Computational Studies Of Triplet State Formation In Zinc Dipyrrin Complexes, Reuben Kwabla Adigbli

Electronic Theses and Dissertations

Zinc dipyrromethene complexes are promising earth-abundant photosensitizers due to their strong visible-light absorption and tunable excited states. To rationally design them for photocatalysis and photodynamic therapy, a molecular-level understanding of triplet-state formation is needed, but details of intersystem crossing remain unclear. To study the effect of π-extension, we synthesized an indole-substituted zinc dipyrrin complex: the dipyrromethane ligand was prepared from indole and mesitaldehyde, oxidized to the dipyrromethene, then coordinated with zinc. DFT and TD-DFT calculations determined ground and excited-state geometries and energies in different solvents, modeled absorption spectra, and visualized charge distributions. The results show how solvent polarity shifts energies …

A Fundamental Study Of Fatty Acid Ionic Liquids And Their Effects On Biomolecules, Achismita Dutta

Theses and Dissertations

Fatty acid ionic liquids (FAILs) are a class of ionic liquids (ILs) with relatively low toxicity and potential applications in biological systems. This study examined the interactions of tetramethylguanidinium decanoate, tetramethylguanidinium octanoate, choline decanoate, and choline octanoate with lipid membranes, proteins, and nucleic acids. Membrane leakage experiments using model lipid vesicles showed that decanoate-based FAILs produced greater membrane permeabilization than octanoate-based analogues, consistent with their higher membrane permeability. These effects were stronger for the ILs than for decanoate alone and occurred below the critical micelle concentration (CMC), suggesting that micelle formation may not be essential for membrane disruption. The ability …

Quantitative Analysis Of Blue 1 Dye In Commercial Sports Drinks By Uv -Vis Spectroscopy And Hplc-Dad, Mikayla Bush

Forensic Science Master's Projects

Food dyes are natural or synthetic substances added to foods, beverages, and cosmetics to enhance color and visual appeal. Although they provide no nutritional value, they are widely used to attract consumers, particularly children. Concerns have been raised about the potential health effects of synthetic dyes, including links to hyperactivity in children, tumor formation at high doses, and possible impacts on gut and brain function. In response, regulatory efforts are ongoing. In April 2025, the U.S. Department of Health and Human Services (HHS) and the Food and Drug Administration (FDA) announced an initiative to phase out petroleum-based food dyes, including …

Catalytic Synthesis Of Protoberberine Alkaloids And Their Evaluation As Selective Dopamine Receptor Ligands, Ashok Reddy Gudipally

Dissertations, Theses, and Capstone Projects

Dopamine regulates motor control, cognition, reward, motivation, and neuroendocrine signaling. Disruption of dopaminergic neurotransmission is closely linked to central nervous system disorders, including Parkinson’s disease, schizophrenia, addiction, and related neuropsychiatric conditions. Because these functions are mediated by multiple dopamine receptor subtypes with distinct roles in physiology and disease, the discovery of subtype-selective ligands remains an important goal in neuropharmacology. Within this context, protoberberine alkaloids, particularly tetrahydroprotoberberines (THPBs), are attractive molecular frameworks because they combine structural complexity with broad biological relevance, including measurable activity in CNS-related diseases. Prior work from our laboratory and others established (–)-stepholidine (1.60) as an important lead …

Development Of Ultrafast Protein Digestion And Standards Free Quantitation Methods For Mass Spectrometric Analysis, Praneeth Ivan Joel Fnu

Dissertations

A wide variety of biologically important molecules, such as enzymes, antibodies, hormones, transporters and receptors are proteins by composition and they play key roles in biological functions such as cellular regulation, communication, metabolism and physiological function. Protein dysfunctions and abnormalities are associated with numerous diseases, making proteins critical targets for understanding disease mechanisms and developing therapeutic interventions. Protein-based therapeutics such as monoclonal antibodies, hormones and vaccines gained popularity due to their high specificity, efficacy, and ability to treat complex diseases that are often difficult to address with small-molecule drugs.

