Organic Chemistry Commons^™

The Development Of Novel Rhenium- And Copper-Based Molecular Catalysts For Applications In Energy Conversion Chemistry, Joseph Michael Lee

Electronic Theses and Dissertations

Since the Industrial Revolution, the consumption of fossil fuels has increased dramatically worldwide. The combustion of fossil fuels leads to the generation of carbon dioxide (CO2) emissions. CO2 is a greenhouse gas, but also a C1 feedstock that could be utilized for the generation of renewable fuels and commodity chemicals. However, CO2 is chemically inert and typically demands strong chemical reductants or very negative potentials before it undergoes conversion into reduced carbon products. The desire to carry out CO2 conversion in the presence of water presents a significant challenge, as protons may be reduced to hydrogen gas rather than facilitating …

Design, Synthesis And Biological Screening Of Novel Cucs-Inspired Estrone Analogs Towards Treatment Of Pancreatic Adenocarcinoma, Khaled Alseud

Electronic Theses and Dissertations

Pancreatic cancer is currently the fourth most deadly type of cancer globally. It is expected to become the second by 2030, due to its poor prognosis and its resistance to the current standard treatment, Gemcitabine. Moreover, the survival rate after treatment is low compared to other cancer types, which suggests an urgent need for new potent and safe treatment agents. Recently, the triterpenoid, cucurbitacin, has shown promising antiproliferative activity against human pancreatic cancer cells in a dose- and timedependent manner, and decreased pancreatic tumor size in combination with gemcitabine in vivo. However, the use of cucurbitacin in clinical studies has …

Theranostics Based On Linear Dendritic Block Copolymers, Jon Williams

Electronic Theses and Dissertations

When combining imaging and therapeutic motifs, known as theranostics, amphiphilic diblock copolymers have a strong precedent of success. These polymers can self-assemble into a variety of morphologies that are known to concentrate in areas of inflammation such as tumors. However, prediction of size and morphology from polymer structure still remains an open challenge. Another system with promise of therapeutic efficacy are tree-like struc- tures known as dendrimers, such as poly(amidoamine) (PAMAM) and bis-(hydroxymethyl) propionic acid (bMPA), which can uptake drugs and dyes into their branches. It is desireable to combine these two motifs, using linear-dendritic block copolymers (LDBCs). These represent …

A Study To Regioselectively Access Fluorinated Triazoles And Isoxazoles, Sweta Adhikari

Electronic Theses and Dissertations

The objective of the thesis is to develop regioselective methods for mono-fluorination of disubstituted triazoles, both 1,4- and 1,5-regioisomer, and isoxazoles. These strategies focus on one-pot direct access to final mono-fluorinated triazoles and isoxazoles. Eventually, these fluorinated substrates will be screened against various biological targets. Similarly, the optimization study of a regioselective method to generate 5-fluoro-1,4-disubstituted triazole was conducted. This reaction also utilized 1,3-dipolar cycloaddition to synthesize fluorinated triazole. However, difluoroalkene was used as a synthetic equivalent of fluoroalkyne for this method. This resulted into the inversion of polarity affording a different regioisomer. Here, fluoronitroalkene was identified as a synthetic …

High Voltage Dye-Sensitized Solar Cells And Molecular Photocatalysis For Co2 Reduction, Roberta Ramalho Rodrigues

Electronic Theses and Dissertations

The development of high voltage solar cells is an attractive way to use sunlight to power electrocatalysts for water oxidation, electrocatalysts for CO2 reduction, and consumer electronics. Through careful molecular dye engineering and redox shuttle pairing, our group has reported a single-junction dye-sensitized solar cell (DSC) employing, for the first time, an iron redox mediator (Fe(bpy)33+/2+) in conjunction with a novel wide band gap dye (RR9). This system generates a high photovoltage of 1.42 V. To the best of our knowledge, this system is the highest photovoltage achieved by a single-junction DSC device without metal oxide doping. The RR9/Fe(bpy)33+/2+ redox …

