Physical Sciences and Mathematics Commons^™

The Novel Chlorination Of Zirconium Metal And Its Application To A Recycling Protocol For Zircaloy Cladding From Spent Nuclear Fuel Rods, Breanna K. Vestal

Doctoral Dissertations

A novel protocol has been developed for the chemical removal of zirconium alloy (Zircaloy) cladding from spent nuclear fuel rods and subsequent isolation and purification of nuclear-grade zirconium chloride derived therefrom. This protocol is based on the chemistry developed from two new scientific findings.

First, two new oxidative chlorination reactions have been discovered for zirconium metal. In both solvents, zirconium can be quantitatively chlorinated at temperatures less than 150°C, with the operative equations seen below. In sulfur monochloride, the reaction is completed in 2 – 4 hours via surface etching, exhibiting 0^th order kinetic behavior. The elemental sulfur byproduct …

Geothermal Energy And Its Impacts On The Environment, Aditi Gorthy, Nathan Tran, Laureen Pierre-Louis

Mako: NSU Undergraduate Student Journal

From the multitude of energy sources that we have developed throughout the eons, renewable energy or “clean energy” has been on the rise to combat global warming and climate change which burning nonrenewable sources of energy have contributed to. Before geothermal energy is used as part of the mainstream energy sources some aspects must be analyzed and resolved. Unfortunately, geothermal power plants still release pollutants, such as carbon dioxide and sulfur dioxide, into the environment and cause general environmental disruptions due to drilling and changes in land formations. Recent and future studies have been and should be conducted to find …

Data Set For "Atmospheric Aging Of Combustion-Derived Particles: Impact On Stable Free Radical Concentration And Its Ability To Produce Reactive Oxygen Species In Aqueous Media", Brian Majestic, Heather L. Runberg

Chemistry and Biochemistry: Data Sets

Environmentally persistent free radicals (EPFR) are an emerging pollutant found in soot particles. Understanding how these change as they move through the atmosphere is important to human health. Here, soot was generated in the laboratory and exposed to simulated sunlight. The concentrations and characteristics of EPFR in the soot was recorded. Additionally, formation of hydroxyl radical from the photoactivated soot was measured.

Acetylacetone Oxidation At Room Temperature: A Multiplexed Photoionization Mass Spectrometric Investigation, Study Of The Russell Intermediates In Gas Phase Reactions, And The Investigation Of Oxidation Reaction Products Of Ethanol At Room Temperature, Sara Gallarati

Master's Theses

This thesis presents the combustion study of acetyl acetone using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at 298 K. The experiments were performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source of the Lawrence Berkeley National Laboratory. The reaction of acetyl acetone with chlorine (Cl) radicals was analyzed based on their photoionization spectra and reaction kinetic profiles.

Additionally, a study of the Russell intermediate has been performed. Previous to experimentation at the Advanced Light Source, computational analysis has been investigated to evaluate compounds that could possibly lead to the formation of a stable species. The …

Expanding The Polymer Zwitterion Library – Novel Phosphonium-Based Polymer Zwitterions And Analogous Structures, Marcel U. Brown

Doctoral Dissertations

This dissertation encompasses the synthesis, characterization and application of novel polymer zwitterions that significantly expand the library of available zwitterionic polymers. Their facile synthesis is facilitated by the preparation of a novel functional sultone precursor molecule, which can be ring-opened by commercially available phosphine, amine and sulfide nucleophiles, affording phosphonium, ammonium or sulfonium sulfonate monomers, respectively. Most notably, this work describes the invention of phosphonium-based polymer zwitterions, establishing a new class of zwitterionic polymer structures with unique solution and interfacial properties. Furthermore, the incorporation of these phosphonium sulfonates into block copolymer architectures with conventional polymer zwitterions, and the resulting switchable …

