Physical Sciences and Mathematics Commons^™

Synthesis Of Oxyquinoliziniporphyrins And Pyridoquinoliziniporphyrins, Emma Cramer

Theses and Dissertations

N-confused porphyrins are porphyrin analogues that introduce a nitrogen outside of the macrocyclic cavity. Two novel N-confused type porphyrins were targeted for this study. Both syntheses use the key intermediate 4-quinolizone. Previous studies of N-confused pyriporphyrin showed that the system is nonaromatic and resembles structurally analogous benziporphyrins. However, modifications to systems of this type can introduce aromatic characteristics. The first system targeted introduced a quinolizone subunit into a porphyrin system. Quinolizone contains a thermodynamically stable amide and this unit disrupts the aromatic pathway. However, dipolar resonance contributors can potentially reinstate some aromatic character. A quinolizone dialdehyde was condensed with tripyrranes …

Aqueous Kinetics Of Α-Hydroxyhippuric Acid Derivatives Bearing Electron-Withdrawing Groups As A Function Of Ph And Buffer Catalysts, Mohamad Imad Rafie

Theses and Dissertations

It has been shown that carbinolamides are intermediates in the enzyme-catalyzed synthesis of -amidated peptides. Although carbinolamides are important intermediates in the production of these hormones and have roles in other biological venues, little attention has been given to their mechanisms of reaction in water, and, thus, it is difficult to speculate how their reaction would be enzymatically catalyzed. The purpose of the work presented here was to synthesize structural analogs of the biological intermediates and study their mechanism of breakdown in water. -Hydroxyhippuric acid, a substrate for the enzymatic system, provides an easily modified template for the study of …

The Development Of A New Entry Point Into Enantiomerically Enriched Sulfinyl Derivatives, Jessica Shaw

Theses and Dissertations

Optical probes may be used as reliable tools for detecting and imagining the inside of cells for medical diagnostics. Among available options, the use of thiol probes is of interest as thiols are present in nearly all cells and their levels are tightly regulated, thus any variation is associated with disease. A proper thiol bioimaging probe must have a thiol cleavage group/reactive group and a fluorophore. It is found that novel sulfinate aryl ester (phenoxysulfinate esters) probes selectively cleave thiols at physiological pH and show much promise as effective tools for bioimaging.

In this context, the synthesis of the related …

Rapid Vertical Flow Assay On Aunp Plasmonic Paper For Sers-Based Point Of Need Diagnostics, Richard Frimpong

Theses and Dissertations

SERS based immunoassays for point-of-care diagnostics is a promising tool to facilitate biomarker detection for early disease diagnosis and control. The technique is based on a sandwiched system in which antigen is first captured by a selective substrate and then labeled by an extrinsic Raman label (ERL). Here, we report on the use of gold nanoparticle modified filter paper as a novel capture membrane in a vertical flow format. This vertical flow configuration affords reproducible flow of sample and label through the capture substrate to overcome diffusion limited kinetics and significantly reduced assay time. The filter paper was selected due …

Adsorption Behavior Of Chemically / Charged Modified Antibodies On Gold Nanoparticles, Samuel Okyem

Theses and Dissertations

Gold nanoparticles (AuNPs) have been exploited in the various domains of science such as drug delivery, bio-sensing, immunoassays and environmental sensors, due to their optical properties and intriguing surface chemistry. Different scientific procedures have been used to effectively immobilize antibodies onto AuNPs. Although acceptable outcomes have been achieved in the immobilization of antibodies onto AuNPs, the sensitivity of these immobilized antibodies to target antigen or binding sites is limited due to improper orientation of the antibodies. Also, the possibility of nanoparticle aggregation when exposed to proteins limits its biomedical applicability.

