Physical Sciences and Mathematics Commons^™

Application Of Functionalized Organosilicas In Adsorption Of Nitrates, Stephen Amoako

Electronic Theses and Dissertations

This study addresses the critical environmental issue of elevated nitrate levels in water bodies, primarily due to excessive use of nitrogenous fertilizers and improper waste disposal. It focuses on reducing nitrate concentrations in polluted water to permissible levels through the effectiveness of hybrid materials in nitrate adsorption. We synthesized nine amino-functionalized adsorbents using grafting and sol-gel techniques. Batch adsorption tests confirmed the high nitrate adsorption capacities of these adsorbents, with sol-gel materials showing the highest efficiency due to their abundant amino group contents. Among these, the surfactant-free, sol-gel adsorbent was the most effective, combining ease of synthesis with cost-efficiency. Our …

Excited State Processes In Radical Elaborated Platinum Donor-Acceptor Complexes, Sangita Paudel

Chemistry and Chemical Biology ETDs

Organo-transition metal complexes are being widely studied to understand their photophysical properties for their wide range of applications as efficient emitters in organic light emitting diodes (OLEDs), light emitting electrochemical cells (LEECs), etc. Cyclometalated organo-transition metal complexes such as cyclometalated square planar platinum(II) complexes are becoming suitable candidates for such applications because of their highly efficient luminescence. Understanding the excited properties of such complexes is useful in designing highly efficient and color tunable phosphors with desired excited state lifetimes. We aim to explore the influence of radical substituents on electronic structure, luminescence quantum efficiencies, and excited state lifetimes by synthesizing …

Positron Emission Tomography In Oncology And Environmental Science, Samantha Delaney

Dissertations, Theses, and Capstone Projects

The last half century has played witness to the onset of molecular imaging for the clinical assessment of physiological targets. While several medical imaging modalities allow for the visualization of the functional and anatomical properties of humans and living systems, few offer accurate quantitation and the ability to detect biochemical processes with low-administered drug mass doses. This limits how physicians and scientists may diagnose and treat medical issues, such as cancer, disease, and foreign agents.

A promising alternative to extant invasive procedures and suboptimal imaging modalities to assess the nature of a biological environment is the use of positron emission …

Non-Destructive Determination Of Surface Area In Reverse Phase Chromatographic Columns, Margaret Figus

Seton Hall University Dissertations and Theses (ETDs)

Excess adsorption isotherms of acetonitrile and methanol from water were measured on eight commercial columns. Columns used in this study represent the latest examples in column development and include three different poroshell columns (Kinotex C18, Ascentis C18, and Halo C18) as well as conventional columns with significantly different adsorbent geometries (Allure C18, YMC C18) and various hybrid-silica columns (Gemini C18, Xterra C18, and XBridge C18). Comparison of the excess adsorption isotherms measured on all these columns and expressed in surface-specific form demonstrated significant similarity of the adsorption properties of all columns, which allows the introduction of the Standard Excess Adsorption …

Advancing Coupled Cluster Methods: Tensor Factorization And Analytic Gradient Implementation, Tingting Zhao

Chemistry Theses and Dissertations

With the rapid advancement of computing capabilities, computational chemistry has become increasingly indispensable in both experiment design and the interpretation of experimental outcomes. Wave-function-based quantum mechanistic methods are highly sought after for their ability to provide high-accuracy data and their potential for systematic improvement. However, to extend their applicability to larger molecules, it is essential to employ rank-reducing approximations to these methods. This dissertation dedicates Chapters Three and Four to the development of rank-reduced methodologies. Additionally, beyond single-point energies, molecular geometries and properties of molecule-excited states hold paramount importance across diverse fields of chemistry. Hence, Chapter Five presents the work …

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 …

Synthesis And Characterization Of Indole-Based Zinc Dipyrrin Photosensitizers, Jean-Pierre Sanza

Electronic Theses and Dissertations

Metal complexes of dipyrromethene (dipyrrins) used as sensitizers in photocatalysis offer a way to harness solar energy in chemical bonds to create new fuels. This offers the dual role of reducing fossil fuel dependence and atmospheric CO₂ levels. Traditionally, metal dipyrrin complexes are synthesized using substituted pyrroles, aldehydes, and transition metals. Indoles have a more expanded pi-electron system and their dipyrrin-type complex may exhibit visible light absorption, suggesting that they can act as photosensitizers for CO₂ reduction processes. A novel indoledipyrromethene was synthesized using unsubstituted indole and mesitaldehyde. The complex exhibits visible light absorption at 422 nm. Its …

