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Studies Of Novel And Well-Defined Dinickel Architectures Utilizing An N-Atom Bridge, David Anthony De Los Santos

Theses and Dissertations

There has been a growing interest in organometallic chemistry to utilize late Earth-abundant metals towards challenging molecular functionalization of abundant feedstocks to value-added products. There is precedent of utilizing cooperativity to try and address some of the shortcomings of traditional mononuclear complexes by integrating metal-metal and or metal-ligand cooperativity to facilitate multi-electron transformations. The utility of a redox-noninnocent scaffold allows for the metal centers to be stable over a range of oxidation states, using the ligand to store electrons. Despite recent progress, complexes harnessing cooperative states towards challenging transformations is still an emerging field. Our group has synthesized a multinucleating …

Synthesis Of Nano-Microstructured Barium Titanate (Batio3) Incorporated In Pvdf-Hfp/Peo For Sustainable And Green Energy Generation, Rigobert Ybarra Jr.

Theses and Dissertations

The global reliance on fossil fuels and natural gas, has largely dominated the energy production field, but due to finite resource depletion and escalating greenhouse gas emissions, the immediate exploration of sustainable energy alternatives to mitigate climate change and ensure resource security has been a major concern. There has been extensive research into other more renewable methods of energy production such as wind and hydropower. Of these current energy generation types there are many areas of untapped potential from the mechanical movements generated ambiently not only in the large scale of power generation but also on a smaller scale. The …

Electrochemiluminescence Using Pencil Graphite Electrodes And Screen-Printed Carbon Electrodes Interfaced With A Simple Imaging System, Sandra Ehigiator

Electronic Theses and Dissertations

Electrochemiluminescence (ECL) is a phenomenon whereby electrochemical reactions generate a product that is capable of emitting light. ECL’s high sensitivity, selectivity, extremely low background, and relatively simple instrumentation make it particularly well-suited for chemical sensing and biosensing strategies. Here we report a simple ECL imaging system based on a camera interfaced with a zoom lens to compare pencil graphite electrode (PGE) and screen-printed carbon electrode (SPCE) arrays as ECL platforms. With this system, ECL signals generated from tris(2,2′- bipyridine)ruthenium(II) chloride hexahydrate ([Ru(bpy)3]2+) using co-reactant tri-n-propylamine (TPA) were linear with respect to [Ru(bpy)3]2+ concentrations from 9 to 450 μM. Detection limits …

A Chemical And Historical Analysis Of Beer: Discovering Brewing Styles And Beer Stages, Alexander Taylor '24

Honor Scholar Theses

This interdisciplinary project is designed to explore both the compositional qualities of beer during the brewing process and its impact on society from a cultural, economic, and social viewpoint. Comparing various styles of beer against each other in a historical, societal, and chemical lens allows for a deeper understanding of what creates a beer’s identity, and what makes it different from other styles. Here we analyzed two different styles of beer, a bock lager and a saison ale, in order to determine their chemical composition through their developmental stages to their final product. Based on previously published research and extended …

Design And Application Of Smart Systems To Address Analytical Problems, Lucas B. Ayres

All Dissertations

This dissertation is a multidisciplinary effort that integrates low-cost analytical instrumentation, redox chemistry, and artificial intelligence to overcome existing limitations in the fields of wearable sensing technology, Deep Eutectic Solvents (DES), and antioxidant chemistry. The overall goal behind each implemented strategy is to enhance the accuracy, efficiency, and accessibility of analytical processes and technologies. A general overview of the thesis, along with the research outcomes is included in Chapter One. The theoretical framework of this dissertation is presented in Chapter Two. Chapter Three describes the development of a wearable platform (sensor and instrumentation) to rapidly detect (~20 minutes) S. aureus …

Characterizing Modulators Of Protease-Activated Receptors With A Calcium Mobilization Assay Using A Plate Reader, Jacob T. Derousse, Chris Dockendorff

Chemistry Faculty Research and Publications

Changes in calcium concentration in cells are rapidly monitored in a high-throughput fashion with the use of intracellular, fluorescent, calcium-binding dyes and imaging instruments that can measure fluorescent emissions from up to 1,536 wells simultaneously. However, these instruments are much more expensive and can be challenging to maintain relative to widely available plate readers that scan wells individually. Described here is an optimized plate reader assay for use with an endothelial cell line (EA.hy926) to measure the protease-activated receptor (PAR)-driven activation of G_αq signaling and subsequent calcium mobilization using the calcium-binding dye Fluo-4. This assay has been used to …

Modeling Sex-Specific Changes In Myocardial Fibrosis, Grace Martin

Chemical Engineering Undergraduate Honors Theses

Heart disease the leading cause of death for both men and women in the United States. Cardiac fibrosis, or accumulation of extracellular matrix proteins in the heart, can occur after a heart attack and increase the risk for further complications. Current treatments for heart disease do not include extracellular matrix regulators, partly due to the complicated signaling network responsible for the production of these proteins. By using a computational model of the signaling network in cardia fibroblasts, the relationship between particular molecules and downstream extracellular matrix production can be examined.