There is some evidence that the surface charge of antibodies …

Investigating The Reversibility Of Protein Adsorption On Gold Nanoparticles And The Role Of Free Thiol, Awosiji Olatunde Awotunde

Theses and Dissertations

Protein-gold nanoparticle (AuNP) bioconjugates have many potential applications in nanomedicine. A thorough understanding of the interaction between the protein and AuNP is critical to engineering these functional bioconjugates with desirable properties. In this work, we investigate the role of free thiols presented by the protein on the stability of the protein-AuNP conjugate. Human serum albumin (HSA) was modified with 2-iminothiolane (Traut’s reagent) to introduce additional thiols on the protein surface, and three variants of HSA were synthesized to present 1, 5, and 20 free thiols by controlling the molar excess of the chemical modifier. Protein exchange studies on AuNPs were …

Oxadiazinones As Chiral Auxiliaries: Chiral Templates For Asymmetric Conjugate Addition In The Synthesis Of ( R )-( + )-Tolterodine, Fatima Olayemi Obe

Theses and Dissertations

The stereoselective formation of carbon-carbon bonds through the process of conjugate addition has proven to be a very important methodology in synthetic organic chemistry. In this context, oxadiazinones are chiral auxiliaries that have been applied in the asymmetric aldol addition reaction to synthesize valuable synthetic fragments such as the aldol side chain of the multi-drug resistance medicinal agent, hapalosin. This thesis describes efforts that were directed towards employing oxadiazinones as chiral scaffolds for the process of asymmetric conjugate addition with the ultimate objective of using this methodology in the preparation of medicinal agents such as Tolterodine. Preliminary efforts focused on …

Syntheses, Characterization, And Preliminary Evaluation Of Potential Ruthenium Anticancer Complexes Containing Schiff Base Ligands, Stephen Mensah

Theses and Dissertations

Platinum-based drugs have over the years been administered in the treatment of tumours.

Unfortunately, platinum resistance and the severe side effects associated with the treatments has necessitated the research for new anti-cancer drugs. Ruthenium(II) and Ruthenium(III) complexes have shown promise as useful alternative anticancer agents. The lead candidates include the Ru(II) complex RAPTA-C, a ruthenium(II)-arene complex [Ru(η6-p-cymene)Cl2(1,3,5-triaza-7-phosphaadamantane)] and the Ru(III) complex NAMI-A [imidazoleH][trans-Ru(imidazole) (dimethyl sulfoxide)Cl4]. Both compounds have shown potent cytotoxic activity in several primary human tumor models. Unfortunately, NAMI-A could not advance in clinical evaluations due to limited efficacy in vivo, while the clinical evaluation of RAPTA-C is unknown. …

Potential For On-Site, Prosecutorial Evidence From Drug Residues Collected On Plasmonic Paper: A Pilot Study For Sers-Psi-Ms, Daniel S. Burr

Theses and Dissertations

Given the potential impact of improvements to on-site drug testing, as well as recent, successful displays of paper spray ionization mass spectrometry (PSI-MS) in this regard, this thesis pilots the implementation of Raman spectroscopy as a compliment to MS for field-based confirmatory drug testing. Surface enhanced Raman scattering (SERS) is utilized for applications to trace detection. Two-tiered analysis of individual drug samples is enabled using triangularly-cut plasmonic papers, from which both SERS and PS-MS analysis may be performed. Several drug compounds, representative of traditional and emerging drug types, are examined by these techniques, both separately and as a fully integrated, …

Effects Of Electrical Stimulation On Glioma Cells In Vitro With Implications For Treating Chronic Pain: Development Of A Model System, David C. Platt

Theses and Dissertations

Glial cells comprise over 70% of the central nervous system cells and exhibit diverse functions including regulation of synaptic transmission, neuron protection/repair, maintenance of neuronal metabolism, and are implicated in the development of persistent neuropathic pain. In addition, a perturbation in the concentration of intracellular reactive oxygen species (ROS) and reactive nitrogen species (RNS) has likewise been associated with the development of a chronic pain state. This perturbation in ROS/RNS creates an environment of oxidative stress. However, the mechanism by which the pain signal transmission is modulated, and the roles ROS play in the perpetuation of the pain state are …

