) particles were tethered to carboxylic-acid-functionalized multi-walled carbon nanotubes (COOH-MWNT) using sonication. The resulting composite (CoO/COOH-MWNT) was applied to glassy carbon electrodes for detecting DA within the 0.5-5 µM range and 10-100 µM range. Current versus concentration was measured using cyclic voltammetry. Different parameters such as loading, pH and sonication times (0 to 60 min) were varied to optimize current response. Good selectivity was found against uric acid and ascorbic acid. The (CoO/COOH-MWNT) composite was characterized by attenuated total reflection infrared spectroscopy (ATR-IR), Raman spectroscopy, Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).
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    ADDITIONAL CHARACTERIZATION OF ADENOSINE NUCLEOSIDASE FROM ALASKA PEA SEEDS
    (Middle Tennessee State University, 2017-04-17) Alruwaili, Awatif Hanif ; Kline, Paul ; Burden, Donald ; Miller, Justin ; Chemistry
    Adenosine nucleosidase was purified from Alaska pea seeds six days after germination. A 3-fold purification has been reached with a 0.56 % recovery. The purification scheme involved ammonium sulfate precipitation between 30% and 60% saturation, followed by ion exchange chromatography on a DEAE column. A final chromatography step used a hydroxyapatite column. The subunit molecular weight of adenosine nucleosidase was determined by SDS-PAGE to be 26.7 kD. The Michaelis constant, Km, and the maximum velocity, V max, for inosine were determined to be 377.7 141.7 M and 0.00078 0.000106 M/min respectively.
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    ADDITIONAL CHARACTERIZATION OF ADENOSINE NUCLEOSIDASE FROM ALASKA PEA SEEDS
    (Middle Tennessee State University, 2017-04-17) Alruwaili, Awatif Hanif ; Kline, Paul ; Burden, Donald ; Miller, Justin ; Chemistry
    Adenosine nucleosidase was purified from Alaska pea seeds six days after germination. A 3-fold purification has been reached with a 0.56 % recovery. The purification scheme involved ammonium sulfate precipitation between 30% and 60% saturation, followed by ion exchange chromatography on a DEAE column. A final chromatography step used a hydroxyapatite column. The subunit molecular weight of adenosine nucleosidase was determined by SDS-PAGE to be 26.7 kD. The Michaelis constant, Km, and the maximum velocity, V max, for inosine were determined to be 377.7 141.7 M and 0.00078 0.000106 M/min respectively.
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    ADDITIONAL CHARACTERIZATION OF ADENOSINE NUCLEOSIDASE FROM ALASKA PEA SEEDS
    (Middle Tennessee State University, 2017-04-17) Alruwaili, Awatif Hanif ; Kline, Paul ; Burden, Donald ; Miller, Justin ; Chemistry
    Adenosine nucleosidase was purified from Alaska pea seeds six days after germination. A 3-fold purification has been reached with a 0.56 % recovery. The purification scheme involved ammonium sulfate precipitation between 30% and 60% saturation, followed by ion exchange chromatography on a DEAE column. A final chromatography step used a hydroxyapatite column. The subunit molecular weight of adenosine nucleosidase was determined by SDS-PAGE to be 26.7 kD. The Michaelis constant, Km, and the maximum velocity, V max, for inosine were determined to be 377.7 141.7 M and 0.00078 0.000106 M/min respectively.
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    Adenosine Deaminating/ Hydrolyzing Enzymes from Alaska pea seeds (Pisum sativum)
    (Middle Tennessee State University, 2017-07-17) Thicklin, Lendsey Breanna ; Kline, Paul ; Burden, Andrew ; Miller, Justin ; Chemistry
    Nucleoside deaminases and nucleoside hydrolases are essential within the purine salvage pathway to recycle purine bases to promote cellular functions such as DNA synthesis, cytokinin metabolism, and more. Plants such as the Alaska pea (Pisum sativum) rely heavily on these enzymes, yet the enzymatic and structural characterizations of these proteins are limited. A 67 kilodalton (kDa) protein was isolated from germinated Alaska pea seeds with a 103 fold purification and 2.8 % recovery. The analysis of the enzymatic activity of this protein revealed adenosine is metabolized to inosine, adenine, and hypoxanthine suggesting a bifunctional enzyme combining nucleosidase and deaminase activities. This dimeric protein had an inosine Michaelis constant of 268 μM 78 μM. The optimum pH for enzymatic activity was determined to be pH 6. Research involving plant based nucleoside deaminases and nucleoside hydrolases can provide an origin of reference in the development of compounds that can be used as herbicides.
