Physical Sciences and Mathematics Commons^™

Syntheses, Photophysics, & Application Of Porphyrinic Metal-Organic Frameworks, Zachary L. Magnuson

USF Tampa Graduate Theses and Dissertations

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface …

Synthetic Studies Of Potential New Ketogenic Molecules, Mohammad Nazmus Sakib

USF Tampa Graduate Theses and Dissertations

The ketogenic diet has gained popularity in the past few decades among people and physicians due to its various health benefits. A significant amount of research has been done for the modification of the original ketogenic diet and investigation of its potential health benefits. However, synthesis of novel ketogenic compounds as a dietary supplement has not received the same level of attention. That is the primary objective of this research project. The first chapter of this manuscript describes the synthesis of various short and medium chain esters of different polyols that have been done so far, and areas of their …

Coupling Chemical And Genomic Data Of Marine Sediment-Associated Bacteria For Metabolite Profiling, Stephanie P. Suarez

USF Tampa Graduate Theses and Dissertations

Marine sediment-associated bacteria house many new and exciting novel secondary metabolites. These metabolites can be tested for bioactivity against various types of cancer and fungal, bacterial, and viral infections. In this thesis, we investigated the combination of biosynthetic gene cluster information with mass spectra to perform a chemical profiling of sediment- associated bacteria. Furthermore, we utilized a scoring technique to provide an identification and confidence score to each annotated compound. The sediment was collected from east Arthur Harbor, Palmer Station, Antarctica, at depths of 20 ft and 60 ft. After plating on agar, 52 unique bacterial strains were isolated, with …

Developing New Strategy Toward Ruthenium And Gold Redox Catalysis, Chenhuan Wang

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) The discovery of triazole-modified Ru carbene catalysts for alkene metathesis and dynamic covalent chemistry; 2) The study of ligand assisted gold oxidative addition toward aryl iodide to achieve the alkene difunctionalization; 3) Gold redox catalysis via chiral P,N-chelating ligands. In the first part, the 1,2,3-triazole coordinated ruthenium carbene complexes (TA-Ru) were reported for the first time as a new class of modified Grubbs catalyst to achieve challenging olefin metathesis at higher temperatures without catalyst decomposition. With this new TA-Ru catalyst, cross-metathesis (CM), ring-closing metathesis (RCM) and dynamic covalent chemistry (DCvC) were achieved. The …

Affordances And Limitations Of Molecular Representations In General And Organic Chemistry, Ayesha Farheen

USF Tampa Graduate Theses and Dissertations

Molecular representations that show chemical bonding are ubiquitous in general and organic chemistry. These help in communicating chemistry concepts that are fundamental to understanding how and why molecules interact. The goal of this dissertation work is to offer an evidence-based report on the affordances and limitations of the variety of molecular representations by chemistry topic. The variety of representations investigated are chemical formula, Lewis dot structure, line-angle diagram, ball and stick, space filling, and electrostatic potential maps. Five studies were conducted with general and organic chemistry students and three key findings emerged. First, affordances and limitations of molecular representations are …

Chemical Analysis Of Metabolites From Mangrove Endophytic Fungus, Sefat E Munjerin

USF Tampa Graduate Theses and Dissertations

Natural products hold a significant place in drug discovery for their abundant and unique secondary metabolites. These secondary metabolites which encompass a range of organic compounds such as alkaloids, phenols, peptides, flavonoids, polyketides, and terpenoids, can easily be exploited for drug development. Endophytic fungi, residing harmoniously with its host, have emerged as generous producers of bioactive secondary metabolites, displaying efficacy against a wide array of human pathogens, including the challenging ESKAPE pathogens.

The research explores endophytic fungi and their prospective for drug discovery and development through the synthesis of distinctive secondary metabolites. Endophytic fungus, HM13-26C-2B, collected from Honeymoon Island, Florida …

Development Of Antiviral Peptidomimetics, Songyi Xue

USF Tampa Graduate Theses and Dissertations

Protein-protein interactions (PPIs) are essential for biological processes and are associated with a number of diseases, including cancer, infectious diseases, and neurodegenerative diseases. As a result, modulation of PPIs has been recognized as one of the most promising strategies to develop the novel drugs. Peptide modulators always exhibit higher specificity and affinities with targets than small compounds or monoclonal antibodies, but their broad medicinal effectiveness is constrained by their poor bioavailability and biostability. Peptidomimetics, which have been developed to mimic the structure as well as function of bioactive peptides and proteins, have shown excellent potential in protein surface mimicry and …

