Organic Chemistry Commons^™

Computer-Aided Development Of Novel Antioxidants, Rita Bernadett Vlocsko

Graduate Doctoral Dissertations

Physiological redox homeostasis is a fine balance between prooxidants and antioxidants that are integrated elements of several reduction-oxidation mechanisms at molecular, organellar, cellular and tissue levels. When this equilibrium is disrupted and prooxidants become dominant, the body relies on endogenous and exogenous antioxidants to counterbalance the dysregulation and ultimately prevent the progression of oxidative stress. Reactive species (reactive oxygen species, reactive nitrogen species, or reactive sulfur species) are significant contributors to prooxidant activity. Over the years, substantial knowledge has been accumulated regarding their origin and roles in disease development, leading to the discovery and development of antioxidants that effectively target …

Arylation Of Nitrogen, Oxygen And Carbon Nucleophiles By Aryl(Tmp)Iodonium Salts, Joseph Jordan Hatton

Dissertations and Theses

Substituted aromatic rings are present in industry in a plethora of organic molecules such as pharmaceuticals, agrochemicals, materials and beyond. Therefore, methods for broadly installing aryl rings into other compounds to create substituted aromatic rings are valuable to many organic chemists. Historically these transformations are achieved through methods such as nucleophilic aromatic substitution and metal catalyzed cross-coupling. Nucleophilic aromatic substitution is a user-friendly method in this space but is limited by reliance on specific electronics. Metal catalyzed cross-coupling reduced the dependence on electronics in this space, but metals are generally unattractive reagents due to high costs, toxicity and challenges with …

Synthesis Of A Halogenated Glyoxime For Cobalt Deposition Suppression, Liam S. Allen

Honors Theses

Dr. Qiang Huang at the University of Alabama is a chemical engineering professor and works on the electrodeposition of metals to create circuitry. During this process suppressive molecules may be added to control help the process. This project focuses on synthesizing an alpha-halogenated glyoxime to test whether the compound is a more effective suppressant in comparison to regular glyoximes. More specifically the target chemical is called bromo-dimethylglyoxime which is created in a two-stage reaction. The starting material, diacetyl monoxime, is brominated at the alpha carbon position. The product of this reaction, officially called bromodimethylglyoxalmonoxime, is then reacted with hydroxylammonium chloride …

Sulfhydryl-Functionalized Diarylethenes: Synthesis, Photoswitching, And Fluorescent Properties, Pramod Aryal, Jonathan Bietsch, Gowri Sankar Grandhi, Josh Choi, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Sulfhydryl group (SH) plays important roles in reactions with various functional groups, especially in biologically active systems. Photoswitchable diarylethene (DAE) derivatives have demonstrated applications in many research fields. Among the many classes of diarylethene derivatives, thiol derivatives have not been extensively explored. In this study, we systematically synthesized and characterized a series of bis-thiol functionalized dithienylethene derivatives. The thiol groups in this series are attached directly to the thiophene, or through a phenyl or methylene linker. Each series incorporated both dithienyl cyclopentene and hexafluorocyclopentene bridges and total six thiol substituted diarylethenes were synthesized. Among the six sulfhydryl DAE derivatives, four …

Photoflow Synthesis And Characterization Of Cis- And Trans-N-Isohumulone, Gregory M. Giovine, Bradley Gallow, Trevor Smith, Bruce Hamper

Undergraduate Research Symposium

Previously published efforts by the Hamper group demonstrated the viability of photochemistry in the isomerization of n-humulone to n-isohumulone. Photochemical isomerization reactions of n-humulone performed under 400nm light over 8 hours resulted in high yields (84% reported) of largely trans-n-isohumulone (>95%). These promising results invited further examination of the photochemical process and the application of photoflow procedure. Herein we report the beginnings of a comprehensive slate of n-humulone isomerization reactions performed under iterative photoflow conditions.

The Potential Importance Of Microenvironment On Polymer Bound Chemical Reagents, Nathan Joseph Halsteter

Theses and Dissertations

In this thesis will provide a brief history of polymer bound reagents, their uses, and advancements. The importance of polymer microenvironments will be explored using a model kinetic resolution reaction utilizing polymer bound reagents to observe how changes in a polymer’s microenvironment effects the yield and selectivity of a reaction. It was found that there are copious factors that affect polymer bound reagents, and no direct conclusion could be drawn from the study.

