Chemistry Commons^™

Advanced Analytical Method Development: From Highly-Enrolled Classroom To Data-Intensive Proteomics, Laxmi Sinduri Vuppala

USF Tampa Graduate Theses and Dissertations

In analytical chemistry, method development is key to identifying, separating, and quantifying chemical components of interest systems. The chemical aspects are fundamental to understanding the subject of any analytical system, whether in academic research, industry, or government. These methodologies serve as a bridge between the classroom, where students are taught to be curious and enlightened, and research, where one strives to contribute. The Ph.D. dissertation integrates advanced methodologies in basic and applied research and advanced instrumentation, but the core criteria for validation remain the same. As part of chemical education curriculum development, a large cohort of undergraduates performed two gas …

Large Area Projection Sintering Of Semicrystalline Polymers And Part Analysis Of The Printed Specimens, Taranjot Kaur

USF Tampa Graduate Theses and Dissertations

As the requirements posed to products have increased in recent years. The trend towards individualized serial products steps up the need for respective manufacturing techniques to be more and more flexible. Conventional techniques of serial production, such as injection molding, are unable to fully meet the requirements of this trend. Additive manufacturing techniques generate components directly from a CAD data set while requiring no specific mold, producing minimal waste, and reaching satisfactory geometric accuracy. This is how, as opposed to conventional techniques, they comply with these increased demands to processing technology. Over the last two decades, the research community has …

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 …

Improved Performance Of Silica-Supported La0.5Ba0.5Feo3 In The Reverse Water Gas Shift - Chemical Looping Process For Carbon Dioxide Reduction – A Density Functional Theory Study, Jiawei Guo

USF Tampa Graduate Theses and Dissertations

Global warming is increasingly obvious, and the reduction of greenhouse gases is an effective way to heal. Increasing the efficiency of catalysts that is applied in the industry can significantly reduce the emission of greenhouse gases. Reverse water gas shift chemical looping (RWGS-CL) is a promising reaction to convert CO2 to CO. La0.5Ba0.5FeO3 (LBF) is a good candidate for RWGS-CL, which shows increased conversion yield when supported on silica. This research focuses on identifying the mechanism of RWGS-CL via silica-supported LBF by exploring the oxygen vacancy formation energy (EO-vac). Density Functional Theory (DFT) is a powerful computational method to solve …

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 …

Synthesis And Antibacterial Testing Of Novel Thiosulfonate Compounds, Lindsay I. Blume

USF Tampa Graduate Theses and Dissertations

Methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Staphylococcus aureus (VRSA) are increasing concerns in the medical community. In addition to the threat of Staphylococcus aureus, the increase in number and severity of infections caused by other antibiotic-resistant bacteria is problematic to human health, particularly among the ESKAPE pathogens (Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter). The antibiotics like the penicillins and cephalosporins used commonly to treat MRSA, VRSA, and ESKAPE pathogens have continued to decline in the effectiveness. Our laboratory has developed a number of new families of anti-MRSA and anti-VRSA antibacterial compounds. In this thesis, …

An Investigation Into The Protein Dynamics And Proton Transfer Mechanism Of Class-A Β-Lactamase (Ctx-Ms) By Nmr Spectroscopy, Radwan Ebna Noor

USF Tampa Graduate Theses and Dissertations

Extended-spectrum β-lactamases (ESBLs) of different Enterobacteriaceae (e.g. Escherichia coli, Klebsiella pneumoniae) have developed significant resistance mechanisms against antibiotics. ESBLs, like class A CTX-Ms (cefotaximases) enzymes hydrolyze the β-lactam ring of different antibiotics such as penicillins and third-generation oxyimino-cephalosporins. Although CTX-Ms are repeatedly found in many clinical and community settings, molecular-level information on their function/activity is currently limited to structural studies performed by X-ray crystallography. In order to gain further insights into the structure and functions of this class of proteins, it is also essential to fully understand their dynamic and chemical properties in solution. In order to better understand the …

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 …

Measuring And Improving Student Attitude In College-Level Chemistry: A Novel Survey Methodology And Social-Psychological Interventions, Ying Wang

USF Tampa Graduate Theses and Dissertations

Students’ attitude has been an important focus in the chemistry education community. However, there is a lack of research in evaluating interventions aiming to improve students’ attitude. Social-psychological interventions (SPIs), brief interventions that target students’ subjective experiences, were demonstrated to improve students’ attitude in instructional settings. In addition, accurately measuring students’ attitude helps researchers better understand the impact of the intervention. Therefore, the major goal of this work is to explore practices, particularly a novel survey methodology and a social-psychological intervention (SPI), to facilitate measuring and improving students’ attitude in college-level chemistry courses. This work also paid particular attention to …