Synthesis Of Small Molecule Modulators Of Non-Traditional Drug Targets, Jamie Nunziata

USF Tampa Graduate Theses and Dissertations

This work details the effort toward structure-activity-relationship (SAR) studies and synthesis of the small molecule modulators of two non-traditional drug targets. The first part of this manuscript (chapters 1–2) will discuss the collaborative work and synthesis of an inhibitor of Slingshot Homology 1 (SSH1) with the potential therapeutic application toward Alzheimer’s Disease (AD) treatment. The second part (chapters 3–6) will discuss the synthetic efforts toward modulation of a protein target known as STING, or stimulator of interferon genes, with the therapeutic application toward autoimmune disease or anti-tumor activity.

AD is a progressive and degenerative illness that holds the title of …

Applications In Opioid Analysis With Faims Through Control Of Vapor Phase Solvent Modifiers, Nathan Grimes

USF Tampa Graduate Theses and Dissertations

Field Asymmetric Ion Mobility Spectrometry (FAIMS), often coupled with mass spectrometry (MS), offers rapid analytical ion filtration, useful in reducing matrix interference and differentiating isomeric compounds. This study focuses on augmenting FAIMS-MS analyses through the incorporation of gas phase solvents, or "modifiers," inducing dynamic microsolvation, a particularly potent method of analysis enhancement.

Initially, the research utilized a bubbler-based system, incorporating a humidity sensor, improving modifier concentration control when using water. Our application in opioid detection and differentiation revealed considerable advancements. Notably, an increased peak capacity in an opioid mixture and successful separation of the isobaric opioid pair, alfentanil and ortho-isopropyl …

Synthesis, Characterization, And Separation Of Loaded Liposomes For Drug Delivery, Sandra Khalife

USF Tampa Graduate Theses and Dissertations

Liposomes are viable candidates for drug delivery vehicles due to their ability to protect loaded compounds, dampen side effects of drugs, and be delivered to target sites in the body. The amphipathic nature of these lipid vesicles makes them very customizable through careful selection of bilayer and aqueous core components as well as synthetic and downsizing methods. However, synthetic methods may result in unencapsulated compounds remaining present alongside loaded liposomes, which require removal before the liposome suspension can be used.

This work explores the use of model DOPC as well as DOPC and CHOL liposomes and the methods that were …

Investigation Of Challenging Transformations In Gold Catalysis, Qi Tang

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) Divergent gold catalysis for alkyne trifunctionalization, encompassing three distinct modes to achieve the simultaneous formation of C-N, C-O, and C-C bonds in a single step 2) the study and development of a new method to synthesize azaborine derivatives; and 3) the construction of benzotriazole boranes (BTAB) as stable four-coordinate N-B heterocycles through gold-catalyzed alkyne hydroboration.

In the first part, alkyne trifunctionalization via divergent gold catalysis will be introduced. This novel approach involves a sequence of reactions that combine gold π-activation, vinyl gold nucleophilic addition, and gold (III) reductive elimination. By utilizing this methodology, …

Gold-Catalyzed Diyne-Ene Cyclization: Synthesis Of Hetero Polyaromatic Hydrocarbons And 1,2-Dihydropyridines, Jingwen Wei

USF Tampa Graduate Theses and Dissertations

Homogeneous gold catalysts are known as a powerful tool for selectively activating alkynes and are well-developed in the construction of C-C, C-N, and C-O bonds to form complex compounds that are widely used in pharmaceuticals, industries, agriculture, etc. The investigation of gold(I) catalysis on conjugated diyne (compounds having two acetylene groups) enriches the complexity of the bond construction and allows the building of interesting skeletons in organic synthesis. One typical kind of substrate, diyne-ene, has both a conjugated diyne part and a 1,6- enyne part. We developed a new methodology to allow its divergent synthesis to heterocycles.

This dissertation mainly …

Supramolecular Architectures Generated By Self-Assembly Of Guanosine And Isoguanosine Derivatives, Mengjia Liu

USF Tampa Graduate Theses and Dissertations

This dissertation is primarily divided into three parts: 1) Anion, solvent-mediated, tunable self-assemblies of isoguanosine (isoG). 2) Post-assembly modification of the non-covalent isoG-pentaplex for Cesium extraction. 3) Supramolecular asymmetric amine catalysis.