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    Adenosine Deaminating/ Hydrolyzing Enzymes from Alaska pea seeds (Pisum sativum)
    (Middle Tennessee State University, 2017-07-17) Thicklin, Lendsey Breanna ; Kline, Paul ; Burden, Andrew ; Miller, Justin ; Chemistry
    Nucleoside deaminases and nucleoside hydrolases are essential within the purine salvage pathway to recycle purine bases to promote cellular functions such as DNA synthesis, cytokinin metabolism, and more. Plants such as the Alaska pea (Pisum sativum) rely heavily on these enzymes, yet the enzymatic and structural characterizations of these proteins are limited. A 67 kilodalton (kDa) protein was isolated from germinated Alaska pea seeds with a 103 fold purification and 2.8 % recovery. The analysis of the enzymatic activity of this protein revealed adenosine is metabolized to inosine, adenine, and hypoxanthine suggesting a bifunctional enzyme combining nucleosidase and deaminase activities. This dimeric protein had an inosine Michaelis constant of 268 μM 78 μM. The optimum pH for enzymatic activity was determined to be pH 6. Research involving plant based nucleoside deaminases and nucleoside hydrolases can provide an origin of reference in the development of compounds that can be used as herbicides.
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    ALKYLATION OF 2,4,5-TRIIODOIMIDAZOLE MOLECULES
    (Middle Tennessee State University, 2015-02-01) Griffiths, Elsbeth Ariel ; Handy, Scott ; Bicker, Kevin ; Dunlap, Norma ; Van Patten, Greg ; Chemistry
    Alkylated 2,4,5,-triiodoimidazole molecules could be of interesting in a variety of situations, including pharmaceuticals and complex molecule synthesis. The most obvious route to such compounds is the alkylation of 2,4,5-triiodoimidazoles with alkyl halides. Interestingly, little has been reported in this area. In conjunction with our interest in highly iodinated compounds, we undertook a study of this alkylation. Reactions of various types of alkyl halides were studied. In most cases, reactions were performed at room temperature in dimethylformamide (DMF) with potassium carbonate, although some less reactive alkyl halides required heating. The future goal is to use these alkylated triiodoimidazoles in energetic and biological applications. In an attempt to synthesize energetic binders to replace current isocyanate-based binders, my target begins with 2,4,5-triiodoimidazole which is alkylated on one of the nitrogens using allyl bromide. The tethered alkene can be later used to crosslink the final polymer, replacing the isocyanate crosslinker. These energetic binders make transporting volatile materials safer. This stabilization is provided by a surrounding structure of the binder molecule, that upon crosslinking will combine to become larger units. The resulting matrix makes the explosive more thermodynamically stable by being able to absorb more shock.
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    AMINO ACID SEQUENCE OF NUCLEOSIDE HYDROLASES FROM PLANTS
    (Middle Tennessee State University, 2014-06-24) Ogorodnik, Kateryna V. ; Kline, Paul ; Burden, Donald ; Farone, Mary ; Chemistry
    Nucleoside hydrolases are key enzymes of the purine salvage pathways of various bacteria, yeast, parasitic protozoa, insects, fish, and plants. While the structures of nucleoside hydrolases from parasitic protozoans have been extensively studied, almost no structural information beyond subunit molecular weights is available for nucleoside hydrolases from plants.
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    Analysis of Static Correlation using Atomic Populations of Effectively Localized Electrons (APELE)
    (Middle Tennessee State University, 2019) Lewis, Conrad Dane ; Chemistry
    Static or nondynamic correlation is an effect where the single-reference approximation fails to adequately describe a molecular system.1 Systems dominated by nondynamic correlation require multi-reference (MR) methods, such as full-configuration interaction (FCI) or multi-configurational self-consistent field theory (MCSCF), which are impractical for most systems due to their high computational complexity. Most functionals in Density Functional Theory (DFT) fail to describe such systems due to the ever-elusive exchange-correlation term (EXC).2,3 In order to avoid using MR methods a number of diagnostics have been proposed that allow the user to determine the quality of their single-reference solution.4{7 It has been show through preliminary tests that some of these diagnostics prove not to be size-extensive, while simultaneously being computationally complex themselves. Using the Kong-Proynov ‘16 / Becke ‘13 (KP16/B13) functional, atomic populations of effectively localized electrons (APELE) are generated and compared against current diagnostics to estimate nondynamic correlation.1,8 It is also shown that the APELE method is size-extensive and correlates well with wave-function based diagnostics.