Use Of Molecular Logic Gates For The Tuning Of Chemosensor Dynamic Range, Orhan Acikgoz

Undergraduate Honors Theses

The first molecular logic gates were created in the 1990s; integrating such logic gates into fluorescent chemosensors allowed for the detection of different types of ions in solution. In this study, we have developed a new use of molecular logic gates by having two of the same type of binding site. The two binding sites on a fluorophore that both detect Na⁺ ions led to an increase in the detection limit compared with the chemosensor with a single binding site. Since the two sodium binding sites create an AND logic gate, two sodium ions are needed to generate a …

Mathematical Modeling And Examination Into Existing And Emerging Parkinson’S Disease Treatments: Levodopa And Ketamine, Gabrielle Riddlemoser

Undergraduate Honors Theses

Parkinson’s disease (PD) is the second most common neurodegenerative disease across the world, affecting over 6 million people worldwide. This disorder is characterized by the progressive loss of dopaminergic neurons within the substantia nigra pars compacta (SNpc) due to the aggregation of α-synuclein within the brain. Patients with PD develop motor symptoms such as tremors, bradykinesia, and postural instability, as well as a host of non-motor symptoms such as behavioral changes, sleep difficulties, and fatigue. The reduction of dopamine within the brain is the primary cause of these symptoms. The main form of treatment for PD is levodopa, a precursor …

Process Modeling The Neuroprotective Effects Of A Plant-Based Diet On Parkinson's Disease, Julia Mitchell

Undergraduate Honors Theses

Parkinson's disease (PD) is a progressive neurodegenerative disorder characterized by motor symptoms such as tremors, bradykinesia, rigidity, and postural instability. Recent research suggests an avenue for potential neuroprotection through dietary intervention, specifically the adoption of a plant-based diet. A plant-based diet predominantly comprises foods derived from plants, emphasizing fruits, vegetables, grains, legumes, and nuts while minimizing or excluding animal products. This thesis aims to explore the biochemical pathways implicated in PD progression and the potential impact of dietary choices on these pathways. The investigation focuses on several key pathways: alpha-synuclein aggregation, the blood-brain barrier crossing of levodopa, oxidative stress, ferroptosis, …

Harnessing The Power Of Virtual Reality For Organic Chemistry Education, Jungmin Shin

Undergraduate Honors Theses

Understanding organic chemistry concepts heavily relies on visualization of the geometry of molecules and spatial arrangement of molecules during mechanisms. 2D textbook depictions have their limitations in visualizing the three-dimensionality of organic chemistry. Student learning outcomes could be greatly improved from 3D visualizations of these topics. This project explores the potential of an emerging technology, Virtual Reality (VR), being incorporated as a teaching resource for organic chemistry.

This paper discusses two trials for evaluating the potential of VR as a teaching resource for organic chemistry in select topics of the Diels-Alder reaction and R/S configurations and stereoisomers. The Diels-Alder reaction …

Modeling Group 3 Medulloblastoma: Describing The Interconnected Pathway Of The Most Common Pediatric Brain Cancer, Amber Cantú

Undergraduate Honors Theses

Group 3 medulloblastoma is one of the most common pediatric brain cancers. Affecting infants and children, this cancer has the worst prognosis of the medulloblastoma group. Current treatments use surgical resection, radiation, and chemotherapy to afflict the cancer, however no cure has been found. This project aims to model one of the many pathways being investigated in Group 3 medulloblastoma which may be used to synthesize future treatments. Specifically, showing the interconnections between various precursors of BCL-xL, an antiapoptotic protein, and how these factors influence the progression of the disease. Scientific databases were used to find previous research articles which …

Synthesis And Characterization Of Silver(I) And Manganese(Ii) Complexes With Thione Imidazoles, Shannon Keyser, Audrey Lawrence, Jaime M. Murphy Ph.D.