Biological sex is an important factor for cardiac health and …

Selective Transfection Of A Transferrin Receptor-Expressing Cell Line With Dna-Lipid Nanoparticles And Synthesis Of Parasite-Derived Glycans As Biomarkers For Leishmaniasis, Irodiel Vinales Lozano

Open Access Theses & Dissertations

Despite notable progress in lipid nanoparticle (LNP)-mediated gene delivery, achieving selective transfection of specific cell types, such as cancer cells, remains a significant hurdle, hindering the advancement of innovative gene therapies. In this study, we engineered an LNP formulation encapsulating plasmid DNA (pDNA) encoding the monomeric Green Lantern (mGL) fluorescent reporter protein. The DT7 peptide ligand targeting human transferrin receptor 1 (hTfR1) was also conjugated to the LNP surface for targeted delivery to hTfR1-expressing cells. Optimization of LNP composition yielded favorable particle diameter, ζ-potential, yield, and pDNA encapsulation efficiency. Evaluation of transfection selectivity using a panel of two engineered cell …

Relations Between Printability And Rheology In A Ceramic Paste Extrusion Process, Nicholas Durand

Open Access Theses & Dissertations

Ceramic additive manufacturing (AM) uses the same fundamentals as material extrusion (MEX) that utilizes polymers or resins for printing applications. Ceramic AM uses the same process of slicing an STL file to determine a toolpath for the printer that will facilitate material deposition to manufacture full parts; ceramic AM also provides a low-cost advantage when compared to processes that require high powered lasers for melting metal powders or heated nozzles used for dispensing thermoplastics. Despite having the similar design freedom and ability for rapid prototyping that other printing methods benefit from with the addition of low cost, ceramic AM has …

Analysis Of Additively Manufactured Inconel 718 Combustion Behavior In Promoted Oxygen Environments, Dominic George Dieguez

Open Access Theses & Dissertations

Promoted combustion testing is a vital tool for engineers to establish the combustion and flammability characteristics of materials (metallic or otherwise) in oxygen enriched environments. Historically, much of the established data for metallic promoted combustion has been with regards to materials in their cast and wrought forms. However, with the emergence of additive manufacturing as a preferred method of fabrication, the need exists to evaluate how metals in that form behave. Recent testing has demonstrated that even if a metal or alloy is nominally the same with regards to chemistry, flammability between samples in the wrought form can differ significantly …

Table Of Contents

Journal of the South Carolina Academy of Science

No abstract provided.

Engineering Multifunctional Silicon Nanostructures From Biorenewable Cellulose Nanocrystals, Nancy Chen

All Dissertations

The imperative search for alternative materials to address the pressing demand for advance energy storage is underscored by the escalating environmental predicaments. Lithium-ion batteries (LIBs) with graphite anodes have become the benchmark in energy storage; however, they are approaching a saturation point in terms of energy density. Silicon emerges as a promising contender to supplant graphite, owing to its profuse availability, cost-effectiveness, and impressive specific capacity of 4200 mAh g^-1. By integrating silicon anodes, LIBs stand to undergo a radical transformation, markedly diminishing in weight and size, thus heralding a novel wave of compact, lightweight energy storage systems. …

Structure-Property Relationship Studies Of Electrically Conductive Metal-Organic Framework Materials, Shiyu Zhang

All Dissertations

Electrically conductive metal-organic frameworks (EC-MOFs) are among the most promising materials due to their tunable structures, properties, and diverse functions. However, the lack of comprehensive understanding of their structure-property relationship hinders the development of EC-MOFs. My dissertation focuses on the design, construction, and structure-property relationship studies of EC-MOFs.

Chapter 1 describes how MOFs' structural features and compositions affect the electronic properties and demonstrates conductive mechanisms and the corresponding design strategies to develop EC-MOFs.

