Physical Sciences and Mathematics Commons^™

Synthesis And Characterization Of Acetaminophen-Derived Nanoparticles: A Novel Approach To Inhibit Fibril Formation, Hannia Elena Mendoza-Dickey

Open Access Theses & Dissertations

In the realm of nanotechnology, nanoparticles (NPs), have garnered significant notoriety in recent scientific research due to their unique physical and chemical properties, such as fluorescence emissions, nanoscale dimensions (typically <1000 nm), ease of surface modification, and biocompatibility. Nanoparticles have shown their potential across a variety of areas, including advanced industrial applications and cutting-edge biomedical research. Considering their cost-effective synthesis, they have shown promise as therapeutic agents for a variety of bioimaging and biomedical applications. This thesis describes the synthesis and detailed analysis of acetaminophen-derived nanoparticles. Techniques such as Dynamic Light Scattering (DLS), Thioflavin T (THT) assay, Attenuated Total Reflectance Infrared Spectroscopy (ATR-IR), 1H NMR spectroscopy, and Ultraviolet-Visible Spectroscopy (UV-VIS) were utilized for structural and functional assessments. Acetaminophen derived nanoparticles (ANPs) exhibit potential to hinder the amyloidogenic conversion of soluble amyloid-forming proteins into their toxic form. The novelty of this research focuses on the utilization of chemical structures capable of traversing the Blood Brain Barrier (BBB) to mitigate xenotoxicant-induced neuronal damage, a notable contributor to neurodegenerative disorders. This thesis describes the synthesis and characterization of acetaminophen derived-nanoparticles (ANPs). Our nanoparticles possess anti-amyloidogenic properties as evidenced by their ability to disrupt in the soluble-to-toxic trajectory of HEWL. The prevalence and evolution of amyloid fibrils are consistent features in the pathology of neurodegenerative diseases such as Parkinson's disease (PD), Alzheimerâ??s Disease (AD), and Huntingtonâ??s Disease (HD), as well as metabolic disorders like Type 2 diabetes (T2D). The relationship between amyloidogenic pathways and these disorders highlights the imperative for enhanced understanding and the formulation of specific therapeutic interventions.

Syntheses, Photophysics, & Application Of Porphyrinic Metal-Organic Frameworks, Zachary L. Magnuson

USF Tampa Graduate Theses and Dissertations

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface …

Terahertz From Electrons, Electronics From Terahertz, Clayton D. Moss

Theses and Dissertations

Time-domain terahertz spectroscopy (THz-TDS) is a valuable technique for studying collective ultrafast phenomena. Several mechanisms exist for converting ultrashort optical laser pulses into coherent THz sources. Broadband THz pulses can be obtained from electron currents in air plasma, which requires combinations of different colors of light to be most effective. I report multi-color generation schemes of THz pulses that deliver coherent THz output. Experimental and theoretical work using the photocurrent model describe ways to use non-harmonic color combinations to utilize several sources of light available in a table-top laser setup. Additionally, THz-TDS is used to study a variety of ultrafast …

High Resolution Intracavity Laser Absorption Spectroscopy Of Transition Metal-Containing Diatomic Molecules, Kristin Bales

Dissertations

Three transition metal-containing diatomic molecules have been studied using intracavity laser spectroscopy. Many of the transitions were recorded using a Fourier-transform spectrometer for detection, allowing collection at Doppler-limited resolution for the gas phase molecules. Several vibrational bands in two electronic transition systems of tantalum fluoride (TaF) have been analyzed, and new molecular constants provided. Transitions involving six electronic states of tungsten sulfide (WS) have been analyzed, with new and updated constants provided, including a deperturbation analysis of three vibrational bands in two of the states. Finally, a fresh perspective on two electronic states of tungsten oxide (WO) included a deperturbation …

Analysis Of Polymer-Coated Bullets Using Spectroscopic Methods, Liana R. Albano

Student Theses

Polymer-coated bullets have gained popularity because they can reduce the user’s exposure to heavy metals in the ammunition. The synthetic jacket, which surrounds the lead core, is advantageous because it prevents metal-on-metal contact between the bullet and the bore. A challenge for firearms identification is that polymer-coated bullets do not retain unique markings that can be used to identify the gun, the way standard metal-coated bullets do. However, metal-coated bullets will result in a similar challenge if the bullet is too deformed once it is recovered. Another issue is that the composition of the polymer coating was never disclosed by …

Fabrication, Measurements, And Modeling Of Semiconductor Radiation Detectors For Imaging And Detector Response Functions, Corey David Ahl