Honors Theses

Coordination polymers are chemical complexes with versatile applications such as catalysts, electrical conduc-tors, non-linear optics, magnetics, chemical sensing, and molecular storage. The polymers are comprised of a repeating series of metal-ligand complexes, which form various structures in varying ratios depending on the metal and ligand used. Certain metal-ligand combinations have shown particular promise as potentially being polymers or, if not polymers, possessing other useful features such as electromagnetic conductivity. Complexes were synthesized using silver(I) and manganese(II) with the ligands methimazole, 2-mercaptoimidazole, and thiocarbanilide with counterions of either chloride or nitrate. These com-plexes were characterized using elemental analysis, infrared spectroscopy, and …

Molybdenum Alkylidyne Complexes With Phenoxide Ligands For Alkyne Metathesis, Marvin L. Stewart Jr

LSU Doctoral Dissertations

Abstract

Alkyne metathesis is a powerful synthetic tool, which provides easy access to complex organic molecules in a single-step. It is a dynamic covalent reaction that scrambles alkynes, carbon-carbon triple bonds (C≡C). Molybdenum- or tungsten-alkylidyne (Mo≡C, W≡C) complexes are typically used as catalyst to cleave and reform alkyne bonds. Our goal has been to gain a deeper understanding of the intrinsic differences between functional ligands by the development of novel phenoxide ligands.

In chapter 2 we explore the detailed synthesis of novel phenoxide podand ligands in an effort to identify their mo-alkylidyne complexes. We were able to synthesize a variety …

Multi-Scale Simulations Of Dynamic Protein Structures And Interactions, Yumeng Zhang

Doctoral Dissertations

Intrinsically disordered proteins (IDPs) are functional proteins that lack stable tertiary structures in the unbound state. They frequently remain dynamic even within specific complexes and assemblies. IDPs are major components of cellular regulatory networks and have been associated with cancers, diabetes, neurodegenerative diseases, and other human diseases. Computer simulations are essential for deriving a molecular description of the disordered protein ensembles and dynamic interactions for mechanistic understanding of IDPs in biology, diseases, and therapeutics. However, accurate simulation of the heterogeneous ensembles and dynamic interactions of IDPs is extremely challenging because of both the prohibitive computational cost and demanding force field …

High Resolution Mass Spectrometry As A Platform For The Analysis Of Polyoxometalates, Their Solution Phase Dynamics, And Their Biological Interactions., Daniel T. Favre

Doctoral Dissertations

Polyoxometalates (POMs) are a class of inorganic molecule of increasing interest to the inorganic, bioinorganic and catalytic communities among many others. While their prevalence in research has increased, tools and methodologies for the analysis of their fundamental characteristics still need further development. Decavanadate (V10) specifically has been postulated to have several unique properties that have not been confirmed independently. Mass spectrometry (MS) and its ability to determine the composition of solution phase species by both mass and charge is uniquely well suited to the analysis of POMs. In this work we utilized high-resolution mass spectrometry to characterize V10 in aqueous …

Development Of Salinomycin Derivatives As Potential Anticancer Agents, Viren Soni

Theses and Dissertations

Salinomycin is a poly-ionophore antibiotic that was originally isolated from Streptomyces albus by Miyazaki and colleagues from Kaken Chemicals Co., Ltd., Tokyo, Japan. Salinomycin exhibits antimicrobial activity against Gram-positive bacteria including Bacillus subtilis, Staphylococcus aureus, Micrococcus flavus, Sarcina lutea, Mycobacterium spp. Some filamentous fungi, Plasmodium falciparum, and Eimeria spp. as well as protozoan parasites responsible for the poultry disease coccidiosis. Hence, it is used in veterinary medicine. In 2009 Gupta et al demonstrated that salinomycin selectively killed human breast cancer stem cells (CSCs) with great efficacy, and the mechanism of action of this novel CSCs molecule was explored. To name …

Stereospecific Cross-Coupling Reactions Of Vinyl Triflates And An Investigation Of The Synthesis And Reactivity Of Activated Alkyltricyclohexylstannanes, Pejman Ghaemimohammadi

Dissertations, Theses, and Capstone Projects

Organic chemistry exists in all aspects of everyday life from polymers to pharmaceutics. Formation of carbon-carbon bonds is essential for the synthesis of complex organic compounds. This goal can be achieved by using transition metal catalysts. Second-row transition metals such as Pd, Pt, Rh, and Ir have shown remarkable efficacy in these reactions. Metal-catalyzed cross-coupling reactions form carbon-carbon bonds between electrophiles and nucleophiles using transition metal catalysts. Pd is mainly used in this reaction.