Asymmetric, Carboxy And Ester Functionalized Fluorophthalocyanines: Synthesis, Adsorption, And Reactivity, Sean J. Scally

Seton Hall University Dissertations and Theses (ETDs)

Strong electron-deficient compounds, fluorinated metal phthalocyanines (F_xPcM), exhibit enhanced photosensitizing properties, making them optimal candidates for photocatalytic studies. Perfluoroalkyl-substituted phthalocyanines are notably thermally robust materials that are chemically inert and resistant to electrophilic, nucleophilic, and radical, including reactive oxygen species (ROS) attacks. These properties can be attributed to their ‘Teflon-like’ inert organic shield that surrounds a reactive metal center, as well as their complete (x = 16, 40, 64), or almost complete (x = 48) lack of C-H bonds. Third-generation, functionalized, asymmetric phthalocyanines are of interest due to their ability to bind to oxidic supports via a carboxyl …

Bottom-Up Mechanochemical Synthesis Of Nanographene, Sarah Kerr

Honors Theses

This research explores the application of mechanochemistry in the bottom-up synthesis of nanographene, specifically focusing on the mechanochemical Diels-Alder (DA) reaction. The study investigates the effect of different reaction conditions and dienophiles on the mechanochemical DA reaction, aiming to optimize reaction efficiency and yield using a ball mill. The initial trials with a sterically hindered dienophile (2) and an electron-deficient diene experienced repeated failure, while reactions using dienophile (B), a terminal alkyne showed more promising results. Various variables were examined, including reaction time, jar size, ball size, ball number, shaking frequency, liquid-assisted grinding (LAG), heating, and diene to dienophile ratio, …

Development Of Mixed O/S-Donor Imidazole Thione Ligands For Trivalent Lanthanide/Actinide Separations, Rhianna Wolsleger

All Dissertations

Separation of lanthanides and actinides is difficult due to their very similar size and charge. Increasing selectivity for actinides over lanthanides is possible by incorporating a softer, more polarizable donor atom into a chelating ligand, since the softer donor atom is capable of greater orbital overlap with the 5f orbitals of the actinides vs the 4f orbitals of the lanthanides. Sulfur-containing imidazole thione chelating ligands have not been investigated for this purpose but possess a resonance structure that puts significant negative charge on the sulfur, enabling it to form strong metal-sulfur bonds compared to other sulfur-containing ligands such as thioethers …

Synthesis, Characterization, And Redox Properties Of Select 1,4-Diazocine-6,11-Diones Towards An Electrochromic Dye-Set, Jeffrey Scott Richards

Open Access Theses & Dissertations

The daily consumption of personalized digital visual information depends on the current purview of electronic-based displays. Present manufacturers utilize modern technologies, such as LCD, OLED, QLED, and electronic ink, or "E Ink," in their devices to display text, pictures, and other forms of media to individual users. However, as modern society continues to rely on the use of digital displays, the demand for low-power alternatives will continue to rise as their application in varying scenarios is realized. Currently, "E Ink" technology continues to grow as the dominant solution in the e-readers and digital signage marketplace, and can even be seen …

Synthesis Of Novel Five-Membered Heterocycles As Bioactive Agents, Subrata Roy

Student Theses and Dissertations

This dissertation outlines the synthesis of various types of heterocyclic small molecules across three chapters. The first chapter discusses the efficient synthesis of seventy-one fluorinated pyrazole molecules and thirty-five 3,4-dihydroxy and 4-hydroxy phenyl-substituted thiazole molecules. These molecules were designed and synthesized for their potential antibacterial properties. The second chapter discusses the synthesis of fused thiazole molecules with enone-based steroidal natural products. This chapter reports on sixty-five novel fused thiazole molecules distributed across three libraries featuring different steroidal natural products: ethisterone, bisnoralcohol, and diosgenin. These molecules were designed and synthesized as potential anticancer agents. The third chapter comprises the development of …

Click-Based Synthesis Of Hemibastadin Derivatives And Their Applications As Antimicrobial And Biofilm Inhibiting Agents, James B. Daniel Iii

Longwood Senior Thesis Proposal

Antimicrobial agents are one of the most important tools used in the medical industry. With the ever growing numbers of antibiotic resistant bacteria, new strategies have been developed to combat them, one of which being biofilm inhibiting agents. A class of molecules called hemibastadins, first discovered from sea sponges, have been of recent interest in the field. Building from previous work done in this lab on hemibastadins, a hemibastadin derivative containing a triazole in place of the oxime has been identified as a potential antibiofilm agent. This work will target a derivative that will more closely mimic the hemibastadins found …

Refining Chlorosulfonation Methods For The Synthesis Of A Perfluoroalkyl Arylsulfonimide (Pfsi) Monomer, Ainsley P. Foster, Ben Varney, Hua Mei