Chapter 2 describes the synthesis, characterization, electronic and optical properties of four novel alkali-metal-based (Na, K, Rb, and Cs) 3D-MOFs with continuous tetrathiafulvalene tetracarboxylate (TTFTC) π-stacks, systematicly …

Carbon "Quantum" Dots: Structures, Properties, And Issues, Weixiong Liang

All Dissertations

Carbon dots (CDots) are small carbon nanoparticles (CNPs) with effective surface passivation. The effective passivation has been achieved by the surface functionalization of pre-existing CNPs with organic molecules, mostly molecules containing primary or secondary amine moieties. In the studies highlighted in this dissertation, CNPs were functionalized by selected organic molecules, including especially the use of radical addition reactions, to generate CDots with strong absorption and bright fluorescence emissions. A good demonstration of the approach was the N-ethylcarbazole (NEC) radical addition to CNPs under microwave irradiation. Spectroscopy and microscopy methods were employed to characterize the resulting NEC-CDots, and the results …

Synthesis, Electrical Conductivity, Electrocatalytic Activity For Water Splitting, And Pseudocapacitive Properties Of Perovskite Oxide Derivatives., Kinithi Meththa Kumari Wickramaratne

Electronic Theses and Dissertations

Developing green and sustainable energy solutions is crucial to addressing the energy and environmental challenges. Hydrogen is an attractive candidate given its high energy density and low carbon emission compared to gasoline and coal. Electrochemical water splitting through a water electrolyzer is recognized as a green method for generating hydrogen and oxygen gases. Developing cost-effective electrocatalysts to reduce overpotential in hydrogen and oxygen generation is essential for the overall process. The growing interest in perovskite oxides as versatile and sustainable catalysts is driven by their compositional flexibility, tunable electronic structure, earth abundance, and inherent catalytic performance. In our research, we …

Sustainable Methodologies For Synthesis Of Small Organic Molecules Using Micellar Catalysis., Deborah Sam Ogulu

Electronic Theses and Dissertations

Organic synthesis is a critical process in the creation of small molecule pharmaceuticals and agrochemicals. However, most methods for synthesizing these small molecules rely on toxic organic solvents as the reaction medium which account for approximately 80% of pharmaceutical waste. Moreover, many catalytic reactions require expensive endangered precious metals like palladium and costly metals. This dissertation presents research that aims to develop sustainable, eco-friendly reaction conditions to address these issues. We developed a ligand-free bimetallic nanocatalyst for the hydrogenation of unsaturated enones. This ligand-free nanocatalyst was prepared from nickel and ppm loading of palladium and was stabilized by harnessing the …

Investigations Into The Expansion Of Breslow-Type Intermediate Reactivity Via Radical C-N Bond Homolysis, Jacklyn J. Kubik

Graduate Theses and Dissertations

The Breslow intermediate is a key intermediate in catalytic transformations like the benzoin condensation and Stetter reaction. These intermediates were first postulated by Ronald Breslow in 1958. Since then, a number of researchers have sought to prove their existence and expand upon the reactions possible using these intermediates. In the sixty plus years since this intermediate was first postulated the reaction scope has expanded significantly, Breslow and breslow-type intermediates have expanded to encompass benzothiazoles, imidazoles, benzoimidazoles, triazoles, thiadiazoles, diamino type structures, and most recently pyridine structures. The expansion of these reactions has opened up new avenues of exploration and previously …

Silver Nanoparticle Biosynthesis Utilizing Ocimum Kilimandscharicum Leaf Extract And Assessment Of Its Antibacterial Activity Against Certain Chosen Bacteria, Horyomba Siaka Ouandaogo, Souleymane Diallo, Eddy Odari, Johnson Kinyu

All Peer-Reviewed Publications

The use of plants in the biological production of silver nanoparticles for antibacterial applications is a growing field of research. In the current work, we formulated Ocimum kilimandscharicum extracts using silver nanoparticles, and evaluated its potential antibacterial activity. Aqueous and methanol plant extracts were used to reduce silver nitrate at different time intervals (30 to 150 minutes) and pH (2 to 11). The UV-visible absorption spectrum recorded for methanol and aqueous extracts revealed a successful synthesis of AgNPs for methanol and aqueous extracts. The antimicrobial activity of the AgNPs was evaluated against Escherichia coli ATCC 25922, Salmonella choleraesuius ATCC 10708, …

Chemical Composition, Fate, And Toxicity Of Dissolved Hydrocarbon Oxidation Products In High Latitude Aquatic Environments, Maxwell Louis Harsha