Effects Of Halogen Bonding And Nir Tuning Of Dyes For Dye-Sensitized Solar Cells, Alexandra Baumann

Electronic Theses and Dissertations

With current energy demands being met through the utilization of energy sources such as petroleum, natural gas, and coal, the non-renewable nature of these sources will eventually approach depletion as world wide energy consumption increases yearly. As a result the need for a renewable energy alternative has become imminent. One appealing alternative that has gained considerable attention since its development due to a low cost and a high solar to electric conversion efficiency are dye-sensitized solar cells (DSCs). This dissertation describes efforts to design and synthesize improved organic dyes utilizing three analogous methods: first, through decreasing non-productive pathways such as …

Syntheses Of A Tin (Iv) Meso-Tetra(4-Pyridyl) Porphyrin Dichloride-Tetrachlorobis (Bipy)2 Ruthenium (Ii) Complex And Studies Of Photophysical Properties Of 1-Nitropyrene, Phillip Sharp

Electronic Theses and Dissertations

Development of a photosensitizer that can work in both aerobic and anaerobic environments would increase the robustness of the cancer treatment known as photodynamic therapy. The development of a photosensitizer was first attempted by synthesizing a tin (IV) meso-tetra (4-pyridyl) porphyrin dichloride-tetrachlorobis (Bipy)₂ ruthenium (II) complex. The synthesize of the tin porphyrin was done by a method from literature and had a percent error of 31.58 and 37.31 when comparing the theoretical percentages of carbon (55.39) and nitrogen (12.92) meaning that photosensitizer was not synthesized.

The second type of chromophore that was studied was 1-nitropyrene do determine if it …

Extraction And Purification Of Biologically Active Metabolites From Rhodococcus Sp. Mtm3w5.2, Mohrah Alenazi

Electronic Theses and Dissertations

Rhodococcushas been recognized as a potential antibiotic producer. Recently, a strain of Rhodococcussp. MTM3W5.2 was isolated from a soil sample collected in Morristown, Tennessee and was found to produce an inhibitory compound which is active against other related species. The purpose of this research is to extract, purify and analyze the active metabolite. The compound was extracted from RM broth cultures and purified by preliminary fractionation of crude extract through a Sephadex LH-20 column. Further purification was completed using semi-preparative reversed phase column chromatography. Final purification was obtained using multiple rounds of an analytical C18 HPLC column. Based …

Steric Effects Of Alkyl Ammonium Salts On The Combustion Of Exchanged Smectite Clays, Celeste A. Keith

Electronic Theses and Dissertations

Bomb calorimetry was explored as a new method for determining the cation exchange capacity (CEC) of clays. Smectite clays were modified with several alkyl ammonium salts varying in number of carbons and the spatial orientation of the carbons about the central nitrogen atom. The clays used, standards purchased from the Source Clay Repository, have CECs of 44, 80, 88, and 120 meq/100 g. Theoretically, the combustion energy of the organo-clays should be approximately the same for each salt. Any differences in energy would be due to the different structures of the salts and how they are oriented in the interlamellar …

Long-Range Electrostatic Interactions In Gold Catalysis And Fluorinating Reagent Development., Zhichao Lu

Electronic Theses and Dissertations

Our research focus is on applying two long range electrostatic interactions--coulombic interaction between ion pairs and hydrogen bonding—to two tasks: exploring counterion effects in gold catalysis and utilizing hydrogen bonding for fluorinating reagent development. Cationic gold catalysis is considered one of the most important breakthroughs in organic synthesis over the past two decades. A wealth of empirical information on counterion effects is now available regarding homogeneous gold catalysis. However, the rational understanding of the counterion effect on reactivity is still elusive. We proposed a widely applicable model to rationalize the kinetic effect in gold catalyzed reaction. We first solved the …

Synthesis And Characterization Of Biodiesel Fuels From Furfuryl Alcohol And Spent Coffee Grounds, Amanda Raley