SPARK Symposium Presentations

Proton-exchange membrane (PEM) fuel cells are sources of energy that are clean, quiet, and highly responsive to changes in power needs, making them promising for use in automobiles and other portable power devices. The electrolyte of a PEM cell–the layer responsible for conductivity–is a polymer membrane, commonly consisting of perfluoroalkyl sulfonic acid (PFSA) polymers. In place of the PFSA polymers, perfluoroalkyl arylsulfonimide (PFSI) polymers are expected to improve the efficiency of PEM fuel cells with better stability and proton conductivity. The trifluovinylether (TFVE) aryl perfluorosulfonamide monomer is a new PFSI monomer proposed to fulfill these benefits once polymerized. The previous …

Developing Phenanthroimidazole-Based Fluorescent Sensors For Efficient Analyte Detection, Brian Kellogg

Masters Theses & Specialist Projects

The highly efficient design and synthesis of organic fluorophores with an excellent quantum yield have received extensive attention. Compared with instrumental techniques, fluorescent sensors derived from organic small molecules offer many impressive benefits, such as selective detection, lower cost, and higher efficiency. Various detection mechanisms such as colorimetric, ratiometric, and fluorescence turn on/off have been reported for single analyte detection. Developing molecular probes that are capable of detecting two (or more than two) different analytes (cations, anions, and/or biomolecules) had emerged as a new research area and attracted considerable attention in the field of chemo- and biosensors.

Phenanthroimidazole represents a …

Refining Chlorosulfonation Methods For The Synthesis Of A Perfluoroalkyl Arylsulfonimide (Pfsi) Monomer, Ainsley P. Foster, Benjamin Varney, Hua Mei

Science University Research Symposium (SURS)

Proton-exchange membrane (PEM) fuel cells are sources of energy that are clean, quiet, and highly responsive to changes in power needs, making them promising for use in automobiles and other portable power devices. The electrolyte of a PEM cell–the layer responsible for conductivity–is a polymer membrane, commonly consisting of perfluoroalkyl sulfonic acid (PFSA) polymers. Perfluoroalkyl arylsulfonimide (PFSI) polymers are expected to improve the efficiency of PEM fuel cells through optimal stability and proton conductivity. The trifluovinylether (TFVE) aryl perfluorosulfonamide monomer is a new PFSI monomer proposed to fulfill these benefits once polymerized. A six-step synthesis route was initially designed to …

Synthesis Of Portions Of An Acinetobacter Baumannii Lipooligosaccharide (Los), Brandon Conrad

LSU Doctoral Dissertations

Glycoconjugate vaccines have become an effective strategy for protection against an array of globally persistent diseases resulting from pathogenic bacteria such as Haemophilus influenzae type b (Hib), Neisseria meningitidis, and Salmonella enterica serotype Typhi. Comprised of a carbohydrate (referred to as glycan) covalently inked to a carrier protein, these vaccines can initiate adaptive immunity by inducing B and T cell responses once in the lymphatic system. This is particularly relevant for infants two years of age and younger whose immune systems are not fully developed. A continuously emerging threat in clinical settings, Acinetobacter baumannii is a Gram-negative bacterium …

Towards Carbon Dioxide Reduction: Synthesis And Characterization Of Ccc-Nhc Pincer Iron Complexes., Joshua Mensah

Theses and Dissertations

The industrial revolution came with its downside of emission of greenhouse gases into the atmosphere. The NOAA reported in 2019 that, of the greenhouse gases emitted into the atmosphere, CO2 contributed to about 80% of the increased greenhouse gases hence the need for CO2 Sequestering and Storage (CSS) and ultimately leading to Carbon Capture and Recycling (CCR) as a viable option to convert CO2 into useful forms. The race to find the best catalyst for CCR has led to the synthesis of many organometallic compounds. Pincer complexes catalyzed CO2 reduction has gained notoriety recently because of the tunability and robustness …

Synthesis, Molecular Characteristics, And Antibacterial Assessment Of Marine Hydroid Aqueous Extract-Based Silver Bio-Nanoparticles, Fredryk Mandey, Aulia Rhamdani Arfan, Rugaiyah Andi Arfah

Makara Journal of Science

This investigation aims to synthesize, analyze the molecularity, and test the ability of bacterial inhibition capability of silver nanoparticles that have been synthesized by simply mixing silver nitrate and aqueous extracts of marine natural products with and without the addition of amylum as a stabilizing agent. This research, with and without the addition of amylum as a stabilizing agent, obtained 39.0 and 55.2 mg of solids of round-shaped morphology silver nanoparticles with diameters of 87.9 and 103.0 nm., respectively. In addition, the antibacterial testing assay against Staphylococcus aureus and Escherichia coli showed some considerably good results. S. aureus with the …