LSU New Orleans Theses and Dissertations

Oil spilled in aquatic environments undergoes abiotic and biotic oxidation processes that produce hydrocarbon oxidation products (HOPs). HOPs rapidly diffuse in the water column, persisting and readily bioavailable to aquatic organisms. Characterizing HOPs is challenging because most of the mixture resides in the unresolved complex mixture (UCM). Understanding of the formation, fate, and toxicity of HOPs in high latitude environments remains limited. This research addresses these gaps through a comprehensive experimental approach, utilizing various analytical techniques including nonvolatile dissolved organic carbon (NVDOC) analysis, ultrahigh-resolution mass spectrometry, tandem mass spectrometry, inductively coupled plasma mass spectrometry, and fluorescence excitation-emission matrix spectroscopy. Additionally, …

Boron-Doped Diamond As A Resilient Electrode Material In Molten Salts, Hannah Katherine Patenaude

UNLV Theses, Dissertations, Professional Papers, and Capstones

Molten salt chemistry has a range of applications within nuclear technology, including for the Molten Salt Reactors (MSRs) and pyroprocessing to recover valuable actinides for energy and national security needs. However, the high-temperature, corrosive nature of molten salts makes them particularly challenging to deploy on an industrial scale and study in benchtop measurements. Material accountability and corrosion monitoring of MSR fuels are essential components to the successful deployment of MSRs, and electroanalytical techniques like cyclic voltammetry (CV) and spectroelectrochemistry (SEC) can provide a wealth of information to describe salt systems in situ. To perform such measurements, it is imperative to …

Electrocatalytic Degradation Of Bisphenol A Using Nickel Sulfide Supported On Graphene Oxide And Cobalt Sulfide Supported On Graphene Oxide Composite Materials, Katherine Ellynn Wright

Theses and Dissertations

The degradation of bisphenol A (BPA) by nickel sulfide supported on graphene oxide (NiS/GO) and cobalt sulfide supported on graphene oxide (CoS/GO) composite materials was investigated. The catalysts were studied to determine the optimal conditions for BPA degradation using electrocatalysis. Electrocatalytic trials were performed using varying parameters, which included electrolyte concentrations of 1.0 g/L, 2.0 g/L, and 4.0 g/L Na2SO4, pHs of 2, 4, and 6, and constant currents of either 0.100 A or 0.200 A. During the reaction samples were taken before the current was applied and 30 minutes and 60 minute intervals to observe the degradation of …

Bridging The Gap Between Molecular Components And Functional Electronic Chemical Sensing Devices With 2d Layered, Conductive Metal–Organic Frameworks, Emma Katherine Ambrogi

Dartmouth College Ph.D Dissertations

Layered, conductive framework materials are a class of materials with properties that make them ideal sensing materials in electronic chemical sensors. My thesis is focused on the development of these materials for electrochemical sensing of liquid phase analytes, and on understanding the material–analyte and material–electrode interfaces, and their self-assembly and deposition onto surfaces.

Chapter 1 provides a summary of the use of layered conductive metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) in electronic chemical sensors, detailing the materials and sensor architectures employed, and the analytes detected. Relevant performance metrics are compared, and investigations into material–analyte interactions are highlighted.

Chapter …

An Examination Of The Teaching And Learning Of Resonance In General Chemistry I And Organic Chemistry I Using Variation Theory, Sabrina Barakat

UNLV Theses, Dissertations, Professional Papers, and Capstones

Resonance is a fundamental chemistry concept first introduced to students in General Chemistry I, reintroduced in Organic Chemistry I, and then utilized throughout other higher-level chemistry courses. A molecule or ion can be said to exhibit resonance when it can be represented by two or more chemical structures (i.e., Lewis structures) that differ only in their arrangement of electrons. In other words, resonance represents the electronic structure of a molecule or ion when a single Lewis structure does not adequately depict the true distribution of electrons. The molecule or ion is best represented as a combination of all of the …

Performance Effects Of Dissociated Hydrogen In Nuclear Thermal Propulsion Engines, Richard Adam Gorrell

UNLV Theses, Dissertations, Professional Papers, and Capstones

Nuclear thermal propulsion (NTP) research considers hydrogen dissociation as negligible to design and analysis of propulsion engines. This study reintroduces chemically reacting flow to NTP engine analysis for investigation of the dissociation effect on engine performance. A first-principles approach observes the basic chemical mechanism and reaction within the high-speed, high-temperature NTP flow to baseline expected atomic hydrogen levels and validate equilibrium. A surface reaction study looks into hydrogen absorption through dissociation and its effect on the boundary layer, and bulk flow. For total performance, the resulting dissociated flow is analyzed through nozzle expansion and performance metrics calculated.