Electronic Theses and Dissertations

ABSTRACT

Biodiesel can be synthesized using several different triacylglycerides, alcohols, and catalysts. In this study, fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs) were produced from their respective alcohols and coffee oil, using either a basic (K₂CO₃) catalyst or an acidic catalyst (H₂SO₄). Fatty acid furfuryl esters (FAFurEs) were produced using commercially-purchased cooking oils (canola, olive, corn, sunflower, and peanut) with furfuryl alcohol, a basic (K₂CO₃) catalyst, a co-solvent (THF), and an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate). All samples were produced using either conventional heating methods …

Brønsted Acid Catalyzed Carbon-Carbon Bond Forming Reactions, Jiangyue Miao

Electronic Theses and Dissertations

The focus of this research project lies in the development of new methodology in the field of Brønsted acid catalysis enabling rapid synthesis of medicinally relevant compounds. It is foreseen that small molecule sulfonic acids evaluated in this research project will unveil new asymmetric carbon carbon bond forming reactions between substrates hitherto unexplored with Brønsted acid catalysis. It has been established that strong Brønsted acids, such as phosphoric acids, are capable of mediating highly selective transformations operating through unique mechanistic manifolds.

Specific focus for the sulfonic acid catalysts was geared towards asymmetric coupling reactions with synthetically useful precursors such as …

Selective Carbon-Carbon Bond Formation Promoted By Divalent Samarium Reagents, Christopher David-James Aretz

Electronic Theses and Dissertations

Three efficient methods for synthesis of five membered carbocycles, a highly understudied product motif in samarium(II) chemistry, were explored and optimized. These methods utilized simple starting materials to generate linear substrates with functional groups that are reactive towards samarium(II) iodide. The three methods explored were the Reformatsky-aldol, Reformatsky-alkylation, and pinacol cyclizations. The critical discovery for efficient formation of the Reformatsky-aldol and pinacol carbocycles products was the use of lithium bromide. This addition of lithium bromide facilitates easy in situ formation of samarium(II) bromide. The Reformatsky-alkylation cyclization was a newly realized reaction employing samarium enolates. Two of the three methods, the …

Molecular Level Encapsulation Of Chromophores Using Pillar[5]Arenes For Enhanced Photostability, Manik Gudimani

Electronic Theses and Dissertations

Organic π-conjugated materials have been researched extensively for a number of applications including organic photovoltaics, electrooptic (EO) modulation, solid-state lasing, organic light emitting diodes (OLEDs), biological imaging and sensing, chemical sensing and ligands for photocatalysts. These organic optoelectronic materials have one major issue that affects its performance and lifetime—photostability. For some applications, hermetical packaging, which is expensive, is required to prevent degradation by light and oxygen. Photooxidation occurs when a material is exposed to light and causes structural and chemical changes leading to photodegradation of the material. The two primary degradation mechanisms responsible for photooxidation involve superoxide radical anion and …

Fast Isotope Ratio Mass Spectrometry (Firms): A Tandem Mass Spectrometry Technique For The Rapid And Semi-Comprehensive Evaluation Of Isotope Ratios, Fredrick Ochieng

Electronic Theses and Dissertations

Isotope ratios (IRs) are a measure of the variation in abundance of light isotopes versus heavy isotopes of an element, e.g. ¹H/²H,¹²C/¹³C, and ¹⁴N/¹⁵N. Because IRs change as a molecule undergoes certain chemical and physical processes, they represent unique fingerprints that can be used to trace the source of a chemical compound. Current techniques for determination of IRs each have major limitations, such as loss of structural information, vulnerability to contamination, high cost, large sample size requirements, low precision, limited applicability, and lengthy analysis. Fast Isotope Ratio Mass Spectrometry (FIRMS) …

Lignin Depolymerization: Mechanistic Analysis, Optimization And Application, Eric Michael Nagel