Synthesis And Metalation Of Internally Alkylated Porphyrinoids, Alissa Nicole Latham

Theses and Dissertations

The mechanism behind alkyl migration in palladium(II) benzocarbaporphyrins was investigated through the synthesis of a 23-methylcarbaporphyrin. It was found that palladium insertion led to methyl group migration to C21 and it is proposed that this occurs through an oxidative addition onto the palladium metal center, followed by a reductive elimination to transfer the methyl to the internal carbon. A similar rearrangement was observed when 23-methylcarbaporphyrin was reacted with [Rh(CO)2Cl]2 and resulted in the formation of a rhodium(III) complex containing a three-membered rhodacycle. The syntheses of rhodium(I) and rhodium(III) derivatives of other carbaporphyrins, including 21- and 22-methylbenzo-carbaporphyrins, were probed and four …

Synthesis And Characterization Of A Series Of Vanadium ( Iv ) Complexes With The Kläui Ligand, Xiao Wu

Theses and Dissertations

Cyclopentadienyltris (dibutyl phosphito-P) cobaltate, {(C5H5)Co[(OR)2PO]3}– (R=Bu), is a tripodal ligand and also called Kläui ligand (R=Bu). The synthesis and characterization of several vanadium(III) and vanadium(IV) complexes containing Kläui ligand (R=Bu) as the catalytic models to catalyst the oxidation reaction of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-benzoquinone (3,5-DTBQ) are detailed here. Chapter II details the synthesis of the supersandwiches and Kläui ligand (R=Bu). Chapter III details the synthesis of vanadium monomeric complexes containing Kläui ligand (R=Bu). Chapter IV details the vanadium dimeric bridging complexes synthesized by different vanadium monomers from Chapter III. Chapter V details the catalytic activities of these vanadium complexes.

Alkyne Combustion: Experimental And Computational Studies Of Formyl Radical Production, Matthew Charles Drummer

Theses and Dissertations

The United States consumed a total of 97.4 trillion BTUs of energy in 2016 with over 80% of that energy consumption source being fossil fuel combustion. Before a combustion reactions reaches its end products, a number of intermediate products form and may react with other abundant atmospheric species to form aerosol particles and acid rain, both of which have potentially negative impacts on both human-made structures and the natural environment.

In an effort to counteract the consequences of fossil fuel combustion, scientists are interested in understanding the reaction mechanisms of hydrocarbon combustion reactions to understand which intermediate products form and …

Kinetic Characterization Of Listeria Monocytogenes 2-C- Methyl-D-Erythritol 4-Phosphate Cytidylyltransferase ( Cms ) Enzymes Using High Performance Liquid Chromatography ( Hplc ), Mark Oblazny

Theses and Dissertations

Infectious diseases, with increasing prevalence of antibiotic resistant bacteria, coupled with the declining rate in discovery of antimicrobial agents, impose one of the most significant threats to human health. Here we identify 2-C-methyl-D-erythritol 4-phosphate cytidylyltransferase (CMS) as a valid target for antibiotic development which is an enzyme in pathogenic organisms that leads to the biosynthesis of isoprene precursor molecules. Isoprene molecules are one of nature’s most common building blocks that are vital to many biological metabolic processes and are synthesized via the mevalonic acid dependent (MVA), or methylerythritol phosphate (MEP) pathway. Vertebrates utilize the MVA pathway, while many pathogenic bacteria …

The Biochemical Assessment Of Two Secreted Acid Phosphatases From Leishmania Tarentolae, Their Response To Electric Fields, Glycosidase Incubation, And / Or Vanadium, Benjamin M. Dorsey

Theses and Dissertations

Leishmaniasis, as defined by the Center for Disease Control and Prevention, is a neglected tropical disease with 1.6 million new cases reported each year. However, there is yet to be safe, effective, and affordable treatments provided to those affected by this disease1. Still underappreciated as a potential pharmaceutical targets, especially for cutaneous leishmaniasis infections, are the two isozymes of secreted acid phosphatase (SAP); secreted acid phosphatase 1 (SAP1) and secreted acid phosphatase 2 (SAP2). These enzymes are involved in the survival of the parasite in the sand fly vector, and the prevention of host macrophages from forming parasitophorous vacuole and …