Contra-Thermodynamic Halolactonization Of Lactam-Tethered 5-Aryl-4(E)-Pentenoic Acids For The Flexible And Stereocontrolled Synthesis Of Fused Lactam-Halolactones, Timothy K. Beng, Claire Borg, Morgan J. Rodriguez

All Faculty Scholarship for the College of the Sciences

Halolactonization of alkenoic acids enables the construction of oxygen-heterocycles via intramolecular halonium-induced nucleophilic addition. Although the literature is currently inundated with halolactonizations of 5-aryl-4(E)-pentenoic acids that predictably afford the 6-endo cyclization adducts, methods that reliably alter the innate regioselectivity bias to instead deliver the thermodynamically less favored 5-exo cyclization products are relatively rare. Here, we attempt to bridge this gap and have found mild conditions for contra-thermodynamic halolactonization of lactam-tethered 5-aryl-4(E)-pentenoic acids that lead to the formation of trans-fused lactam-γ-lactones. The natural proclivity for these 5-aryl-4(E)-pentenoic acids to undergo 6-endo cyclization is overridden and 5-exo-trig cyclization predominates. The success of …

Sulfur Behavior In The 1257 Ce Samalas Magma (Lombok, Indonesia) As Revealed By Volcanic Apatite, Yasmin Jackson

Earth Sciences Theses and Dissertations

Explosive volcanic eruptions can inject massive amounts of volatiles, including SO₂ and H₂S, into the stratosphere, inducing drastic tropospheric cooling via sulfate aerosols. Greenland and Antarctic ice cores record evidence of these substantial releases of SO₂ and H₂S, including the massive release during the ultraplinian 1257 CE Samalas eruption. The 1257 CE Samalas eruption is estimated to have released ~158 Tg of SO₂, making it the largest volcanogenic release of SO₂ within the last 2000 years. Vidal et al. (2016) propose that most of this sulfur (S) was hosted in a …

Comparing Computational Methods By Stretching Diatomic Molecules, Aaron Mitchell

Undergraduate Student Research Internships Conference

A comparison of functionals was done by comparing full electron density profiles along the bond axis of H₂ and N₂. Additionally, based on the success of the (HF)-DFT method, the goal of this project was to compare the mRKS method to (HF)-DFT.

Stereocontrolled Access To Δ-Lactone-Fused-Γ-Lactams Bearing Angular Benzylic Quaternary Stereocenters, Timothy K. Beng, Morgan J. Rodriguez, Claire Borg

All Faculty Scholarship for the College of the Sciences

C-fused γ-lactam-lactones are resident in several bioactive molecules, including anticancer agents such as omuralide. In this embodiment, we report mild conditions for the catalytic halolactonization of lactam-tethered 5-aryl-4(E)-pentenoic acids. The use of dichloromethane as the solvent and Ph₃PS as the catalyst led to predominant 6-endo-trig cyclization and furnished the trans-fused-γ-lactam-δ-lactones. The transformation is modular, regioselective, chemoselective, and diastereoselective. The γ-lactam-δ-lactones bear angular quaternary benzylic stereocenters, which is noteworthy since the presence of a quaternary carbon in bioactive small molecules often promotes an element of conformational restriction that imparts potency, selectivity, and metabolic stability. The …

Targeting Heat Shock 27 Kda Protein Induces Androgen Receptor Degradation, Yaxin Li

ETD Archive

Glioblastoma (GBM) is the most common and aggressive brain tumor, with very poor prognosis. Androgen receptor (AR) plays a significant role in the progression of GBM, and anti-androgen agents have the potential to be used for the treatment of GBM. However, AR mutation commonly happens in GBM, which makes the anti-androgen agents less effective. Heat shock 27 kDa protein (HSP27) is a well-documented chaperone protein to stabilize AR. Inhibition of HSP27 results in AR degradation regardless the mutation status of AR, which makes HSP27 a good target to abolish AR in GBM. Identified compound I ((N-(3-((2,5-dimethoxybenzyl)oxy)-4-(methylsulfonamido) phenyl)-4-methoxybenzamide) inhibits GBM cell …

Dr. Lawrence J. Berliner, Anit Tyagi

DU Undergraduate Research Journal Archive

An interview with Dr. Lawrence J. Berliner.