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    ANALYSIS OF VOLATILE ORGANIC COMPOUNDS (VOCs) FROM HYDRAULIC FRACTURING FACILITIES IN KARNES COUNTY, TEXAS AND IDENTIFICATION OF VOCs IN SHELBY COUNTY, TENNESSEE
    (Middle Tennessee State University, 2017-11-12) Keith, Ki-In ; Chong, Ngee ; Burden, Donald ; Wang, Chengshan ; Chemistry
    Volatile organic compounds (VOCs) are emitted by several sources and have the ability to cause short and long-term adverse health effects. In Karnes County, Texas, a high activity of hydraulic fracturing on the Eagle Ford Shale is the major source of VOC emissions. In Shelby County, Tennessee, automobile exhaust, household products, and industrial facilities are the main sources of VOC emissions. Air samples were collected in Karnes County and Shelby County and analyzed using gas chromatography-mass spectrometry (GC-MS) with a cryogenic preconcentrator outfitted with a glass bead trap and a Tenax trap. The EPA TO-15 method was applied to analyze TO-15 compounds in Karnes County and non-TO-15 compounds in Shelby County. Samples collected in Karnes County were also analyzed using Fourier transform infrared spectroscopy (FT-IR) with a 10-meter gas cell to detect low molecular weight compounds. Benzene, toluene, ethylbenzene, xylene, and methane were commonly detected compounds near oil and gas facilities in Karnes County, Texas. In Shelby County, Tennessee, acetonitrile, cyclohexene, and cyclohexanone were frequently detected at relatively high concentrations.
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    ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN AIR SAMPLES BY INFRARED SPECTROSCOPIC ANALYSIS OF SORBENT TUBE SAMPLES
    (Middle Tennessee State University, 2013-12-03) Lampert, Craig Allen ; Chong, Ngee ; WANG, CHENGSHAN ; DING, KEYING ; Chemistry
    Volatile organic compounds (VOCs) have typically been analyzed using gas chromatography/mass spectrometry (GC/MS), which offers low detection limits and high specificity in identifying compound structures. FTIR has the advantage of high speed, internally calibrated, and sensitive for analyte detection down to parts-per-billion levels. FTIR can also analyze multiple components simultaneously by spectral deconvolution. Preconcentration with a sorbent tube is prescribed by the EPA method and offers a better option for environmental samples because the concentrations of analytes tend to be significantly lower in the ambient air than industrial emission sources. The research goal of this project is to develop a method for analyzing low molecular weight VOCs with the use of sorbent tube technology in conjunction with a Varian 7000 FTIR. For future work, the technology developed through this research can be combined with remotely controlled sampling modes to facilitate airborne sampling at high altitudes or near industrial emission stacks.
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    CHARACTERIZATION OF ADENOSINE NUCLEOSIDASE FROM ALASKA PEA SEEDS
    (Middle Tennessee State University, 2015-06-22) Shamsuddin, Abdullah Khairuddin ; kline, paul ; burden, donald ; bicker, kevin ; Chemistry
    Adenosine nucleosidase was purified from Alaska pea seeds five days after germination. A 4-fold purification has been reached with a 1.3 % recovery. The subunit molecular weight of adenosine nucleosidase was determined by mass spectrometry to be 26,103 daltons. The number of subunits was 1. The Michaelis constant, Km, and the maximum velocity, V max, for adenosine were determined to be 137 48 M, and 0.34 0.02 M/min respectively.
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    CHARACTERIZATION OF ADENOSINE NUCLEOSIDASE FROM SOYBEAN SEEDS (Glycine max L.)