Given the important role of proteins in a variety of biological …

Synthesizing Viscoelasticity: Living Polymers, Micro-Macro Relations, And Paths For Resolution, Adam M. Hasler

Graduate Masters Theses

This thesis investigates the relationship between macroscopic rheological signals and underlying microscopic dynamics in complex fluids, specifically focusing on ”living polymers” within the cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal) surfactant system. The research addresses the inverse parameterization problem, demonstrating how bulk measurements like zero-shear viscosity can mask fundamentally different physical topologies, such as purely cylindrical, reptating micelles versus highly branched networks. Through the successful synthesis of viscoelastically ”degenerate” samples, the study utilizes an array of characterization techniques including frequency sweeps, Large Amplitude Oscillatory Shear (LAOS) to resolve these unique underlying states. Furthermore, the work explores further avenues of study …

Electrolyte Development And Interfacial Reactions At Multivalent Metal Anode For Next Generation Energy Storage Systems, Leslie Gates

Graduate Masters Theses

The increasing demand for safe, sustainable, and high-performance energy storage systems has driven significant interest in multivalent-ion batteries, including aluminum, magnesium, and zinc-based systems. These technologies have attracted attention due to their high theoretical energy densities, natural abundance, low cost, and environmentally benign nature. However, their development remains hindered by a limited fundamental understanding of electrolyte development and interfacial processes at the electrode–electrolyte interface, where complex electrochemical interactions govern battery performance and stability.

This thesis investigates electrode–electrolyte interactions in both a novel aluminum electrolyte and divalent magnesium and zinc systems. Beginning with the development and characterization of a novel aluminum …

Multicomponent Reaction-Initiated Synthesis Of Polyheterocyclic Compounds, Ashutosh Nath

Graduate Doctoral Dissertations

Efficient synthesis of novel heterocycles with biological interest remains a challenge in modern organic chemistry. This dissertation presents the development of efficient synthetic strategies that combine multicomponent reactions (MCRs) with sequential reactions for rapid access a diverse array of polyheterocyclic compounds. The projects are: 1) Groebke-Blackburn-Bienaymé (GBB) reaction followed by N-acylation and Friedel-Crafts (FC) cyclization for the construction of imidazopyridine- and indole-fused azepinones involving an unusual ring-expansion process. 2) Modified GBB condensation products for intramolecular Diels-Alder (IMDA) cycloaddition and dehydrative re-aromatization to access imidazopyridine-fused isoquinolinones. 3) Integration of the Ugi-three component reaction (Ugi-3CR) and Pictet-Spengler (PS) reaction followed by …

Correlative In Situ Nonlinear Optical Characteriztion Of Plasmonic Colloidal Nanoparticle Growth Dynamics, Stena C. Peterson

LSU Doctoral Dissertations

Colloidal noble metal nanoparticles are of extreme interest as nanomaterials and for the wide variety of their possible applications in nanomedicine. The unique linear and nonlinear optical processes associated with these nanomaterials can be studied using a variety of spectroscopic techniques including extinction, second harmonic generation (SHG), and two-photon fluorescence (TPF) spectroscopy. In order to better understand and optimize these nanomaterials for their desired applications, it is important to investigate the growth and photophysical dynamics associated with gold nanoparticles, silver-gold core-shell (Ag-Au CS) nanoparticles, and gold-silver-gold core-shell-shell (Au-Ag-Au CSS) nanoparticles in addition to how their size, surface morphology, composition. and …

Electronic Structure Discretization And Compression Using Diagonal Basis Sets, Casey Lee Dowdle

Dartmouth College Ph.D Dissertations

Numerically solving the electronic structure problem is a fundamentally difficult problem due to the exponential growth in the dimension of the Hilbert space as the system size increases. In order to solve problems at a chemically relevant accuracy, both the choice of basis set and numerical method are important factors that are intrinsically connected.