Fermenting Solutions To New World Problems: Bioremediation Of Blue Agave And Cocoa Pod Wastes, Daniel Hart

Theses and Dissertations

Waste, minimizing it, and maximizing profit from it are major foci of most agricultural production processes today. Waste from two major production processes, namely tequila production and cocoa production, share several characteristics. Both these processes are still carried out as they have been for hundreds of years. They are both relatively concentrated in location; all tequila is produced in a small region of Mexico while cocoa pods only grow in tropical environments within 18° of the equator. In addition, both processes used to produce these commodities remain fairly inefficient; they generate huge amounts of waste that goes mostly unused. With …

Development Of New Routes For The Synthesis Of Carbaporphyrins And Carbachlorins, Navneet Sahota

Theses and Dissertations

Carbaporphyrins and carbachlorins are porphyrin analogs in which one of the nitrogens is replaced with a carbon atom within a porphyrin-like cavity. These systems form stable organometallic derivatives and exhibit unusual chemical reactivity. In the monocarbaporphyrinoids such as benzocarbaporphyrins, one of the pyrrole rings is replaced by an indene unit. Although syntheses of monocarbaporphyrins with fused rings have been widely investigated over the past 20 years, a few examples of carbaporphyrins without fused rings have been reported in the literature.

In this thesis, two projects were conducted to further explore carbaporphyrin and carbachlorin chemistry. The first project utilized a ‘3+1’ …

Formation, Characterization, And Optimization Of Antibody-Gold Nanoparticle Conjugates, Seth L. Filbrun

Theses and Dissertations

Protein modified gold nanoparticle based immunoassays are the basis of many novel detection techniques. There are many groups working on novel immunoassays but there is still much to understand about how many proteins are attached onto each nanoparticle and much to improve on immobilization methods. This thesis work is devoted to improving techniques for the quantification of protein immobilized on the gold nanoparticle and development of a novel approach to immobilize protein independent of pH.

The ability to evaluate antibody immobilization onto gold nanoparticles is critical for assessing coupling chemistry and optimizing the sensitivity of nanoparticle-enabled biosensors. Herein, we developed …

Synthesis And Characterization Of Polycyclic Aromatic Hydrocarbon ( Pah )-Porphyrin Hybrids, Ruixiao Gao

Theses and Dissertations

Carbaporphyrins are porphyrin analogs where one or more pyrrole units are replaced with a carbocyclic ring. Benziporphyrins are porphyrin analogues with a 1,3-phenylene unit replacing one of the pyrrole subunits. Because of cross-conjugation, benziporphyrins are not aromatic species. However, protonation of benziporphyrins can afford some aromatic characteristics. Although the synthesis of many examples of monocarbaporphyrins have been successfully executed, no examples of porphyrinoids with pyrene subunits have been prepared. Pyrene-containing porphyrinoids, which have been named as pyreniporphyrins, are theoretically significant molecules that provide insights into the aromaticity and reactivity of porphyrinoid systems.

In this thesis, two projects were conducted to …

Inhibitory Effects Of Unique Sulfonamides On Leishmania Tarentolae And Potential Pathway Of Inhibition, Jade M. Katinas

Theses and Dissertations

Leishmaniasis is an endemic disease caused by the protozoan parasite Leishmania. Current treatments for the parasite are limited by cost, availability, and drug resistance as the worldwide occurrence of leishmaniasis continues to be more prevalent. Sulfonamides are a class of compounds with medicinal properties that have been used to treat bacterial and parasitic diseases via various pathways. In this study, newly synthesized, unique structural analogs of sulfonamide compounds were assessed for their impact on Leishmania cell viability and potential pathways for inhibition were evaluated. Leishmania tarentolae (ATCC Strain 30143) axenic promastigote cells were grown in BHI medium and treated with …