    (Middle Tennessee State University, 2013-11-13) JarAllah, Lola ; Kline, Dr. Paul ; Chemistry
    The nucleoside salvage pathway plays a key role in the growth and development of plants. The activities of several enzymes of the nucleoside salvage pathway were determined in germinated soybean seeds. One of these enzymes, adenosine nucleosidase, was purified 5 days after germination period. The purification scheme consisted of ammonium sulfate precipitation, ion exchange chromatography, size exclusion, and aminohexyl chromatography. The enzyme was then characterized with regard to its isoelectric point and subunit molecular weight. Adenosine nucleosidase from soybean seeds was determined to most likely be a multimeric enzyme with a subunit molecular weight of approximately 18,000 Da based on SDS-PAGE.
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    Chemistry Teachers’ Journey through Modeling Instruction: From Workshop to Classroom
    (Middle Tennessee State University, 2016-03-25) Frick, Tasha M. ; Phelps, Amy ; Sanger, Michael ; Handy, Scott ; Chemistry
    This presentation will feature case study research that describes the difficulties that four high school chemistry teachers faced while implementing Modeling Instruction into their classrooms. Modeling Instruction is characterized by the development of understanding through cooperative inquiry and collective discourse on a path from concrete to abstract. The complications in transforming a classroom from traditional teacher centered methods to one which focuses on the use of student-centered Modeling Instruction will be thoroughly investigated through the stories of each of the participants. The study begins with observations of the teachers prior to the introduction of Modeling Instruction and follows them into the professional development in the summer, the initial use in the fall term, a follow-up workshop, and finally back into the classrooms. The enlightening findings highlight the difficulties teachers had in aligning the standards, and developing a scope and sequence, as well as reconciling their beliefs about student ability.
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    Comparison of Chlorine Dioxide and Ozone as Oxidants for the Degradation of Volatile Organic Compounds
    (Middle Tennessee State University, 2018) Hoque, Md Abdul ; Chemistry
    The presence of hazardous volatile organic compounds (VOCs) in both indoor and outdoor air is a grave issue in environmental pollution. The exposure of these compounds may cause chronic disease or adverse effects in humans. The major sources of these toxic compounds are due to improper waste disposal by chemical manufacturers, the waste stream from food processing, industrial sources, and decay of living cells. Therefore, the reduction of VOCs by oxidative reactions is the primary goal of this thesis project. Both chlorine dioxide and ozone are used to evaluate the degradation characteristics of dimethyl trisulfide, isoprene, 1-bromopropane, 2,3-butanedione, and 1,1,2-trichloroethane. Gas chromatography coupled to mass spectroscopy (GC-MS) and Fourier Transform infrared spectrometry (FTIR) were used to characterize the gas phase reaction products of these compounds. The results show that dimethyl trisulfide and isoprene were substantially degraded into other by-products, including methane sulfonyl chloride and sulfur dioxide, during oxidation by chlorine dioxide and ozone, respectively. In contrast, 1-bromopropane, 2,3-butanedione and 1,1,2-trichloroethane have slow reaction kinetics and did not break down completely. Degradation of dimethyl trisulfide by chlorine dioxide and ozone follows the second-order kinetics with half-lives of 2.2 min and 24 min, respectively. On the other hand, isoprene follows the first order reaction kinetics with rate constants of 0.4051 min-1 and 0.02244 min-1 and half-lives of 1.73 min and 32 min for degradation using ozone and chlorine dioxide, respectively. The oxidative degradation of 1-bromopropane, dimethyl trisulfide, and 2,3-butanedione by chlorine dioxide was more efficient than their reactions with ozone. However, the degradation of isoprene and 1,1,2-trichloroethane showed a greater reactivity toward ozone compared to chlorine dioxide. Most of the reaction products of oxidative degradation such as acetone, ethanol, formic acid, and dimethyl ether are chemically benign. But there are also by-products such as methane sulfonyl chloride, sulfur dioxide, chloroform, and cyanogen bromide that require further toxicological study.
