Chemistry Commons^™

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. …

Development Of Next-Generation, Fast, Accurate, Transferable, And Polarizable Force-Fields For Heterogenous Material Simulations, Adam E. Hogan

USF Tampa Graduate Theses and Dissertations

Theoretical modeling is extremely useful in guiding to experiment; however quantitatively accurate modeling of energy-relevant small molecule sorption at the heterogeneous interfaces present in metal-organic materials (MOMs) is currently challenging. MOMs are an emerging class of materials consisting of inorganic clusters and organic linkers that offer great potential in the areas of gas storage, gas separation, and catalysis due to the possibility of large surface areas, complex heterogeneous surfaces, and rational designability. Efficient chemical separations involving these materials could reduce the US’s total energy consumption by approximately 10 to 15%. In this dissertation, the parameterization of small molecules and metal …

Conversion From Metal Oxide To Mof Thin Films As A Platform Of Chemical Sensing, Meng Chen

USF Tampa Graduate Theses and Dissertations

Chemical sensor is working as a widely used device which can be applied to the detection of specific chemicals that are existing in the environment especially in gas phase. The detection of combustible and toxic chemicals can be extremely important in the field of both industrial and civil activities. The chemical sensor is commonly operating by utilizing a chemical or physical interaction between the specific chemical compound and the sensing functional unit, to obtain an electronic signal caused by the property change and realize the chemical detection. Traditional chemical gas sensors such as catalytic gas sensor, thermal conductivity gas sensor, …

The Development Of Aapeptides, Lulu Wei

USF Tampa Graduate Theses and Dissertations

Non-natural peptide mimics are referred to as peptidomimetics, which contains unnatural backbones that mimic the primary peptide structure. There are a large number of peptidomimetics that have been developed including α-peptides, β-peptides, peptoids, arylamide oligomers, cationic polymers, and other peptidomimetics in the last decades. Compared to conventional peptides, these peptidomimetics have many advantages such as resistance to proteolysis, improved bioavailability, and reduced immunogenicity. However, the development of peptidomimetics is still far below the expectation due to the limitation of the availability of backbones. It is an urgent need to generate a new diverse library for novel drug discovery, design antimicrobial …

Multifunctional Metal-Organic Frameworks (Mofs) For Applications In Sustainability, Gaurav Verma

USF Tampa Graduate Theses and Dissertations

Climate change, affordable and clean energy, and responsible consumption and production are some of the important goals to be achieved for sustainable development. The current technologies used to address these challenges are energy and resource intensive. Furthermore, there are various limitations related to cost, storage, scalability and safety.Adsorbent materials are seen as a promising alternative remediation system due to their low energy consumption and minimal chemical waste production. However, most of the traditional adsorbents, such as activated carbon and zeolites lack the structural tunability to have long-term effectiveness and their use is limited. As discussed in Chapter 1, metal organic-frameworks …

Sustainable Non-Noble Metal Based Catalysts For High Performance Oxygen Electrocatalysis, Swetha Ramani

USF Tampa Graduate Theses and Dissertations

Current energy crisis has dramatically shifted the focus of technological advancements towards clean and renewable forms of energy. Continued dependence and utilization of fossil fuels has created global awareness on harmful greenhouse gas emissions and climate change. A need for sustainable technology has gained a lot of significance in the recent years. This has led to the development of devices and technologies that rely on environmentally friendly electrochemical conversion and storage of energy. One such advancement that generates electrical energy from chemical reactions is known as fuel cell technology. While fuel cells have demonstrated potential in replacing the conventional technologies …

Design, Synthesis Of Axial Chiral Triazole, Jing Wang

USF Tampa Graduate Theses and Dissertations

This thesis contains three parts: 1) The briefly review of chiral P, N-ligands. 2) The summary of triazole as ligands. 3) The attempt of designing, synthesizing the chiral triazole ligands.

In the first part, we have reviewed all the major P, N-ligands in the history, including how they were synthesized and resolved into single enantiomer. We also used some examples to show their utility potential in different reactions.

In the second part, we summarized the triazole ligands which mainly developed by our group including their structures, their potential and utility in different types of chemical reactions.

In the last part, …

Covalent Organic Frameworks As An Organic Scaffold For Heterogeneous Catalysis Including C-H Activation, Harsh Vardhan

USF Tampa Graduate Theses and Dissertations

Linking small organic molecules into an extended solid usually afford disordered amorphous polymers. The instigation of order into such a material is of profound interest to induce inherent fine control of the overall structure. Covalent organic frameworks (COFs) are new class of porous crystalline material prepared by connecting organic building blocks via strong covalent bonds. The judicious choice of organic monomers can give rise to highly ordered and predictable frameworks with high crystallinity, surface area, and thermal/chemical stability. The role of connecting linkages such as B─O, C─C, C─N extends the principle of fundamental molecular covalent chemistry to the formation of …

Development Of Ultrasonic-Based Ambient Desorption Ionization Mass Spectrometry, Linxia Song

USF Tampa Graduate Theses and Dissertations

Ambient desorption/ionization techniques (ADI) have drawn significant attention in mass spectrometric instrumentation development. The analyte classes that are successfully studied by any ADI mass spectrometry (MS) method strongly depends on how gas-phase ions are generated. Spray-based techniques may ionize molecules across a wide range of mass-to-charge ratios, but are commonly used for polar analyte, however, suffers from severe matrix effect. Contrastingly, methods employing electric (or laser) plasmas are capable of ionization of polar and nonpolar analytes suffering from less matrix effect, but primarily targeting those with low molecular masses. Thus far, developments of universal ionization methods, which do not depend …