Electronic Theses and Dissertations

Lignin is the most abundant aromatic biopolymer and is a potential source for phenolic chemical feedstocks. Lignin is composed of phenolic units connected by more than eight different linkages, the most common being β-O-4 which constitutes 50-60%. The hydrothermal decomposition of a guaiacol based β-O-4 lignin dimer was studied under neutral and basic conditions to elucidate the mechanism of β-O-4 bond cleavage and the formation of downstream products. Phenol-carbonyl condensation and vinyl-ether formation were shown to be the primary causes for low monomer yields under the tested conditions. Three Ni catalyst systems, Ni/C + H₂, Ni/C-Zn, and Ni/Zn, …

A Novel Method For Synthesis Of Hydroxytyrosol, Emmanuel Onobun

Electronic Theses and Dissertations

Hydroxytyrosol, 3,4-dihydroxyphenolethanol, a naturally occurring polyphenol most common in olive tree (Olea europaea), is one of the most effective member of the polyphenols family, because of its remarkable antioxidant activity, its ability to inhibit oxidation of low density lipids (LDL), and its protection against DNA oxidative damage. Hydroxytyrosol, which is widely used in cosmetics and food supplements industries, can be purchased as an olive oil extract that contains low concentration of hydroxytyrosol besides other polyphenols. The price and low natural abundance of hydroxytyrosol make alternative synthetic sources very attractive. In this research, a novel method for the synthesis of pure …

Development Of Recyclable Gold Nanoparticles For Routine Benchtop Catalysis In Organic Transformations., Shengzong Liang

Electronic Theses and Dissertations

Homogeneous gold catalysis is a popular research area due to its high efficiency. Various gold catalysts have been utilized in organic synthesis and their reaction mechanisms are also well understood. However, most gold catalysis suffers from high catalyst loading or catalyst decay problems. In addition, homogeneous gold catalysts are not recyclable. These disadvantages have limited their application in large-scale synthesis and also caused a serious waste of this precious metal. A solution for these problems is to use a recyclable heterogeneous gold catalyst. So in this study, with the aim of making gold chemistry greener we successfully used heterogeneous gold …

Sequential Growth Of Molecular Complexity Via Alternating Ground State And Photochemical Reactions, Haibo Li

Electronic Theses and Dissertations

A new strategy of increasing molecular complexity by post photochemical oxidation followed by secondary intramolecular photochemical reaction is developed. It is based on the mild oxidation of photochemical generated alcohol by primary intramolecular cycloaddition of aromatic o-aminoaldehydes and a secondary intramolecular cycloaddition of aromatic o-aminoketone. Both cycloadditions are triggered via excited-state intramolecular proton transfer (ESIPT). Additionally, an efficient continuous reaction of photocatalyzed 2-nitrobenzyl alcohol intramolecular reduction and aryl nitroso Diels-Alder (NDA) reaction was discovered.

Design, Synthesis And Biological Screening Of Novel Cucsinspired Estrone Analogues Towards Treatment Of Hepatocellular Carcinoma, Mater Hussen Mahnashi

Electronic Theses and Dissertations

Cucurbitacins (CUCS) are natural products with highly oxygenated tetracyclic triterpenes produced mostly by Cucurbitaceae family plant. They are known for their therapeutic efficiency with different biological activities, such as anti-inflammatory, hepatoprotective and anti-cancer. Hepatocellular carcinoma (HCC) is the third leading cause of death worldwide. Previous reports have shown the ability of CUCS to inhibit the growth of hepatocellular carcinoma cell lines (HepG-2) significantly. Structural activity relationship studies suggested the potential of the 23, 24 enone side chain of CUCS to bind to the Epidermal Growth Factor Receptor (EGFR). Due to the limited quantities of CUCS upon isolation and the challenges …

The Decline And Recovery Of Thermal Oxidative Stability Of Ultra-Low Sulfur Diesel Blends, Abigail Schoor Cohen

Electronic Theses and Dissertations

Dissertation supervised by Professor Bruce D. Beaver

The oxidative stability of ultra-low sulfur diesel (ULSD) has generally been expected to continuously decline over time. However, recent studies have suggested that it may fluctuate.^1-2 In this study, the oxidative stability of stored commercially purchased ULSD was monitored with a methanol extraction method.³ In this methodology, proposed by Hardy and Wechter, fuel blends are extracted with methanol before and after thermal stressing.⁴ The methanol-soluble layer contains the oxygenated and oxidizable components of the fuel (SMORS) and the change in this mass upon stressing thus represents the oxidative stability of …