In this thesis, we study the discretization and resulting compression of electronic Hamiltonians using diagonal basis sets. A diagonal basis set approximately diagonalizes the matrix and tensor representations of the one- and two-body potentials. This can reduce storage, simplify matrix-vector products, and lower the complexity of …

Synthesis, Utilization And Biological Evaluation Of Β-Hairpin Peptides As Inhibitors Of Immune Checkpoints, Sarah Naylon

Electronic Theses and Dissertations

Peptide therapeutics have emerged as promising alternatives to monoclonal antibodies because of their smaller size, improved tissue penetration, and synthetic versatility. Yet their broader application is often limited by poor structural stability, rapid clearance, and reduced target residence times. This dissertation describes the design, synthesis, structural characterization, and biological evaluation of β-hairpin peptides as inhibitors of immune checkpoints and as peptide vaccine scaffolds while developing strategies to overcome these limitations. At first a series of antibody-derived β-hairpin peptides (mimics of complementary determining region heavy-chain 3: CDR-H3s) as covalent inhibitors of the PD-1/PD-L1 immune checkpoint were investigated. Electrophilic warheads were incorporated …

Development Of Minimalist Trifunctional Building Blocks For Chemical Biology Probe Synthesis, Luke E. Bohrer

Electronic Theses and Dissertations

The completion of the Human Genome Project in 2003 generated expectations that genomic information would accelerate the discovery of new protein drug targets and FDA-approved therapies. However, many small-molecule drug candidates continue to fail in clinical trials, and much of the human proteome remains undercharacterized in terms of structure, function, and disease relevance. Chemical tools are therefore essential for defining protein function, mapping protein interactions, and identifying disease-associated molecular mechanisms. Among these tools, small-molecule chemical probes provide a powerful strategy for connecting biological activity with target identification, functional analysis, and the development of effective therapies.

This dissertation describes the development …

Real Bullets, Plastic Guns: Evaluating The Strength Of 3-D Printed Gun Parts, Maria Latenia Mayol

Student Theses

Privately made firearms (PMFs), often referred to as “ghost guns,” are firearms manufactured or assembled by individuals rather than federally licensed manufacturers. Although the terms are frequently used interchangeably, “ghost gun” more specifically describes an unserialized firearm, whereas PMFs include a broader range of firearms produced through nontraditional manufacturing methods. PMFs may be entirely 3-D printed, assembled from partially completed firearm kits, or constructed by integrating additively manufactured components with commercially manufactured firearm parts. The increasing accessibility of additive manufacturing and widespread dissemination of computer-aided design files have raised concerns about concealment, regulation, and forensic evasion, particularly when factory-manufactured components …

Assessing The Impact Dynamics Of Less Lethal Ammunition, Steven Bermejo

Student Theses

Less-lethal ammunition is widely used by law enforcement as an alternative to lethal force during crowd control, on-street confrontations, and other situations requiring force. Although these projectiles are intended to reduce risk of fatal injury, serious injuries and fatalities have been reported, highlighting the need to better understand the factors that influence their impact behavior. This study evaluated the impact dynamics of four types of 12-gauge less-lethal ammunition, including rubber buckshot, single rubber ball, double rubber ball, and Byrna kinetic projectile, using kinetic energy calculations derived from projectile mass and velocity measurements. In addition, Attenuated Total Reflectance Fourier Transform Infrared …

Effects Of Bidisperse Gold Nanoparticles On Near-Infrared Surface-Enhanced Raman Spectroscopy (Sers) In Quick-Freezing-Induced Gold Nanoparticle Aggregates (Qfiaas), Elissa M. Dojka

Forensic Science Master's Projects

Gold nanoparticle (AuNP) aggregates formed via rapid freezing in liquid nitrogen exhibit strong near-infrared (NIR) plasmonic coupling. These quick-freezing-induced AuNP aggregates (QFIAAs) form moderately sized, colloidally stable structures that remain suspended for over three months, supporting a variety of analytical applications. Mechanistically, QFIAA formation arises from the confinement of nanoparticles and ions within advancing ice grain boundaries during freeze-concentration. This mechanical crowding promotes extreme physical proximity while simultaneously elevating local ionic strength, which screens electrostatic barriers to drive the assembly of dense, tightly coupled plasmonic networks.