The structural conformational design of the isoG decamer was employed for systematic investigations involving various substituted groups at the C8 position of purine and ribose. A series of isoG analogs with C8-phenyl substitutions were synthesized and utilized for Cesium coordination. The proximity between purine and ribose structures limited pentaplex formation for C8-phenyl substituted isoG derivatives. Based on this observation, a deoxy isoG derivative with a modified ribose was employed …

Enhanced Methods In Forensic Mass Spectrometry For Targeted And Untargeted Drug Analysis, Dina M. Swanson

USF Tampa Graduate Theses and Dissertations

Forensic science has long used mass spectrometry for the analysis of drugsand metabolites. Traditionally, screening methods consisted of color tests or immunoassay and confirmation methods used gas chromatography with mass spectrometry, which was considered the gold standard for identification. In the last several decades, advances in liquid chromatography with mass spectrometry (LCMS) have brought this technology to the forefront of forensic drug identification. Drug identification in forensic drug chemistry and forensic toxicology has become increasingly challenging due to the rapid increase in illicit drug analogs including novel opioids such as fentanyl analogs. Traditional screening methodologies are often unable to identify …

Apkcs Role In Neuroblastoma Cell Signaling Cascades And Implications Of Apkcs Inhibitors As Potential Therapeutics, Sloan Breedy

USF Tampa Graduate Theses and Dissertations

Neuroblastoma (NB) is a cancer that develops in the neuroblasts. It is the most common cancer in children under the age of 1 year, accounting for approximately 6% of all cancers. The prognosis of NB is linked to both age and degree of cell differentiation. This results in a range of survival rates for patients, with outcomes ranging from recurrence and mortality to high survival rates and tumor regression. Our previous work indicated that PKC-ι promotes cell proliferation in NB cells through the PKC-ι/Cdk7/Cdk2 cascade. We report on two atypical protein kinase inhibitors as potential therapeutic candidates against BE(2)-C and …

Diazirines And Oxaziridines As Nitrogen Transfer Reagents In Drug Discovery, Khalilia C. Tillett

USF Tampa Graduate Theses and Dissertations

Synthetic organic chemistry has long served as a driver of innovation in the drug discovery and development process. Given the prevalence of the nitrogen atom in small molecule drugs, improved methods for C–N bond installation are in high demand. Heteroatom transfer reagents such as oxaziridines and diazirines can be used to selectively deliver nitrogen atom(s) to organic compounds. Herein, I’ll describe my work utilizing Armstrong’s oxaziridine (TBDOT) in peptide backbone modification, and diazirines (TPD) in the development of a hydroamination reaction.

Peptide backbone N-amination has emerged as an attractive peptidomimetic strategy in the design of amyloid aggregation inhibitors. In addition …

Study On New Strategy Toward Gold(I/Iii) Redox Catalysis, Shuyao Zhang

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) the study of ligand assisted gold oxidative addition toward aryl iodide to achieve the alkene difunctionalization. 2) The selective arylation reaction via electrochemical anode oxidation promoted gold redox chemistry. 3) The π acid reactivity of gold redox chemistry under electrochemistry conditions.

In the first part, the gold-catalyzed intermolecular oxyarylation of alkene is reported. This work employed the oxidative addition of aryl iodide to Me-DalphosAu+ for the formation of Au(III)-Ar intermediate. The better binding ability of alkene over O nucleophiles ensured the success of intermolecular oxyarylation, giving desired products with broad substrate scope and …

Measurement In Chemistry, Mathematics, And Physics Education: Student Explanations Of Organic Chemistry Reaction Mechanisms And Instructional Practices In Introductory Courses, Brandon J. Yik

USF Tampa Graduate Theses and Dissertations

The work in this dissertation is presented in two parts. The first part (Chapters 3 and 4) details work relating to students’ explanations of reaction mechanisms in organic chemistry. The second part (Chapters 5 and 6) details work relating to the evaluating the uptake of research-based instructional practices in introductory chemistry, mathematics, and physics courses.