Diazonium 4-(Trifluorovinyloxy) Perfluorobutanesulfonyl Benzenesulfonimide Zwitterionic Monomer Synthesis, Isaac D. Addo

Electronic Theses and Dissertations

3-Diazonium- 4-(trifluorovinyloxy) - perfluorobutanesulfonyl benzenesulfonimide zwitterionic monomer (see figure 1) is proposed to be polymerized and further act as a new electrolyte for Polymer exchange membrane fuel cells (PEMFCs). One reason is that, the aromatic trifluorovinyl aryl ether (TFVE) group can easily be homopolymerized to aromatic perfluorocyclobutane (PFCB) polymer. Furthermore, the diazonium moiety in the monomer is expected to covalently attach the electrolyte to the carbon electrodes support. The perfluoroalkyl(aryl) sulfonimide (PFSI) pendant provides good chemical and mechanical stability as well as better proton conductivity. Several multi-step synthetic schemes are designed to obtain such monomer from perfluoroalkyl(aryl) sulfonimide (PFSI). Among …

Silver-Polymer Nanocomposites, Anita N. Paul

Electronic Theses and Dissertations

The objective of this research was the development of an efficient method for the preparation of silver-polymer nanocomposites containing finely dispersed silver nanoparticles. The surface of nanosilver was functionalized by thiolation with 2-aminoethanethiol. Amino-modified nanosilver was covalently bonded to polyacrylic acid, biodegradable polymers like acid terminated polylactic acid, ester terminated poly(DL-lactide-co-glycolide) and acid terminated poly(DL lactide-co-glycolide) in the presence of diisopropylcarbodiimide by carbodiimide method. Esterification of the carboxyl groups of Ag-polyacrylic acid by hydrochloric acid in methanol resulted in the formation of a stable colloidal dispersion of Ag nanoparticles in the polymer matrix. It was observed that not just acid …

Extraction, Purification And Characterization Of An Antibiotic-Like Compound Produced By Rhodococcus Sp. Mtm3w5.2, Pushpavathi Reddyvari Manikindi

Electronic Theses and Dissertations

The bacterium Rhodococcus is a potential source for novel antimicrobial metabolites. Recently, the Rhodococcus strain MTM3W5.2 was isolated from a soil sample collected from Morristown, East Tennessee and was found to produce an inhibitor molecule that is active against similar Rhodococcus species. The aim of this research is to extract, purify, and characterize the active compound. The compound was obtained from both agar and broth cultures of strain MTM3W5.2 and purified by primary fractionation of crude extract on a Sephadex LH-20 column, followed by semi-preparative reversed phase column chromatography. Final purification was achieved using multiple rounds of an analytical C …

Chemoselective Reactions And Their Applications In Metabolite Isolation And Analysis., Sadakatali Shokatali Gori

Electronic Theses and Dissertations

Chemoselectivity is the preferential reaction of a reagent with a select functional group among other plausible reactions. This dissertation describes chemoselective reagents and methods explored to develop more accurate, efficient and high-throughput means to quantify metabolites containing either thiol, carboxylic acid or 1,2-diol moieties directly from biological mixtures. Chapter 1 discusses how dysregulation of thiol- or carboxylic acid-containing metabolites is either the cause or effect of cellular dysfunction. Quantifying such metabolites is important in discovery of pathways to understand etiology of diseases. Chapter 1 also discusses the need for sustainable syntheses using renewable resources and describes the traditional methods for …

Synthesis Of Two Monomers For Proton Exchange Membrane Fuel Cells (Pemfcs), Abdulmajeed A. Alayyaf

Electronic Theses and Dissertations

The overall goal of this research is to synthesize two different monomers for proton exchange membrane (PEM) Fuel Cells. Such monomers are proposed to be polymerized to improve the efficiency and compatibility of electrodes and electrolytes in PEM fuel cells.