Doctoral Dissertations

In the first part of this dissertation, we cover the development of a diamond semiconductor alpha-tagging sensor for associated particle imaging to solve challenges with currently employed scintillators. The alpha-tagging sensor is a double-sided strip detector made from polycrystalline CVD diamond. The performance goals of the alpha-tagging sensor are 700-picosecond timing resolution and 0.5 mm spatial resolution. A literature review summarizes the methodology, goals, and challenges in associated particle imaging. The history and current state of alpha-tagging sensors, followed by the properties of diamond semiconductors are discussed to close the literature review. The materials and methods used to calibrate the …

Total Absorption Spectroscopy Of Mo-106 And Tc-106, Michael Cooper

Doctoral Dissertations

Total absorption spectroscopy is a method of gamma-ray spectroscopy that has gained prominence in the past several decades, as nuclear data revisions are performed on older nuclear data, which is often incomplete. A strong understanding of underlying nuclear data, particularly fission and beta decay data, is essential for nuclear reactors and nuclear fuel decay heat. This PhD work involves the analysis of fission fragments 106Mo [Mo-106] and 106Tc [Tc-106]. These neutron rich isotopes contribute upwards of 6% of the cumulative fission yield of 241Pu [Pu-241] fission, and 4% of 239Pu [Pu-239] fission. Prior data for these two fission fragments only …

Determining Bond Strengths And Dissociation Dynamics Of Diatomic Metal-Containing Ions By Photofragment Imaging, Schuyler P. Lockwood

Doctoral Dissertations

Studies of simple metal ion – ligand complexes have primarily focused on understanding their roles in activating C-H and C-C bonds. However, data are often lacking on the fundamental properties of these species, which can have unusual bond orders and cluttered electronic structures with many states of multi-reference character, complicating their treatment in theoretical studies. Experimental work determining high-precision bond energies, ground state identities and excited state dynamics of a wider variety of metal-containing ions is needed to establish a robust set of well-characterized benchmark molecules. This work describes studies of the energetics and dynamics of several MX⁺ species, …

Novel As-S-Se Compositions Of Solution-Processed Chalcogenide Thin Films For Infrared Optics, Annabella Orsini

Physics and Astronomy Honors Papers

Chalcogenide glasses (ChGs) have a wide range of interdisciplinary applications. In industry, ChGs are used to vastly improve infrared sight abilities. There are, however, improvements that can be made to the films’ stability, cost, and flexibility. Our project seeks to produce thin films that have these improvements, with capabilities comparable or better than what is widely used in the field. Thin films created through solution-based processes have proven to be much more flexible in comparison to bulk glass versions. Other elements in Group 16, such as Sulfur and Selenium have shown across literature to be a cost-effective alternative to Tellurium …

Synthesis And Characterization Of Mixed Ligand Complexes Of Ruthenium(Ii) Containing 2,2’-Bipyridine And 3,3’-Dimethyl-1,1’- Methylenebisimidazolium Ligands; A New Synthetic Approach, Matthew Schneider

Theses and Dissertations

Research into solar cells has been prioritized given the global demand for better renewable energy technologies. This demand is a result of the long-term use of fossil fuels, which generates significant pollution in highly populated urban areas. One potential solar cell technology is the dye-sensitized solar cell (DSSC). This kind of solar technology utilizes organometallic dyes to expand the types of wavelengths solar cells can use to generate electricity.12 Ruthenium(II) metal complexes of this type have been investigated heavily for this purpose.13,14,36 The main reasoning behind this is the metal-to-ligand charge-transfer (MLCT) phenomenon that such complexes exhibit. MLCT has often …

Emission Spectroscopy Of Ingaas Quantum Dots Via High-Resolution Fabry-Perot Interferometer, Raju Bhai Kc

Graduate Theses, Dissertations, and Problem Reports

Single photons emitted from self-assembled quantum dots have been widely studied to use as a promising qubit for quantum information processing. Therefore, it is critical to fully understand the emission spectra from the quantum dot's excitation if we want to use a single photon as a quantum bit. It is almost impossible to produce rotationally symmetric quantum dots due to various growth conditions and restrictions. So the real quantum dots do not have a perfectly symmetric structure. A broken rotational symmetry causes an asymmetric exchange interaction between electron and hole, leading to a fine structure splitting between two excited states. …

Certainty Is Wild And Weaving: Analyzing The Clouds Of Venus, Grace Sanger-Johnson