Transition metal-catalyzed cross-coupling reactions that form a bond between two C(sp²) carbons have been widely studied over the past decades. C(sp²)-C(sp^{3 …}

Studies Of Oxidopyrylium Ylide Dimers And Their Utility In The Synthesis Of Densely Functionalized Troponoids, Daniel V. Schiavone

Dissertations, Theses, and Capstone Projects

Herein, we describe our efforts to investigate mechanistic considerations of oxidopyrylium ylides and their use in cycloadditions to form complex bicyclic structures and the advancement of these cycloadducts to the synthesis of densely functionalized tropolones. This work also describes applications of tropolones as biologically relevant structures and dynamic fluorophores.

In Chapter 1, we expand upon previous studies done in the Murelli Lab describing the ability of 3-hydroxy-4-pyrone derived oxidopyrylium dimers to revert back to ylides in situ and as result can be used as a clean oxidopyrylium ylide source in accessing oxabicyclic compounds. Intermolecular cycloadditions of these ylides can be …

Rational Design Of Peptide-Based Materials Informed By Multiscale Molecular Dynamics Simulations, Dhwanit Rahul Dave

Dissertations, Theses, and Capstone Projects

The challenge of establishing a sustainable and circular economy for materials in medicine and technology necessitates bioinspired design. Nature's intricate machinery, forged through evolution, relies on a finite set of biomolecular building blocks with through-bond and through-space interactions. Repurposing these molecular building blocks requires a seamless integration of computational modeling, design, and experimental validation. The tools and concepts developed in this thesis pioneer new directions in peptide-materials design, grounded in fundamental principles of physical chemistry. We present a synergistic approach that integrates experimental designs and computational methods, specifically molecular dynamics simulations, to gain in-depth molecular insights crucial for advancing the …

Evaluating The Reliability And Accuracy Of Alchemical Binding Free Energy Methods And Calculations, Fnu Sheenam

Dissertations, Theses, and Capstone Projects

Molecular recognition plays a crucial role in various biological processes, such as enzymatic reactions, signal transduction, and genetic information processing. Investigating how proteins selectively bind to their partners is an active research area, but there is a lack of experimental details on protein structures and interactions in molecular complexes. Computational techniques based on macromolecular structures offer a way to predict protein-ligand interactions and explore their recognition mechanisms. Estimating binding affinities, particularly through alchemical binding free energy calculations, has become valuable in supporting drug discovery. This work introduces new methodologies, utilizing the Alchemical Transfer Method, to address issues like poor convergence …

Analyzing Novel Metal Alloys For Glucose Sensing And Electrocatalysis, Anna Grace Boddy

Theses and Dissertations

In pharmaceutical and medicinal chemistry, metals and metal alloys often receive less attention compared to biological or organic compounds due to many factors including toxicity in the body for drug development or the cost of these metals. However, metals can play an important role in pharmaceuticals, having an impact on original cancer drugs, such as platinum used for head and neck tumors. Electrocatalysis is also another topic that receives less attention over topics such as chromatography in pharmaceuticals due to its potential toxic catalysts and voltages that could be harmful to the body. Electrocatalytic sensors can play an important role …

Development Of Stochastic And Time-Dependent Quantum Chemical Methods For Accurate Description Of Light-Matter Interactions With Applications In Photoionization And Inverse Photoemission In Nanomaterials, Nicole Spanedda

Dissertations - ALL

There are three main focuses of this work. First, the theoretical details of the Stratified Stochastic Enumeration of Molecular Orbitals (SSE-MO) method is presented, along with its application for calculating ionization potentials (IPs) of quantum dots. The SSE-MO method can readily be applied for the purpose of efficiently and accurately calculating ionization potentials, by constructing the frequency-dependent self-energy operator and then subsequently, solving the associated Dyson equation. Constructing the frequency-dependent self-energy operator is challenging because the scaling of the computational cost with respect to system size, becomes prohibitive for large systems, such as quantum dots. This is due to the …