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 …

Understanding Students’ Global Interdependence In Science Instruction, Walter S. Smith

Journal of Global Education and Research

Multiple American educational organizations such as the National Education Association, Association for Supervision and Curriculum Development, and the Council of Chief State School Officers have advocated for globalizing the K-12 curriculum. The National Science Teaching Association (NSTA) in a position statement on international education and the Next Generation Science Standards have produced goals and standards for internationalizing the science curriculum by addressing topics such as climate change, environment, and disease that cross borders. In contrast to those pronouncements on the curriculum, this article views global science education through an instructional lens that focuses on a students’ global interdependence in science …

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 …

Vermiculations In Painted Caves: New Inputs From Laboratory Experiments And Field Observations, Perrine Freydier, Eric Weber, Jérôme Martin, Pierre-Yves Jeannin, Béatrice Guerrier, Frédéric Doumenc

International Journal of Speleology

Vermiculations are aggregates of small particles commonly found on cave walls. They are a major concern for the conservation of painted caves, as they can potentially alter valuable prehistoric cave paintings. A previous rheological study of fine sediment deposits on cave walls revealed that this material can undergo a solid-to-liquid transition triggered by variations in the chemical composition of the water film on the wall. Such a transition could occur at the origin of vermiculations by allowing the sediment to flow under low mechanical stress. In this work, we provide quantitative information on the conditions leading to this transition and …

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 …

Prospective Chemistry Teachers’ Evaluations About The Instruction Of The Graphic Organizers Course, Canan Nakiboglu

University of South Florida (USF) M3 Publishing

Graphic organizers (GOs) are visual teaching and learning tools that provide an organized expression of knowledge by explaining concepts and events. If the teachers incorporate the GOs into their lessons as instructional material and assessment tools, they can make the teaching period more effective and also help their students' understanding of the chemistry subjects. In this study, the prospective chemistry teachers (PCTs) attended a Graphic Organizers Course, and then their opinions regarding the evaluation of the course were taken. A total of 43 PCTs, 32 female and 11 male, who took the course in four different semesters, participated in this …

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 …

Preparation And Characterization Of Single Layer Conducting Polymer Electrochromic And Touchchromic Devices, Sharan Kumar Indrakar

USF Tampa Graduate Theses and Dissertations

Electrochromic devices (ECDs) have triggered great interest because of their potential applicability in energy-efficient buildings and low power display systems, including reflective type smart windows/mirrors and wearable-flexible devices. In the past decades, electrochromic technologies with different device structures and materials have been proposed. The idea of employing a simple device structure with a durable, cost effective electrolyte is crucial to designing and manufacturing high-performance ECDs. With this idea in mind, this thesis describes the various efforts to develop a simple ECD comprising of a composite single active layer gel electrolyte, sandwiched between two transparent conducting electrodes, lasting over 10,000 cycles …

Novel Synthetic Ketogenic Compounds, Michael Scott Williams

USF Tampa Graduate Theses and Dissertations

The ketogenic diet has grown in popularity in the last decade as a weight loss tool. Research into the diet’s effects on the body have revealed a variety of other health benefits. The use of exogenous ketone supplements to confer the benefits of the diet without strict adherence to it represents an exciting new area of focus. Synthetic ketogenic compounds are of particular interest that has received very little emphasis and is an untapped area of focus for chemical synthesis.

The first chapter of this manuscript provides an overview of the history of the ketogenic diet along with a summary …

Design, Synthesis And Testing Of Bioactive Peptidomimetics, Sami Abdulkadir

USF Tampa Graduate Theses and Dissertations

Proteins are complex macromolecules that are responsible for almost all biochemical processes and play vital roles in signaling pathways, metabolic pathways, and all other cellular functions. Proteins accomplish this by interacting with other proteins and macromolecules like DNA and RNA, for instance, as transcription factors. As such, we can find protein interactions behind every cellular action or inaction, and it is easy to see how protein interactions are crucial in understanding disease processes. Advance in proteomics has particularly provided a wealth of insights into molecular mechanisms of disease processes of cancers and other rare diseases, which has helped identify key …