This study investigates the plasmonic and surface-enhanced Raman scattering (SERS) behavior of bidisperse QFIAA …

Analysis Of Terpenes In Cannabis Flowers Using Gas Chromatography Via Headspace-Solid Phase Microextraction (Hs-Spme), Hannah I. Bergner

Forensic Science Master's Projects

As cannabis commercialization grows, rigorous profiling of cannabinoids, terpenes, and chemical contaminants is legally required for industry standardization and consumer safety. Terpenes are highly volatile components that dictate the unique aromatic profiles and therapeutic properties of cannabis via receptor pathways. This project focused on a gas chromatography-flame ionization detector/mass selective detector (GC-FID/MSD) combined with headspace-solid phase microextraction (HS-SPME) sampling to analyze terpenes present in four cannabis samples. Cannabis samples were tightly sealed in vials (10 mL) and heated to vaporize terpenes in the headspace above the samples, followed by the extraction of the vaporized terpenes using a polydimethylsiloxane (PDMS)-coated SPME …

Developing Solvent Tolerant Microbial Membranes: Lipid Extraction And Laurdan Fluorescence Approaches For Biofuel Optimization, Gladstone Anku

Electronic Theses and Dissertations

The high demand for sustainable energy has increased interest in advanced biofuels, though production is limited by solvent toxicity to microbial hosts. This study investigated the role of lipid composition in modulating membrane fluidity and solvent tolerance using Bacillus subtilis as a model organism. Five strains were cultured, and membrane lipids were extracted and analyzed using thin-layer chromatography and gas chromatography–mass spectrometry; however, inconsistent results limited compositional characterization. To address this problem, reconstituted vesicles composed of phosphatidylglycerol (PG) and phosphatidylethanolamine (PE) were used as model membranes. Membrane fluidity was assessed using Laurdan fluorescence spectroscopy by measuring generalized polarization (GP) values …

Pesticide Dissipation In Agroecosystems – Exploring Pesticide Fate And Transport Mechanisms To Protect Alternative Pollinators, Calvin Luu

All Graduate Theses and Dissertations, Fall 2023 to Present

Honey bees are the most well-known pollinators, but there exists thousands of other bee species that contribute to pollination; one such group of bees are the solitary bees. True to their namesake, solitary bees do not live in hives like honey bees. Some solitary bees, like alfalfa leafcutting bees (ALCB) and blue orchard bees, can pollinate crops more efficiently than honey bees. However, since they live solitary lives, pesticide exposure is much more harmful to their overall population. If one honey bee dies from pesticide exposure, the hive can still survive, and the queen bee will continue producing offspring. If …

Method Validation Of The Cdc Bottle Bioassay And A Historical Record Of Polycyclic Aromatic Hydrocarbons In Glacier National Park, Evah F. Peard

All Graduate Theses and Dissertations, Fall 2023 to Present

Certain contaminants can persist in the environment for long periods of time, build up within living tissues, travel far from their origin, and harm both ecosystems and organisms. This thesis focuses on two types of contaminants: insecticides and polycyclic aromatic hydrocarbons (PAHs). Insecticides are manufactured to control pests while PAHs are found in oil and gas products and can be produced by industry, vehicle engines, and wildfires. Understanding how harmful these contaminants are and where they end up in the environment is critical for protecting environmental health.

First, I evaluated a widely used test developed by the Centers for Disease …

On The Operation Of A Proteomics Core Facility: Selected Mass Spectrometric Studies And Methods, Rachel E. Muriph

Graduate Doctoral Dissertations

Mass spectrometry has become an indispensable analytical platform for investigating complex biological systems owing to its sensitivity, selectivity, and molecular specificity. This Dissertation demonstrates the versatility of liquid chromatography-tandem mass spectrometry (LC-MS/MS) through three studies focused on nanoparticle characterization, protein structural analysis, and plasma proteomics. In Chapter 2, LC-MS methods were developed to characterize novel lipidoid incorporated into lipid nanoparticles (LNPs) and to evaluate their in vivo biodistribution following systematic administration. Comparative proteomic analysis of the resulting protein coronas revealed distinct differences between liver and lung targeting LNP formulations, providing insight into the potential role of adsorbed blood proteins in …