All historic reactor …

Revealing The Three-Dimensional Arrangement Of Polar Topology In Nanoparticles, Chaewa Jeong, Juhyeok Lee, Hyesung Jo, Jaewhan Oh, Hionsuck Baik, Kyoung-June Go, Junwoo Son, Si-Young Choi, Sergey Prosandeev, Laurent Bellaiche, Yongsoo Yang

Physics Faculty Publications and Presentations

In the early 2000s, low dimensional ferroelectric systems were predicted to have topologically nontrivial polar structures, such as vortices or skyrmions, depending on mechanical or electrical boundary conditions. A few variants of these structures have been experimentally observed in thin film model systems, where they are engineered by balancing electrostatic charge and elastic distortion energies. However, the measurement and classification of topological textures for general ferroelectric nanostructures have remained elusive, as it requires mapping the local polarization at the atomic scale in three dimensions. Here we unveil topological polar structures in ferroelectric BaTiO₃ nanoparticles via atomic electron tomography, which …

Development Of Chiral Lewis Base Catalysts For Chlorosilane-Mediated Asymmetric C-C Bond Formations, Changgong Xu

Theses and Dissertations

The chiral hydrazine is a crucial structural motif that serves as pivotal structural elements in numerous natural products and biologically significant molecules. We are particularly interested in the catalytic asymmetric reduction of hydrazones, as well as the catalytic asymmetric propargylation and allenylation of hydrazones, because they provide direct pathways to these enantio-enriched chiral building blocks. In this work, we will explore the potential of two different categories of chiral Lewis base catalysts in the said transformations.

Developed by another student in our group, axial-chiral 3,3’-triazolyl biisoquinoline N,N’-dioxides derived catalysts are tested and demonstrated its capability in activating various hydrazone …

Characterizing The Role Of Chemo-Mechanical Couplings In The Activation Process Of Proteins That Undergo Conformational Changes, Ugochi Isu

Graduate Theses and Dissertations

Proteins are not static entities; rather, they are dynamic macromolecules that undergo conformational changes to perform their biological functions. These structural transitions are often coupled to chemical events such as lipid interactions, or changes in the cellular environment. Understanding the intricate interplay between chemical perturbations and the resulting mechanical response is crucial for elucidating the activation mechanisms of proteins. This dissertation aims to characterize the role of chemo-mechanical couplings in the activation process of two G protein-coupled receptors (GPCRs): Cannabinoid Receptor 1 (CB1) and Metabotropic Glutamate Receptor 1 (mGluR1). We employ molecular dynamics simulations to investigate the conformational landscapes of …

Two Studies: Aromatization-Driven Ring Opening Functionalization Of Unstrained Cycloalkanones Through Visible Light Catalysis, And Synthesis Of Amino Endoperoxides Using Self-Doped Titanium Dioxide (Ti3+@Tio2) As A Photocatalyst, Enoch Kudoahor

Graduate Theses and Dissertations

The pharmaceutical industry has been focused on discovering new innovative drugs over the last decade, but the syntheses are either inefficient or the approach to environmental sustainability raises significant concerns. Photochemistry and photocatalysis have found widespread applications in organic synthesis as a result of this pressing issue. Our role as organic chemists is to improve environmental quality by creating a "greener" world through the development of efficient synthetic methods and strategies. Solar energy is now one of the most abundant and renewable natural resources. The emergence of environmental sustainability concerns has led to the development of new techniques for harnessing …

Conversion Of Microcrystalline Cellulose To Hexane Using Hydrogenated Metal Oxides At Low Temperature And Pressure, Mubarak Osman

Electronic Theses and Dissertations

Increasing global energy demand and environmental concerns have fueled the exploration of sustainable and efficient methods for renewable fuel production. The conversion of cellulosic waste to hydrocarbon fuels using hydrogenated metal oxides presents a novel and eco-friendly approach to sustainably address energy demand. In this study, hydrogenated metal oxides were used as catalysts in a relatively low-temperature and atmospheric-pressure environment to facilitate the conversion of cellulosic waste into hydrocarbon fuels. Hydrogenated metal oxides have been introduced as potential hydrogen transfer catalysts. The expected result is the selective conversion of cellulose to hexane at relatively low temperatures, which significantly reduces energy …

Student Self-Efficacy And Attitude In Organic Chemistry: A Comparison Of Two Pedagogical Approaches, Matthew Autry

Arts & Sciences Graduate Student Theses and Dissertations

No abstract provided.