To evaluate learning of organic chemistry reactions, instructors must ask students to construct written explanations of reaction mechanisms. Written assessments should focus on what is happening and why it is happening to promote deeper student understanding. However, for instructors to gain insight into students’ understanding, …

A Protein-Based Therapeutic Combination For The Treatment Of Hard-To-Heal Wounds, Graham L. Strauss

USF Tampa Graduate Theses and Dissertations

Chronic wounds present many clinical challenges in relation to the successful treatment and closure of the damaged tissue. Most current treatment methods focused on one or two aspects to drive wound closure, while most chronic wounds are multifactorial environments with many of those dependencies relying on the termination of one another to effectively gain tissue construction, closure, and full skin thickness and composition. Natural wound healing processes allude to potential biologics that can impede the chronic breakdown of tissue, while restoring deposition of new tissue, and effectively leading to a healed wound. Proteases secreted by the body’s immune system lay …

Metabolomic Analysis, Identification And Antimicrobial Assay Of Two Mangrove Endophytes, Stephen Thompson

USF Tampa Graduate Theses and Dissertations

Natural products have played major roles in drug discovery and provided sources for many new drugs. Secondary metabolites, also called natural products, are organic compounds that are produced from fungi, bacteria, and other living organisms. Secondary metabolites produced by endophytic fungi include alkaloids, phenols, peptides, enzymes, polyketides, and terpenes. Endophytic fungi are rich sources of secondary metabolites and demonstrate bioactivity against many human pathogens including the ESKAPE pathogens. This thesis explores the diverse roles of endophytic fungi and their production of unique secondary metabolites for potential drug discovery and development. Secondary metabolites from two endophytic fungi (EG10-21E-2-HDAC & TAP14-34A-2-HDAC), collected …

Bioactivity Of Suberitenones A And B, Jared G. Waters

USF Tampa Graduate Theses and Dissertations

Throughout human history, natural products have formed the foundation of medicine. In ancient times, a myriad of herbs and fungi have been attributed properties of healing and rejuvenation. Today, that foundation still very much exists, as natural product chemists isolate bioactive compounds from plants, fungi, animals, and microorganisms alike. As more of these secondary metabolites are discovered, scientists pursue more and more sources of biodiversity that may yield new and unprecedented compounds. To this end, Antarctica has become of particular note, as its unique environmental conditions and highly isolated nature make for rare and unusual adaptations in its native wildlife. …

Block Copolymer Directed Self-Assembly: Exploring The Efficacy Of Applications In Semiconductor Fabrication, Jakin Bryce Delony

USF Tampa Graduate Theses and Dissertations

Over the course of the past 80 years, semiconductor devices have become increasingly ubiquitous in everyday life.From constructing mainframes that encompassed entire rooms during the 1940s, to inventing personal computers in the 1980s, to developing progressively faster smartphones and wearable technology in the 2010s, the primary driving force behind the Digital Revolution has been increasing transistor counts, and thus computing power, via incremental improvements in optical lithography. In 1965, Intel co-founder Gordon Moore boldly predicted that the transistor density of semiconductor devices would double approximately every 18-24 months. While this prediction -- now colloquially referred to as Moore's Law -- …

Exploring The Structure And Activity Of Metallo-Tetracyclines, Shahedul Islam

USF Tampa Graduate Theses and Dissertations

Copper as a key component of electron transport chain of eukaryotes is an essential transition metal ion. Copper homeostasis in mammals complex and tightly regulated. Its strong reactivity together with binding with biologically important chemicals can have important repercussions in human health and overall environment. Tetracycline as one of most abundantly used antibiotic of the world has become abundant in the environment as well. Herein in this dissertation we take the journey to explore the complexation of tetracycline with metals in the environment and the intricate interaction between copper and tetracycline by investigating their oxidative behavior once they are complexed. …

Study On New Reactivity Of Vinyl Gold And Its Sequential Transformations, Teng Yuan

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) the study of new reactivity of vinyl gold(I) and synergistic gold-iron catalyzed regioselective crossed aldol reaction. 2) synergistic gold-iron catalyzed amide crossed aldol reaction by using ynamides as ‘masked’ amides. 3) alkyne trifunctionalization via divergent gold catalysis: combining three modes of gold catalysis: π activation, nucleophilic addition of vinyl gold and gold redox catalysis. This novel method affords access to constructing C-N, C-O and C-C bond in one step at mild condition.