Synthesis And Characterization Of Carbon Quantum Dots And Gold Nanoparticles For Norovirus Biosensing Applications In Water Systems, Breanne Evans

Master's Theses

Rapid, reliable detection of viral pathogens remains a significant challenge across water-treatment and environmental monitoring systems, including drinking-water, wastewater, water reuse, and environmental surveillance applications. Waterborne viral contamination can pose substantial public-health risks, making early detection essential for protecting water quality and responding quickly to treatment failures or contamination events. Direct potable reuse (DPR) is one particularly demanding example because it requires continuous verification of treatment performance and the broader need for rapid virus monitoring extends across many water-treatment and environmental surveillance applications. Norovirus is a priority target because of its widespread occurrence in wastewater, environmental persistence, and exceptionally low …

The Study Of Hydrophobic Biomolecules With Matrix Assisted Laser Desorption Ionization Mass Spectrometry And Atomic Force Microscopy, Brandy L. Perkins

LSU Doctoral Dissertations

Abstract

Matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) can be used to obtain localization and chemical information of hydrophobic biomolecules on tissue samples.  A technique has been developed to modify a standard MALDI matrix that improves the selectivity for hydrophobic biomolecules on the tissue sample. The modification involves the use of a Group of Uniform Materials Based on Organic Salts (GUMBOS). GUMBOS are ionic liquids (IL) that are bulky organic ions with a counter ion that can be changed for tuning.  They are more stable than traditional matrices under vacuum.  Unlike traditional IL’s, the GUMBOS melting point ranges …

Effects Of O-Glcnacylation And Phosphorylation On Tau Aggregation By Cd And Tem, Andrew Whyte Jr.

Electronic Theses and Dissertations

Alzheimer’s disease (AD) is characterized by the accumulation of extracellular amyloid-β (Aβ) plaques and intracellular neurofibrillary tangles composed of aggregated tau protein. Among the numerous post-translational modifications that regulate tau function, phosphorylation and O-GlcNAcylation have emerged as key modulators of tau aggregation and pathology. While phosphorylation is generally associated with tau misfolding and fibril formation, O-GlcNAcylation has been proposed to exert protective effects through its interplay with phosphorylation. However, the site-specific structural consequences of these modifications remain incompletely understood.

The objective of this work was to develop synthetic tools for the site-specific incorporation of O-GlcNAc and phosphate …

Information Theory Analysis Of Water Vapor Stable Isotopes From The Sail Campaign, Matthew John Rybecky

Earth and Planetary Sciences ETDs

Understanding the processes that control water vapor isotopic composition in mountain environ- ments is essential for interpreting isotope records and predicting water resource responses to cli- mate change. This thesis applies information theory to continuous, high-resolution water vapor stable isotope measurements from the Surface Atmosphere Integrated Field Laboratory (SAIL) campaign in the East River watershed of Colorado’s Upper Gunnison Basin, spanning the winter- to-spring transition of 2022–2023. The analysis employs Shannon entropy, mutual information, transfer entropy, and joint transfer en- tropy (JTE) to quantify how environmental variables, including surface meteorology, radiation, tur- bulent fluxes, and ERA5 reanalysis products, transfer information …

Elucidation Of Spin-Hamiltonian Parameters Via Spectroscopy, Magnetization, And Computation, Joshua C. Mengell

Chemistry and Chemical Biology ETDs

Molecular Quantum Information Science (QIS) is fundamentally concerned with using spin-systems as quantum bits (qubits) or as sensors. Prerequisite to using molecular systems for QIS applications, it must be understood how one can design molecules with bespoke magnetic characteristics. Herein we study various paramagnetic molecular compounds, describing their complex magnetic characteristics using a spin-Hamiltonian formalism. We utilize various (sometimes novel) methods for determining these spin-Hamiltonian parameters. Many of these molecules possess magnetic characteristics, which make them attractive as qubits or for sensing applications. These characteristics include higher total spin-states (qudits—S_T>1/2), forbidden interstate electronic transitions, systems of spatially distant …