Senior Projects Spring 2023

Supposed detection of phosphine as a biosigature in the clouds of Venus has resulted in a flurry of interest in studying the potential habitability of Venus and other Venus-like exoplanets. However, there are still many unanswered questions about the planet's atmosphere. In this senior project, use spectroscopy to better understand the molecular composition and atmospheric dynamics of Venus. To do this, I analyzed partly-processed spectra from a previously unstudied infrared wavelength obtained at NASA’s Infrared Telescope Facility in July 2021. I developed multiple systems of analysis to extract information from the partly processed data and understand the consequences of this …

Near-Ir Spectroscopic Analysis Of The Primary Volatile Composition Of Long And Short-Period Comets, Younas Khan

Doctoral Dissertations

"Comets are among the most well-preserved objects that formed in the protosolar nebula ∼4.5 Gyr ago. Hence, they are important for understanding various aspects of the formation, evolution, and habitability of the solar system. Multiple primary volatiles (molecules directly sublimating into the coma from the nucleus) emit via rovibrational transitions in the near-IR, providing opportunities to calculate their abundances. To date, only ∼50 comets have been characterized for their primary volatiles, with the short-period Jupiter-family comets (JFCs) being significantly underrepresented. In contrast, hundreds of comets have been sampled at optical/UV wavelengths, primarily for the composition of daughter species, leading to …

Surface Reconstruction In Iron Garnets, Sushree Dash

Dissertations, Master's Theses and Master's Reports

This dissertation presents the results of a study investigating the physical mechanisms underlying an unexpectedly large increase in magneto-optic efficiency observed in iron garnet. Such materials are technologically important for telecommunications due to their nonreciprocal optical action. In the past, our group had found evidence of an enhanced Faraday rotation in bismuth-substituted iron garnet films less than 50 nm thick. Subsequent investigation revealed that this enhancement could be traced to surface effects. This is significant because understanding these phenomena could be used to formulate engineering solutions for device miniaturization. In this dissertation, we present the result of a research project …

Developing Carbon Quantum Dots As A Luminescent Material And Revisiting Ecl And Led Absolute Measurement Methods, Jonathan Ralph Adsetts

Electronic Thesis and Dissertation Repository

Luminescent materials play increasingly important roles in our lives. Improvements in these materials’ quantum efficiencies (QEs), costs and toxicity can greatly reduce the power consumption, price and environmental damage to the planet, respectively. Carbon quantum dots (CQDs) and luminescent materials exhibiting thermally activated delayed fluorescence (TADF) are two interesting materials in these aspects. Furthermore, measurements on electrochemiluminescence (ECL) and electroluminescence of these luminescent materials can quickly evaluate their performance for many applications. In this thesis, controlled CQD syntheses are revealed beneficial to luminescent materials applications. Their film ECL demonstrated relatively stable anionic and cationic radicals leading to high emission at …

Control Of Nonlinear Properties Of Van Der Waals Materials, Rezlind Bushati

Dissertations, Theses, and Capstone Projects

Van der Waals materials are a broad class of materials that exhibit unique optoelectronic properties. They provide a rich playground for which they can be integrated into current on-chip devices due to their nanometer-scale size, and be utilized for studying fundamental physics. Strong coupling of emitters to microcavities provides many opportunities for new exotic physics through the formation of hybrid quasi-particles exciton-polaritons. This thesis
focuses on exploring and enhancing nonlinearity of van der Waals materials through strongly coupling to microcavities. By taking advantage of the stacking order of TMDs, we show intense second-harmonic generation from bulk, centrosymmetric TMD systems. In …

Engineering Rare-Earth Based Color Centers In Wide Bandgap Semiconductors For Quantum And Nanoscale Applications, Gabriel I. López-Morales

Dissertations, Theses, and Capstone Projects

For many years, atomic point-defects have been readily used to tune the bulk properties of solid-state crystalline materials, for instance, through the inclusion of elemental impurities (doping) during growth, or post-processing treatments such as ion bombardment or high-energy irradiation. Such atomic point-defects introduce local ‘incompatible’ chemical interactions with the periodic atomic arrangement that makes up the crystal, resulting for example in localized electronic states due to dangling bonds or excess of electrons. When present in sufficient concentrations, the defects interact collectively to alter the overall bulk properties of the host material. In the low concentration limit, however, point-defects can serve …

Driving Piezochromism And Metallicity In Van Der Waals Materials Under Compression, Nathan Harms