Solid State Synthesis And Characterization Of The Rare Earth-Free Anti-Perovskites Sr2.5-Xba0.5 Al1-Xp Xo4 F ( 0 ≤ X ≤ 0.15 ), Sr3al1-Xy Xo 4 F ( 0 ≤ X ≤ 1 ), And Sr2.5-X/2ba0.5 Al1-Xhfxo4 F ( 0 ≤ X ≤ 0.1 ) As Potential Phosphor Materials, Sean Thomas Keil

Theses and Dissertations

Typical lighting systems such as incandescent and fluorescent bulbs are common in homes but are rather inefficient compared to the newer light emitting diodes (LEDs). LED-based lamps can be constructed to generate white light by combining a red, green, and blue LED, or by using an LED light source (typically with a low wavelength) with a complimentary phosphor coating to produce white light. The latter, known as phosphor-conversion (PC) LEDs, is the primary focus of this research, looking specifically at rare earth-free options for these phosphor coatings.

Anti-perovskites are a potential lattice type for this type of conversion, in particular …

Characterization Of Cytidylyltransferase Enzyme Activity Through High Performance Liquid Chromatography, James Brault

Theses and Dissertations

The cytidylyltransferases are a family of enzymes that utilize cytidine 5â?? triphosphate (CTP) to synthesize molecules that are precursors to membrane phospholipids. There are four well known enzymes: CTP: phosphoethanolamine cytidylyltransferase (ECT), CTP: glycerol-3-phosphate cytidylyltransferase (GCT), 2-C-methyl-D-erythritol-4-phosphate cytidylyltransferase synthetase (CMS), and CTP: phosphocholine cytidylyltransferase (CCT). Previously, a radioisotope tagging method was employed to study cytidylyltransferase catalysis. Using CCT as a model, a method utilizing high performance liquid chromatography (HPLC) was developed to replace the radioisotope scintillation technique. The development of this new HPLC method is cheaper, more efficient, and more accurate than the previously established method.

The targets of separation …

Synthesis And Characterization Of Neo-Confused Porphyrins And Related Systems, Arwa Salem Almejbel

Theses and Dissertations

Carbaporphyrins have been the focus of many studies, and a wide variety of related carbaporphyrinoid systems have been reported. N-confused porphyrins are a class of carbaporphyrins where one pyrrole unit has been inverted. In this work, a newly discovered family of porphyrin isomers where one of the pyrrolic subunits is connected to the meso-bridges in a 1,3-fashion, called neo-confused porphyrins, has been investigated.

Reaction of pyrrole-3-carbaldehydes with acetoxymethylpyrroles and NaH in DMF gave neo-confused dipyrrylmethane dialdehydes. The resulting dialdehydes underwent an acid catalyzed condensation with a dipyrrylmethane to give neo-confused phlorins, and following oxidation with FeCl3 afforded new neo-confused porphyrins. …

Synthesis And Characterization Of Naphthocarbaporphyrins And Related Systems, Eric Grabowski

Theses and Dissertations

Carbaporphyrins are porphyrin analogs in which one of more of the pyrrole units have been replaced with a carbocyclic ring. In this project the cyclopentadiene ring replacing a pyrrole ring has been fused with a naphthalene ring. This is done in order to observe the effects of the naphthalene ring on the spectroscopic properties and reactivity.