The Effect Of Variation Of N-Substituents On Oxidopyridinium Ions In (4+3) Cycloadditions, Zahria Patrick, Madison Clark

Undergraduate Research Symposium

The aim of this research project is to expand the scope of 4 + 3 cycloadduct chemistry by varying functional groups attached to the prerequisite oxidopyridinium ion for each respective cycloadduct product. While N-substitution of the pyridinium precursor is known to proceed smoothly if alkylated by a lone methyl group, we evaluated the effect a larger alkyl group would have on the overall yield of the 4 + 3 cycloadduct product.

Isobutyl triflate, generated from the known reaction between isobutyl alcohol and triflic anhydride, was reacted with ethyl 5-hydroxy-nicotinate to generate the respective N-isobutyl oxidopyridinium ion in quantitative …

Adapting Chiral Gas Chromatography Into Existing Undergraduate Laboratories To Emphasize The Importance Of Stereochemistry, Ken Overway, Barnabas Otoo, Nicholas Griffin, Marshall Ritchie, Tyler Lynn, Kate Dear, Tyler Deutsch, Leigha Dillard

Chemistry Faculty Scholarship

Owing to the critical role of stereochemistry in biotechnology, medicine, and industry, it must be well represented in undergraduate lab curricula. To achieve these stereochemical laboratory requirements without sacrificing existing lab techniques, we modified two standard laboratory experiments to include chiral GC analysis as follows. (1) The extraction of carvone from spearmint leaves and caraway seeds via steam-distillation or other extraction methods is widely used in laboratories for analyzing the stereochemistry of the extracted products. The experiment was modified to include a GC method using a β-DEX 225 column. This allowed the students to compare the retention times of the …

Synthetic Strategies Toward The Development Of Stable Gold-Based Anticancer Agents And Their Mechanistic Insight, Adedamola Arojojoye

Theses and Dissertations--Chemistry

Despite notable advancements in the design and synthesis of novel chemotherapeutic drugs, cancer continues to be a leading cause of death in the United States. Metallodrugs, especially Au complexes, have played a prominent role in the search for the next generation of chemotherapeutic agents. Herein, I report on the synthetic strategies towards the rational design of stable Au (Au)-based agents, study their reactivity in biological environment, and offer insights into the cytotoxic mechanism of action in cancer. Chemotherapeutic Au compounds exist mainly in +I or +III oxidation states. Repurposing of the Au(I) FDA approved auranofin for the treatment of diseases …

Superelectrophile Promoted Syntheses Of Aromatic Spirocycles, Jeffrey Caz Ferreira

Graduate Research Theses & Dissertations

Aromatic spirocycles are crucial organic scaffolds that are at the forefront of innovation in various fields of organic electronics, as well as in drug design. The synthesis of these compounds is challenging, especially on an industrial scale and often have suboptimal yields in many traditional syntheses. New synthetic methodologies are being continually explored for the installation of sp3 hydridized spiro junctions. Our research group, as well as other groups, have done exploration of using superelectrophilic synthetic routes that are nicely applied to the formation of aromatic spirocycles. Most relevant to the results discussed in this dissertation are condensation chemistry using …

The Investigation Of The Antimicrobial And Biofilm-Disrupting Properties Of Synthesized Hemibastadin Derivatives, Antonio Harvey, Andrew A. Yeagley

Longwood Senior Thesis Proposal

We want to investigate structural changes to the core hemibastadin structure while attempting to make these derivatives biologically safer. Since these modifications have never been done before, we will need to design a synthesis of these new molecules. Due to the nature of the molecules (dimers), a divergent synthesis that allows for the creation of both halves simultaneously seems most appropriate. A successful synthesis of these compounds will allow us to further investigate these derivatives for their antimicrobial and biofilm-disrupting properties.