Doctoral Dissertations

Complex chalcogenides provide an important platform to explore the interplay between structure, charge, and spin across pressure-induced phase transitions. Where much of the previous research has been focused on tuning these materials towards the single-layer limit, we instead explore the modification of bond lengths and bond angles under compression. In the first project we revealed piezochromism in MnPS₃. We combined high pressure optical spectroscopy and first-principles calculations to analyze the dramatic color change (green → yellow → red → black) that takes place as the charge gap shifts across the visible and into the near infrared region, moving …

Design And Fabrication Of An Apparatus For Tao High-Resolution Laser Spectroscopy, Timothy Chung

UNLV Theses, Dissertations, Professional Papers, and Capstones

In this study, an apparatus for the high-resolution laser spectroscopy of molecules is designed and constructed. The apparatus is used to identify TaO transitions, but may be used for any other molecular species in the future. It will also later be used for experiments such as quantum logic spectroscopy, which are enabled by attachable chambers that can be supplied with molecules from the apparatus. Several considerations are made to improve the quality and longevity of the apparatus such as regulating the rovibrational states of the produced molecules, optimizing the linewidth of the ionization lasers, reducing noise from sources such as …

Nondestructive Evaluation Of 3d Printed, Extruded, And Natural Polymer Structures Using Terahertz Spectroscopy And Imaging, Alexander T. Clark

Dissertations

Terahertz (THz) spectroscopy and imaging are considered for the nondestructive evaluation (NDE) of various three-dimensional (3D) printed, extruded, and natural polymer structures. THz radiation is the prime candidate for many NDE challenges due to the added benefits of safety, increased contrast and depth resolution, and optical characteristic visualization when compared to other techniques. THz imaging, using a wide bandwidth pulse-based system, can evaluate the external and internal structure of most nonconductive and nonpolar materials without any permanent effects. NDE images can be created based on THz pulse attributes or a material’s spectroscopic characteristics such as refractive index, attenuation coefficient, or …

Monitoring Bacteria Cultures Using Near Infrared (Nir) Binary Spectronephelometry (Bsn), Raman Spectra And Principal Component Analysis (Pca), Steven Ortiz

Dissertations - ALL

Current noninvasive methods cannot continuously and simultaneously monitor the concentrations of cells and media components that define the state of native bacterial cultures, because of changing turbidity. A new technique, binary spectronephelometry (BSN) has the same or better sensitivity and precision for population monitoring as optical density at 600nm (OD600), while simultaneously measuring metabolic processes. The BSN algorithm uses laser induced emission to probe mildly turbid media i.e., propagation of light occurs in the single scattering regime. A BSN "training set" associates a grid of elastic emission measurements, comprising Rayleigh and Mie scattering, and inelastic emission measurements, comprising fluorescence and …

The Exploration Of Small Molecules, Lanthanide Complexes, And Catalysis Using Electronic Structure Theory, Dynamics, And Machine Learning, Gavin Mccarver

Doctoral Dissertations

With the ever increasing availability of computational resources, more challenging chemical systems can be studied. Among these challenges are the rotational and vibrational spectra of diatomic molecules within spectroscopic accuracy, the environmental perturbations induced on a rotating water molecule, the prediction of free binding energies of lanthanide complexes using machine learning, and the study of catalytic mechanisms through a theoretical framework. High levels of electronic structure theory were combined with a rigorous treatment of either the anharmonic vibrational wave functions to study diatomic molecules or the rotational wave functions to study H₂O-pH₂ interactions. The former was initially …

Experimental Investigation Of All-Optical Production Of Metastable Krypton, Joshua Carl Frechem

Physics Theses & Dissertations

Metastable production of noble gases requires significant energy due to their filled valence shells. These transitions from the ground state are in the vacuum ultraviolet and extreme ultraviolet, which are relatively inaccessible to lasers. This necessitates the use of either electron/ion bombardment via inefficient glow discharges or the use of high-power lasers and nonlinear processes. The all-optical production efficiency using these high-power lasers promises to be orders of magnitude higher than glow discharges, but far more costly. This work looks to improve all-optical production of metastable krypton (Kr*) through the use of a commercially available vacuum ultraviolet lamp with a …

Enigma - Ongoing Development Towards Novel Beta-Decay Spectroscopy Station At Isolde, Philipp Wagenknecht

Masters Theses

Beta decay and collinear laser spectroscopy are proven efficient tools to study nuclear structure far from stability. Two areas of significance are investigations into nuclear deformation and shape coexistence, as well as delayed neutron emissions used in nuclear energy applications. This contribution presents the ongoing development towards a novel beta-decay spectroscopy station for the VITO experiment at CERN’s radioactive ion beam facility ISOLDE. The setup will utilize both collinear laser spectroscopy and beta-decay spectroscopy to measure the energy and spin-parities of the ground and excited states of radioactive beams. Initial designs of the support structure, magnetic field, and detector array …