Utilization Of Antibody-Conjugated Gold Nanoparticles, Dynamic Light Scattering And Sers In Influenza Virus Detection, Yen Hoang Lai

Theses and Dissertations

Influenza A H3N2, H1N1, and influenza B viruses primarily cause winter illness in humans, leading to significant morbidity and mortality in the population of the very young, the elderly, and people with chronic disease. In addition to the regular seasonal epidemics of influenza, influenza pandemics associated with the emergence of new influenza A strains are threatening due to high levels of mortality, social disruption, and economic losses. These novel strains are not affected by the human immunity developed to older strains of influenza, therefore can spread readily and infect a vast number of people. The most recent flu pandemic outbreak …

Transition Metal-Olefin Bonding Interactions: A Density Functional Theory Study [ M ( Co ) X ( Æ? 2-C 2 H 3-C 6 H 4-Y) ], Michael John Berninger

Theses and Dissertations

Metal-olefin equilibrium geometries, bond formation energies (Î?E), enthalpies (Î?H), and free energies (Î?G) for a select series of transition (M = Ni, Fe, Cr, Mo and W) metal-olefin carbonyl complexes [M(CO)x(Æ?2-C2H3-C6H4-Y)] have been calculated and compared using density functional theory (DFT), with the BP86 functional under standard state conditions (1 atm, 298.15 K) for the general gas phase formation reaction:

M(CO)x + (C2H3-C6H4-Y) â?? [M(CO)x(Æ?2-C2H3-C6H4-Y)] (1)

Y = NO2, CN, COOH, H, OH, NH2, N(CH3)2

In regards to the electronic modification of the substituent (Y) on styrene at the para position, this study quantitatively investigated the effect of electron-withdrawing and …

An Approach To An Agave Problem: The Bioremediation Of Agricultural Waste By Yeast Fermentations, Joshua Michael Jarodsky

Theses and Dissertations

The agricultural waste products created by industries, such as the Tequila manufacturing industry, create thousands of tons of waste material every year. This agricultural waste often becomes an environmental and ecological problem for fields and surrounding areas. The purpose of this study is to determine the potential of using the yeast Kluyveromyces marxianus 7-1 and Kluyveromyces marxianus 8-1 to ferment the leaf waste from the harvesting of the Agave tequilana as a form of bioremediation. Fermentations (anaerobic, under constant shaking, and at room temperature) were monitored for colony forming units, pH of fermentation broth, concentration of reducing sugars, and protein …

Functional Expression And Characterization Of A Truncated Candida Antarctica Lipase B In Yeast, Samantha Robinson

Theses and Dissertations

Candida antarctica lipase B is an enzyme capable of hydrolyzing ester bonds in a lipid-water interface with potential to become a useful biocatalyst for production of biodiesel fuel. Enzymatically catalyzing the transesterification of triacylglycerides to produce fatty acid alkyl esters (biodiesel) is an environmentally cleaner alternative to the current process which utilizes chemical reagents as catalysts. Optimization and development of strains to express highly active, stable, large quantities of these biocatalysts is essential for inexpensive production of biodiesel. Additionally, lipase enzymes can be immobilized onto a resin, eliminating the need to recover the catalyst from the product and allowing multiple …

Examination Of Quasienantiomers Of Oxadiazinanones Which Fail To Fractionally Crystallize, Patricia Ann Higgins

Theses and Dissertations

This thesis reports the crystallization of two new quasiracemic crystals, the synthesis of a new oxadiazinanone, and the identification of crystals of two new compounds. In previous research the quasiracemates, (5,R,6,S)-4-cyclohexyl-5-methyl-6-phenyl-2H-1,3,4-oxadiazinan-2-one and (5S,6R)-4-isopropyl-5-methyl-6-phenyl-2H-1,3,4-oxadiazinan-2-one, were mixed in solution and crystallized. Instead of fractionally crystallizing, as would be expected, the compounds formed quasiracemic co-crystals. This suggested that other mixtures of oxadiazinanones would be possible candidates for studying compounds which fail to fractionally crystallize.

The first step in the process involves the synthesis of oxadiazinanones, using literature methods. A 4-step process …

Α-Hydroxyhippuric Acid Derivatives: Ph-Dependent Aqueous Kinetics And Buffer Catalysis., Kati Feken

Theses and Dissertations

Synthesis and kinetic investigations of the aqueous breakdown of α-hydroxyhippuric acid derivatives as a function of pH were performed to acquire an understanding of the reactivity of this biologically relevant carbinolamide functionality.