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    A Comparison Study between Coupled and Non-coupled Systems of Poly(3-hexylthiophene) and Fullerene-C60 for the Application of Organic Solar Cells
    (Middle Tennessee State University, 2014-03-28) King, Benjamin Lawrence ; Patterson, Dwight ; Friedli, Andrienne ; Ilsley, William ; Chemistry
    Organic solar cell technology has become one of the fastest growing areas of polymer science due to the world's need for clean, renewable energy. Some of the highest power efficiencies for organic solar cells have been observed in solar cells where a heterogeneous mixture of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) have been used as the active layer. A process called thermal annealing has been used to give high crystallinity for P3HT, improving light absorption and charge transport, but increasing segregation with the electron acceptor PCBM. In the study, the electron donor P3HT was coupled to fullerene-C60. A blend of P3HT and coupled product was compared to a completely non-coupled system to see if there was improvement in the overall efficiency of the organic solar cells. P3HT was synthesized and successfully coupled to fullerene-C60 based on analysis with GC/MS, HPLC, FTIR, and NMR spectroscopy. Synthesized P3HT was found to have only 79% regioregularity and average molecular weights under 3300 Da. The coupled materials were found to have a lower conjugation than the pure P3HT due to disruption to coplanarity by steric hindrance. Through analysis with DSC and TEM, it was discovered that the synthesized coupled material had a negative effect on the P3HT's ability to crystallize in comparison to pure P3HT and the P3HT/C60 blend. Based on power efficiency tests, fabricated solar cells containing the P3HT/coupled material blend were exponentially less efficient than the non-coupled blend of P3HT/C60.
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    Cu(I)-CATALYZED SINGLE STEP ONE-POT SYNTHESIS OF 1,4-DISUBSTITUTED TRIAZOLES USING DEEP EUTECTIC SOLVENT (DES)
    (Middle Tennessee State University, 2013-06-26) Kafle, Arjun ; Handy, Scott ; Dunlap, Norma ; Patterson, Dwight ; Chemistry
    The synthesis of different 1,4-disubstituted-1,2,3-triazoles were carried out in a eco-friendly, cheap and readily available deep eutectic solvent (DES) (1 : 2 molar mixture of choline chloride and glycerol) which involve reaction between alkyl halides or aryl halides, terminal alkynes and NaN3 in presence of Cu(I) catalyst at an ambient temperature giving moderate to high yield. The transformations involving alkyl halides and aryl halides as azide precursors were found to be less effective in DES (1 : 2 molar mixture of choline chloride and glycerol) because of its polar protic nature which decreases the nucleophilicity of nucleophiles via solvation. Interestingly, the use of an organic azide instead of azide precursor was found to give an excellent yield of the triazole products in DES. Aryl halide especially, bromobenzene and its derivative as aryl azide precursors are not generally effective, however this limitation can be overcome using N,N'-dimethylethylenediamine as a ligand for the transformation. High recyclability of the reaction medium was observed during the study. In addition, a drastic reduction in reaction time was observed for the reaction involving benzyl azide and phenylacetylene in the presence of excess sodium azide.
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    DEEP EUTECTIC SOLVENTS (DES) AS CATALYST AND SOLVENT FOR KNOEVENAGEL CONDENSATION REACTIONS
    (Middle Tennessee State University, 2015-11-10) Almuzaini, Hanan ; Handy, Scott ; Ding, Keying ; Bicker, Kevin ; Chemistry
    ABSTRACT
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    DEGRADATION OF PENTOBARBITAL IN VARIOUS SOIL TYPES BY SOLID PHASE EXTRACTION AND LIQUID CHROMATOGRAPHY / MASS SPECTROMETRY
    (Middle Tennessee State University, 2016-07-12) Saha, Anita ; Kline, Paul ; Burden, Donald ; Farone, Mary ; Chemistry
    Pentobarbital is a leading drug for euthanizing large farm animals [Wolfgang et al., 2009]. However, pentobarbital tends to leach into the surrounding soil and become a source of contamination once these euthanized animals are buried. This research was conducted to determine the breakdown rate and extraction efficiency of pentobarbital adsorbed in different types of soil. Additional studies include examining a microbe strain possessing an enzyme capable of breaking down pentobarbital into its metabolites that has leached into the soil.
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    Dendronic Surfaces for the Detection of Explosive Vapors
    (Middle Tennessee State University, 2013-11-18) Kiri, Jabe G. ; Friedli, Dr.Andrienne ; Patterson, Dr. Dwight ; Chusuei, Dr. Charles ; Chemistry
    ABSTRACT