The first target is to synthesize 4-diazonium-3-fluoro PFSI zwitterionic monomer. Three steps were carried out in the lab. First one was the ammonolysis of 3-fluoro-4-nitrobenzenesulfonyl chloride. Second reaction was the bromination of Nafion monomer. The next coupling reaction, between brominated Nafion monomer and the 3-fluoro-4-nitrobenzenesulfonamide, was failed. The obstacles involve the harsh reaction condition and troublesome purification procedure.

The second …

Synthesis Of Diazonium (Perfluoroalkyl) Arylsulfonimide Monomers From Perfluoro (3-Oxapent-4-Ene) Sulfonyl Fluoride For Proton Exchange Membrane Fuel Cell, Faisal Ibrahim

Electronic Theses and Dissertations

Two diazonium perfluoroalkyl arylsulfonimide (PFSI) zwitterionic monomers, 4-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (I) and 4-(trifluoromethyl)-2-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (II) have been synthesized from perfluoro(3-oxapent-4-ene) sulfonyl fluoride (POPF) for proton exchange membrane fuel cells. PFSI polymers are proposed as new electrolytes due to their better thermal stability, inertness to electrochemical conditions, and lower susceptibility to oxidative degradation and dehydration. For a better integration between the electrode and the electrolyte, the PFSI polymers are expected to be grafted onto the carbon electrode via the diazonium moiety.

All the reaction intermediates and the final product were characterized with 1H NMR, 19F NMR and IR …

Quinolines: Novel Synthesis And Derivatives Of Heterocyclic Bioactive Agents, Ginelle A. Ramann

Electronic Theses and Dissertations

Tuberculosis is a pulmonary disease that has ravaged the world throughout history. Even today, many developed and developing countries are experiencing this plight, made worse by the scourge of antibiotic-resistant bacteria.

Mycobacterium tuberculosis's class II fructose-1,6-bisphosphate aldolase presents an interesting target in the design of new therapies against this disease. Previous attempts to construct an inhibitor to this enzyme fell short due to poor selectivity or poor cellular uptake. However a new class of noncompetitive inhibitor based on 8-hydoxyquinoline-2-carboxylic acid presents a fresh approach. Preliminary studies indicate various modifications to this scaffold could be beneficial to its inhibitory efficacy.

Modifications …

Photoassisted Generation Of Complex N, O, S Polyheterocycles, Weston James Umstead

Electronic Theses and Dissertations

This research set out to continue the exploration and diversification of excited state o-azaxylylene cycloadditions, utilizing both pre-photochemical and post-photochemical modifications.

Pre-photochemical modifications came through the addition of heteroatoms, namely nitrogen and oxygen, to the tether that links the unsaturated photopendant to the photogenerated o-azaxylylene. Photochemistry resulted in the formation of new, interesting N, O, S polyheterocycles.

Post-photochemical modifications took place through several different cycloaddition reactions, including a [4+2] hetero-Diels Alder reaction, a [4+2] Povarov cyclization, a [3+2] nitrile oxide addition, and a [3+2] nitrone cyclization. These reactions were applied first to a model system, and then to …

Photogenerated O-Azaxylylenes: Mechanistic Studies And Synthetic Applications, William Cole Cronk

Electronic Theses and Dissertations

This research sets out to build upon excited state o-azaxylylene cycloaddition. The mechanism behind the excitation and cycloaddition process of photogenerated o-azaxylylenes was determined experimentally. Time-correlated single-photon counting, steady-state spectroscopy, triplet quenching experiments, and quantum yield studies provided evidence suggesting that excited state intramolecular proton transfer is followed by intersystem crossing and stepwise addition to the tethered unsaturated pendant.

In keeping with the principles of diversity oriented synthesis, a modular approach was taken to gain access to a diverse array of N,O,S-Polyheterocycles which were modified postphotochemically via Suzuki coupling to yield fused biaryls. Cycloaddition products, outfitted with halogens …