In the first part, a new reaction mode in gold catalysis will be introduced. Due to the protodeauration of vinyl gold …

Developing Efficient Transition Metal Catalyzed C-C & C-X Bond Construction, Chiyu Wei

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) The synergistic Pd/enamine catalysis for asymmetric hydrocarbon functionalization of unactivated alkenes with ketones; 2) Gold redox catalysis with a selenium cation as mild oxidant; 3) HFIP promoted disulfidation and diselenation of alkyne, alkene, and allene.

Palladium-catalyzed alkene activation has its intrinsic limitation: 1) the requirement of a pre-functionalized alkene to form a Pd π-allyl complex; 2) problematic reversible β-H elimination. It always leads to limited reaction scope and losing of the stereochemical control. Synergistic palladium and enamine catalysis was conducted to promote ketone addition to unactivated olefins. A secondary amine-based organocatalyst was identified …

The Photophysical Studies Of Transition Metal Polyimines Encapsulated In Metal Organic Frameworks (Mof’S), Jacob M. Mayers

USF Tampa Graduate Theses and Dissertations

Light harvesting systems provide a platform that converts solar energy into other forms of energy. One of the most common examples of photon capturing and conversion into chemical energy is observed in photosynthetic organisms in both Eurkaroyic and Prokaryotic domains. Nature provides a model for successful light harvesting platforms which includes the compartmentalization of antenna complexes that contain separated donor and acceptor pairs that participate in efficient electron transfer processes. In order to mimic such systems, crystalline porous materials that exhibits regular cavities and pore dimensions provides an excellent starting place. Metal organic frameworks (MOFs) are a class of porous …

Investigation Of Immobilized Enzymes In Confined Environment Of Mesoporous Host Matrices, Xiaoliang Wang

USF Tampa Graduate Theses and Dissertations

Enzyme immobilization in metal-organic frameworks (MOFs) as a promising strategy, is attracting the interest of scientists from different disciplines with the expansion of MOF’s development. Different from other traditional host materials, their unique strengths of high surface areas, large yet adjustable pore sizes, functionalizable pore walls, and diverse architectures make MOFs an ideal platform to investigate hosted enzymes, which is critical to the industrial and commercial process. In addition to the protective function of MOFs, the extensive roles of MOFs in the enzyme immobilization are being well-explored by making full use of their remarkable properties like well-defined structure, high porosity, …

Effects Of Nitrate On Arsenic Mobilization During Aquifer Storage And Recovery, Hania Hawasli

USF Tampa Graduate Theses and Dissertations

Aquifer storage and recovery technology is used to sustain water resources and to prevent saltwater intrusion. The injected water can come from various resources, including treated wastewater. In pilot ASR studies in the Tampa Bay region, researchers found high As concentrations in the recovered water from the oxidation of the arsenopyrite that is embedded in the aquifers. The presence of dissolved O2 in the injected water is a major factor in the arsenopyrite oxidation during ASR, however the effects of NO3- on the arsenopyrite has not been studied yet. This is an important knowledge gap because injected water may contain …

Social Constructivism In Chemistry Peer Leaders And Organic Chemistry Students, Aaron M. Clark

USF Tampa Graduate Theses and Dissertations

Social constructivist learning is a goal in many STEM programs. The goal of this dissertation is to shed light on what that pedagogy looks like in the context of organic chemistry courses and by peer leaders whose job is to implement this pedagogy with general chemistry and organic chemistry students. Learning is complex; the social constructivist ideas presented in this dissertation, however, are a straightforward means for promoting learning. Qualitative and quantitative methods used to explore social constructivist learning are outlined.

Three investigations were conducted: First, approaches to learning by students completing the first semester of a yearlong organic chemistry …

Synthesis Of Small Molecules For The Treatment Of Infectious Diseases, Elena Bray

USF Tampa Graduate Theses and Dissertations

Drug discovery’s impact on modern healthcare cannot be measured. In the past year, the world has watched scientists all around the globe work together to help protect the public from the novel coronavirus pandemic. Although sometimes slow and costly, drug discovery is important for advancing modern society. Drug discovery is at the core of treating diseases and in particular, infectious diseases. In the first chapter an overview of drug discovery will be discussed in a brief manner.

The second chapter will introduce infectious diseases. In modern society, the development of small molecule treatments for treating bacteria, viruses, and fungi has …