Synthetic Studies On Ship Modulators, Hif-2Α Antagonists, And New Rhodium Carboxylate Catalysts, Angela Pacherille

Dissertations - ALL

The PI3K pathway is a major cell signaling axis in eukaryotic cells. This pathway employs the second messenger, inositol phospholipid PI(3,4,5)P3, which is responsible for activating Akt and other kinases creating a cascade of signals. The enzyme, SH2-containing inositol-5’-phosphatase (SHIP), plays a key role in this pathway by maintaining the delicate balance of PI(3,4,5)P3. Modulation of SHIP activity through the use of small molecule inhibitors may be utilized for the treatment of certain types of cancer, Alzheimer’s disease, and diabetes. A high-throughput screen identified the small molecule SHIP1 inhibitor, NSC23922, a mixture of 3α- and 3β-aminocholestane. These diastereomers were synthesized …

Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li

Electronic Thesis and Dissertation Repository

Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.

This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS^-, RSe^-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S^2-, Se^2-) bimetallic complexes. In these studies, the chalcogen …

Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss

Electronic Thesis and Dissertation Repository

N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …

Medicinal Mushrooms: The Extraction And Analysis Of Bioactive Compounds From Hericium Erinaceus And Ganoderma Lucidum Mushrooms., Jhanielle Amanda-Kaye James

Electronic Theses and Dissertations

Medicinal mushrooms, such as Hericium erinaceus (lion's mane) and Ganoderma lucidum (reishi), have a rich history of traditional use in natural remedies, garnering attention for their bioactive compounds and nutritional benefits. Renowned for being protein-rich and low in fat, these fungi exhibit antimicrobial, anti-tumor, antioxidant, anti-diabetic, and anti-hypercholesterolemic properties attributed to their diverse bioactive components, including polysaccharides, proteins, terpenes, sterols, vitamins, polyphenols, and fatty acids. This study aimed to optimize extraction techniques, comparing maceration, ultrasound-assisted maceration, and Soxhlet extraction on fresh and dried lion's mane and reishi mushrooms. Varying solvent polarities and extraction times revealed that 8-hour extractions with dried …

Dynamic Metal-Ligand Interactions In Semiconducting Π-Conjugated Materials, Peter Blake Joseph St Onge

Electronic Theses and Dissertations

Over the years, the development of materials has seen a vast amount of expansion into a variety of disciplines which have demonstrated usefulness in a large span of applications. One of these new and developing themes is the use of metals and ligands which are incorporated into polymers to modify their properties, which can enable different desired properties. Incorporation of metal-ligand complexes in materials chemistry has proven to be an area of rising interest, however, many of these interactions and systems remained completely unexplored. Understanding the key fundamental principles of how these materials can be changed and modified through metal-ligand …

Molecular Understanding And Design Of Deep Eutectic Solvents And Proteins Using Computer Simulations And Machine Learning, Usman Lame Abbas

Theses and Dissertations--Chemical and Materials Engineering

Hydrophobic deep eutectic solvents (DESs) have emerged as excellent extractants. A major challenge is the lack of an efficient tool to discover DES candidates. Currently, the search relies heavily on the researchers’ intuition or a trial-and-error process, which leads to a low success rate or bypassing of promising candidates. DES performance depends on the heterogeneous hydrogen bond environment formed by multiple hydrogen bond donors and acceptors. Understanding this heterogeneous hydrogen bond environment can help develop principles for designing high performance DESs for extraction and other separation applications. This work investigates the structure and dynamics of hydrogen bonds in hydrophobic DESs …

Investigating The Effect Of Relative Humidity On Organic New Particle Formation From The Dark Ozonolysis Of Biogenic Volatile Organic Compounds, Austin Callum Flueckiger

Graduate College Dissertations and Theses

Solid or liquid particulate matter suspended in the air, also known as atmospheric aerosols, are a ubiquitous component of Earth’s atmosphere. It is important to understand the chemical and physical processes that lead to the formation of these aerosols as they have an impact on climate health and human health. An important subset of atmospheric aerosols are secondary organic aerosols (SOA) that form from the gas-phase oxidation of volatile organic compounds (VOCs). VOCs can be emitted via biogenic and anthropogenic pathways, however, global estimates place biogenic sources as the major contributor. Although widely studied, some of the fundamental mechanisms that …