Spectroscopic Measurements Of Meibum Compositional, Structural, And Functional Relationships To Elucidate The Role Of Meibum In Dry Eye., Anthony Chigozie Ewurum

Electronic Theses and Dissertations

The major aim of my dissertation was to investigate the etiology of dry eye disease which affects about 7 million people in the United States, causing symptoms that can lead to visual disturbance. Correlation between dry eye and an abnormal lipid layer of the tear film has been found. Tear film lipids originate mostly from the meibomian glands. Cholesteryl ester (CE) and Wax ester (WE) lipids make up most of the human meibum lipidome and the CE/WE ratio has been shown to decrease in patients with meibomian gland dysfunction. Model studies using synthetic CE and WE, although providing some insight, …

Supertertiary Structural Dynamics Modulate Function In Postsynaptic Density Protein 95, George L. Hamilton Iii

All Dissertations

Proteins, RNA, and DNA serve as the primary sub-cellular machinery that give rise to the necessary functions of life. The long-standing paradigm has been that the structures of biomolecules, or the arrangement of the subunits that make up a biomolecule, determine biological function. However, biomolecules are not static objects. Instead, they often undergo structural rearrangements that are crucial to enabling and regulating their functions. In my thesis I present several studies of the interplay between the structures, dynamics, and functions of biomolecules that combine experimental fluorescence spectroscopy and computational methods to probe these systems at the single-molecule level. In particular, …

Approaches In Molecular Engineering To Optimize The Desired Properties Of Photoactive Molecules, Douglas Joseph Breen

Chemistry and Chemical Biology ETDs

Within this dissertation, photochemical systems that bear significance to next-generation photonic materials and devices are explored. Notable advances in the design, synthesis, and characterization of three distinct groups of photoactive molecules are achieved through molecular design and spectroscopic analysis. First, novel ruthenium sulfoxide complexes bearing substituted phosphine ligands are found to provide extraordinary control over photoisomerization quantum yields. A comparison of these complexes reveals ground-state characteristics that are instrumental in this reactivity, while a novel spectroscopic technique provides rare structural evidence for an O-bonded metastable isomer. Ruthenium complexes bearing chelating carbene-sulfoxide ligands rapidly thermally revert from the O-bonded metastable isomer …

Infrared Investigation Of Lithium Ion Electrolytes: Characterization Of Structure And Dynamics Via Linear And Nonlinear Spectroscopy, Jeramie Christopher Rushing

LSU Doctoral Dissertations

Lithium ion batteries are widely employed in energy storage, but the connection between the molecular interactions in their electrolytes and the macroscopic properties remains elusive. Across three vastly different electrolytes, speciation and dynamics were studied via linear and nonlinear infrared spectroscopy to shed light on this relationship. The impact of mixed solvation on ionic speciation was studied from the perspective of the anion, which revealed a significant energetic favorability for the formation of contact ion pairs in linear carbonate solvents over cyclic carbonates. Infrared spectroscopy and density functional theory calculations described a complete inversion of the speciation due to solvent …

Electron Spin Relaxation Of Nitroxide Spin Labels And Relaxation Processes, Thacien Ngendahimana

Electronic Theses and Dissertations

MTSL is the nitroxide spin label that is most commonly used in site-directed spin labeling. However, due to rotation of its gem-dimethyl groups that average anisotropic interactions, T_m becomes short above about 70 K and this makes DEER experiments difficult at these temperatures. Strategies for decreasing spin echo dephasing and electron spin lattice relaxation rates are important for design of nitroxide spin labels and molecular qubits.

In searching for labels with longer T_m, new nitroxide spin labels devoid of gemdimethyl groups or with more rigid structures were synthesized at the University of Nebraska and pulsed EPR measurements …

Characterization And Coherent Spin Selective Manipulation Of Quantum Dot Energy Levels, Tristan Anthony Wilkinson

Graduate Theses, Dissertations, and Problem Reports

Semiconductor quantum dots (QDs) are promising candidates to fulfill a wide range of applications in real-world quantum computing, communication, and networks. Their excellent optical properties such as high brightness, single-photon purity, and narrow linewidths show potential utility in many areas. In order to realize long term goals of integration into complex and scalable quantum information systems, many current challenges must be overcome. One of these challenges is accomplishment of all necessary computing operations within a QD, which might be enabled by coherent manipulation of single QD energy level structures. In the realm of scalability for quantum devices, a way to …