Synthesis And Characterization Of Colorimetric And Flurometric Chemosensor For Trivalent Metal Ions, Fazila Haque

Honors Program Theses and Research Projects

There are many biological and environmental uses for trivalent metals (like Fe3+, Al3+, and Cr3+) within our daily lives. Whether these trivalent metals are found in deficiency or excess can cause issues within our environment (global warming) or our bodies (can cause problems with our digestive, cardiovascular, and immune systems). Being able to detect them and understanding their importance becomes crucial in our understanding of the world that surrounds us.
/="/">One of the ways we can detect these trivalent metals is through the use of chemosensors. Chemosensors are used to sense analyte (trivalent metal) to produce a signal (fluorescence …

Scandium Triflate-Catalyzed Aromatic Aldehydic C-H Activation, Nicholas Griffin

Honors Projects

Herein described is a scandium triflate-catalyzed C-H activation of commercially available aromatic aldehydes achieved in low yields. The reaction occured in a one-pot synthesis over a two-hour duration and required minimal purification. Inclusion of a fluorine-tagged phenol allowed for reaction monitoring via ¹⁹FNMR.

Design, Synthesis, And Kinetic Study Of The First Generation Phenyloxadiazole Compounds And The Second Generation Phenyloxadiazole Compounds And Highly Selective Hydroboration Of Alkenes, Ketones And Aldehydes Catalyzed By A Well-Defined Manganese Complex, Haisu Zeng

Dissertations, Theses, and Capstone Projects

This thesis focuses on two projects. In the first project, my goal was to discover a new variant of phenyloxadiazole compounds that could exhibit increased thiol-reactivity during bioconjugation processes. To achieve this, I synthesized several phenyloxadiazole derivatives and subjected them to NMR kinetic studies to assess their reactivity with a model thiol. Based on the results, I was able to identify a phenyloxadiazole analog that demonstrated enhanced reactivity, which included a chlorine atom located in the meta-position of the phenyl ring.

I provided a detailed description of the synthesis and characterization of the newly discovered phenyloxadiazole analog and demonstrate its …

Synthesis, Radiolabeling And Evaluation Of A Suite Of Tracers With 44Sc For Detecting Extracellular Dna, Zhiyao Li

McKelvey School of Engineering Graduate Student Theses & Dissertations

Neutrophil extracellular traps involve the rapid translocation of DNA to the outside of the cell under certain stimuli. This structure forms a fibrous network that is able to limit the spread of pathogens and to kill microorganisms. It has also been shown to be present in various pathological processes such as inflammation, autoimmune diseases, and cancer metastasis. Currently, the formation process of NETs in vivo is being extensively studied. However noninvasive detection and quantitation has yet to be achieved. A class of PET tracers are described here that consists of a DNA dye as the backbone that is labeled with …

Green Synthesis Of Glutethimide Intermediate Via Nash Reaction, Zahria Patrick

Undergraduate Research Symposium

The purpose of my research project is to utilize green chemistry principles to synthesize an intermediate for Glutethimide, a drug used to treat patients with insomnia. Many pharmaceutical processes require the use of halide-containing chemicals which are harmful to the environment when discarded as waste. Not only does this waste affect the quality of drinking water and aquatic life, but it affects the economy as well. The cost of waste disposal increases with the increasing difficulty of treating it and thus raises the cost of production for pharmaceutical companies.
The reaction of choice is a nucleophilic aromatic substitution of hydrogen, …

Synthesis And Evaluation Of Sorbicillinoids, Noah Devolve

Honors Program Theses

Sorbicillinoids are a rich family of natural products that have intrigued and inspired scientists since their initial discovery in 1948. A recent report by Zhang et al. detailed the discovery of several new monomeric sorbicillinoids that are particularly interesting as they show nitric oxide (NO) inhibition in RAW264.7 monocyte cell assays and thus possess potential as anti-inflammatory agents. Based on this information, obtaining more of these novel compounds and establishing a preliminary structure activity relationship (SAR) could be achieved by modulating the substitution pattern on the molecules’ benzene ring and varying the alkyl chain length. To this end, a flexible …

Para-Methoxybenzylidene Acetal-Protected D-Glucosamine Derivatives As Ph-Responsive Gelators And Their Applications For Drug Delivery, Jonathan Bietsch, Logan Baker, Anna Duffney, Alice Mao, Mary Foutz, Cheandri Ackermann, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Carbohydrate-based low molecular weight gelators (LMWGs) are compounds with the capability to self-assemble into complex molecular networks within a solvent, leading to solvent immobilization. This process of gel formation depends on noncovalent interactions, including Van der Waals, hydrogen bonding, and π–π stacking. Due to their potential applications in environmental remediation, drug delivery, and tissue engineering, these molecules have emerged as an important area of research. In particular, various 4,6-O-benzylidene acetal-protected D-glucosamine derivatives have shown promising gelation abilities. In this study, a series of C-2-carbamate derivatives containing a para-methoxy benzylidene acetal functional group were synthesized and characterized. These compounds exhibited good …