Exploring The Nature And Role Of Local Cation Ordering In Disordered Rock Salt Cathodes For Li- And Na-Ion Batteries, You Wang

Chemistry and Chemical Biology ETDs

Cation-disordered rock-salt (DRX) cathodes provide a highly tunable platform for next-generation Li- and Na-ion batteries, but their electrochemical behavior is strongly influenced by local structural features hidden in average crystal structures. This dissertation systematically investigates local cation ordering in Li- and Na-based DRX cathodes to understand its effects on Li+/Na+ transport, redox activity, structural evolution, and electrochemical performance. In Li-based systems, Raman spectroscopy and electrochemical analysis reveal that local layered cation ordering in Mn- and Fe-based DRX cathodes is closely correlated with electrochemical behavior. Over-stoichiometric Li-based DRX oxyfluorides further demonstrate that excess Li can regulate local cation ordering, improve Li+ …

Ionophore-Based Plga Nanosensor For Selective Ion Detection And Imaging, Zhiyu Tang

Electronic Theses and Dissertations

Accurate detection of electrolyte ions is essential for biological research, disease diagnosis, and the investigation of cellular function. In this study, we developed ionophore-based PLGA nanosensors for the optical detection of biologically important ions. The nanosensors were prepared by encapsulating ionophores, chromoionophore III, and ion exchangers within PLGA nanoparticles. The resulting nanosensors showed uniform morphology, good colloidal stability, and concentration-dependent optical responses toward Na⁺, K⁺, and Ca²⁺ over the range of 10⁻⁶ to 10⁻¹ M. Reversible fluorescence responses under repeated ion concentration changes confirmed the stability and robustness of the sensors. The nanosensors also demonstrated reliable analytical performance for K⁺ …

The Characterization Of Bridging Waters And Ions In Protein-Rna Complexes, Leslie Duong

Master's Theses

Here we explore the role of bridging waters and ions in protein-RNA complexes. From an initial set of 33 high-resolution X-ray crystal structures, 17 were identified such that protein-RNA complex and component protein and RNA chains were found within 1 pH unit as indicated by crystallization conditions and their diffraction temperatures meeting one of two ranges: above or below freezing. To define an even more realistic set, 12 unbound-unbound and unbound-pseudo-unbound complexes from the 17-set were studied, showing the large fraction of complexes indicating more protein and RNA water hydrogen bonding in their actual interfacial regions as opposed to those …

Atropisomer Mechanochemistry Of Diarylethene Mechanophores: A Study Of Structure-Mechanical Activity Relationships, Cijun Zhang

Dissertations - ALL

Stimuli-responsive organic structures are advanced, intelligent platforms that dynamically adjust their physical or chemical properties—such solubility, or color—in response to external stimuli including light, heat, pH, redox conditions, mechanical force, or magnetic fields. Among these structures, mechanophores represent an important class that is specifically responsive to mechanical force. Synthetic mechanophores can be rationally engineered to exhibit tunable mechanosensitivity as well as tailored chemical and physical properties. In this work, we designed and synthesized a type of atropisomeric mechanophores based on sterically congested diarylethene photoswitches, and systematically investigated their mechanical and photochemical properties. Chapter 1 Chapter 1 provides a general introduction …

Using Low-Frequency Vibrational Spectroscopy To Develop Analytical Profiles For Polymorphic Organic Molecular Crystals, Salvatore Zarrella

Dissertations - ALL

Low-frequency vibrational spectroscopy provides a sensitive approach for characterizing polymorphism and intermolecular dynamics in organic molecular crystals. Terahertz time-domain spectroscopy (THz-TDS) and low-frequency Raman spectroscopy probe collective lattice vibrations arising from weak intermolecular interactions, offering direct insight into crystal packing, phase stability, and structural organization that is often inaccessible to conventional diffraction and mid-infrared techniques. To interpret these modes, experimental measurements are combined with periodic solid-state density functional theory (ss-DFT), which enables vibrational assignments to specific intermolecular motions, and crystal structure prediction (CSP), which maps accessible polymorphic energy landscapes. Together, these methods form a unified experimental–computational framework for understanding molecular …