Parallel Computation Of Feynman Path Integrals And Many-Body Polarization With Application To Metal-Organic Materials, Brant H. Tudor

USF Tampa Graduate Theses and Dissertations

The Space Research Group is a computational outfit, and so the work presented herein will reflect that. Much of our simulation code is developed in-house and so what follows is a small exploration of that development—although the physics underpinning our software development is never ignored for long. Following the programming centric work, the code and the physics are put to the test. The final chapter describes a scientific endeavor in which a new, robust force field has been validated. Indeed, the new potential has taken a first step in proving itself by making accurate predictions in what have historically found …

Synthesizing Laccol Based Polymers/Copolymers And Polyurethanes; Characterization And Their Applications, Imalka Marasinghe Arachchilage

USF Tampa Graduate Theses and Dissertations

In modern world research scopes are highly favored the areas of developing new polymer materials which are more integrated with the environment. Synthesizing eco-friendly, bio degradable polymer materials to replace petroleum based synthetic polymers to utilize in radiation hard applications is one of the main objectives of this study. 'Laccol' extracted from Vietnamese lacquer tree (Toxicodendron succedanea) polymerized with other monomers namely styrene and d-limonene (from citrus waste) respectively to develop copolymers via cationic polymerization. Laccol contains hydroxyl phenyl groups that act as radical scavengers, enhancing radiation resistance via their ability to convert excitation energy into non-chemistry inducing energy in …

An Investigation Of Cross-Links On Crystallization And Degradation In A Novel, Photocross-Linkable Poly (Lactic Acid) System, Nicholas Baksh

USF Tampa Graduate Theses and Dissertations

Polymeric molecular structure consists of repeating units bonded together. Mechanicalproperties can be altered without affecting chemical makeup by altering the number of these units. Small molecules can be introduced and/or polymers can be modified to form bonds between molecular chains. Cross-linking, as this is called, also introduces mechanical variation with minimal effects on chemical composition. Lastly, polymer chains reorient themselves in response to intermolecular forces. This temperature dependent response is known as crystallization. Although chemistry is unaltered, mechanical properties can depend highly on the percent of the sample that is crystallized.

Cross-linking is known to enhance the mechanical properties of …

Using Quantitative Methods To Investigate Student Attitudes Toward Chemistry: Women Of Color Deserve The Spotlight, Guizella A. Rocabado Delgadillo

USF Tampa Graduate Theses and Dissertations

The field of Chemistry Education Research (CER) has been interested in understanding the reasons why students struggle in organic chemistry courses. Reports show that students perceive the material as difficult and have trouble keeping pace with the volume of content taught within the course. Beyond these and other explanations of why students struggle in organic chemistry are affective factors, such as attitude toward chemistry, that influence students’ success and retention in this course. Studies have shown that in many instances, underrepresented groups of students report less positive attitudes than their peers. Of greater concern are the students representing multiple marginalized …

Simulations Of H2 Sorption In Metal-Organic Frameworks, Shanelle Suepaul

USF Tampa Graduate Theses and Dissertations

Metal-organic frameworks are a diverse group of crystalline materials consisting of metal ionscoordinated to organic ligands. Their characteristic high porosity, large surface area along with tunable pore structures and chemical functionalities make them an exceptional candidate for H2 storage applications. Computational studies of H2 sorption in metal-organic frameworks aid in producing molecular-level insights which can facilitate the design of structures with improved performance. In this work, various MOFs were investigated using grand canonical Monte Carlo simulations.

Addressed first are two MOFs with rht topologies which consist of two chemically distinct Cu2+ ions coordinated to triisophthalate ligands. Through electronic structure calculations …

Biosynthetic Gene Clusters, Microbiomes, And Secondary Metabolites In Cold Water Marine Organisms, Nicole Elizabeth Avalon

USF Tampa Graduate Theses and Dissertations

Microorganisms and invertebrate animals from cold water marine environments, such as in Antarctica and in Ireland’s deep sea, are a rich source of secondary metabolites. In this dissertation, research was centered around secondary metabolism and natural product biosynthesis. The projects include the delineation of biosynthetic gene clusters hypothesized to be responsible for the biosynthesis of the palmerolides, stratification of the microbiome of the Antarctic ascidian Synoicum adareanum, genomic and peptidomic analysis of a host-associated Antarctic Pseudovibrio sp., and isolation and characterization of secondary metabolites from the Irish deep-sea coral Drifa sp.

Palmerolide A, the principle secondary metabolite associated with S. …