Prediction And Confirmation Of A Switch-Like Region Within The N-Terminal Domain Of Hsirt1, Angelina T. Huynh, Thi-Tina N. Nguyen, Carina A. Villegas, Saira Montemorso, Benjamin Strauss, Richard A. Pearson, Jason G. Graham, Jonathan Oribello, Rohit Suresh, Brooke Lustig, Ningkun Wang

Faculty Research, Scholarly, and Creative Activity

Many proteins display conformational changes resulting from allosteric regulation. Often only a few residues are crucial in conveying these structural and functional allosteric changes. These regions that undergo a significant change in structure upon receiving an input signal, such as molecular recognition, are defined as switch- like regions. Identifying these key residues within switch-like regions can help elucidate the mechanism of allosteric regulation and provide guidance for synthetic regulation. In this study, we combine a novel computational workflow with biochemical methods to identify a switch-like region in the N-terminal domain of human SIRT1 (hSIRT1), a lysine deacetylase that plays important …

The Effects Copper Has On Casting Glass, K. Malika Haver

Honors Projects

The aim of this honors project was to discern the difference between how various types of copper reacted with glass. The two disciplines that were connected were chemistry and glassblowing. The basic components learned in chemistry were applied to glass with an end goal of a project installation that visualized the discoveries with copper. The glassblowing technique used was lost wax casting, and the two types of copper used were copper foil and fine copper metal powder. The copper was found to turn the glass into various blues with the intensity and darkness of the blues being dependent on the …

Applied Math In Introductory Chemistry, Ji Kim, Grace Pai

Open Educational Resources

Students, particularly those who are non-science majors, often struggle with college-level science courses required for graduation due to the applied mathematics needed to successfully complete the course. This resource includes four activities on the topics of units and measurements, dimensional analysis, density, and gases. These topics were specifically designed to teach the mathematics embedded in these topics in a culturally responsive way. Throughout the activities, we incorporate these four elements of culturally relevant pedagogy (Ladson-Billings, 2009) in order to engage students in successfully solving basic mathematics in chemistry while promoting their interest in learning chemistry.

Biochemical Characterization Of Induced Pluripotent Stem Cell-Derived Cardiomyocytes As A Model Of Barth Syndrome, Alisha J. House

ETD Archive

Barth Syndrome (BTHS) is an X-linked inborn error of metabolism (IEM) which manifests as a multi-systemic disease. One of the primary symptoms is dilated cardiomyopathy, and alongside the cardiovascular disease that arises, patients often experience metabolic abnormalities such as 3-methylglutaconic aciduria, growth retardation, and neutropenia. There has been a need for the development of a suitable in vitro modeling system which will accurately recapitulate the biochemical and physical nature of BTHS. The purpose of this project has been to develop a model for studying the biochemical pathogenesis of Barth Syndrome using human induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CMs). To achieve …

A Damaged Reputation: Nuclear Depictions In Entertainment Media, Alexander Cannon

Chemistry & Biochemistry Student Scholarship

This paper, originally written for Dr. Adamus Liotta in an honors chemistry class, explores the possibility of a significant influence over public common sense found in the depictions of entertainment media. Through careful analysis and interpretation of Godzilla, The Simpsons, Fallout, and Call of Duty, this paper finds a synergy throughout this diverse range of audience, medium and historical origin, which culminates in an effect much greater than the sum of its parts. This effect frames nuclear science, of any kind, in a hyperbolically catastrophic and horrific light, reinforcing an excessively cautious, pessimistic public perspective on nuclear technology …

Synthesis Of Phosphonate-Based Diimide Ligands, Kenya V. Medina, Adelani Pius

St. Mary's University Honors Theses and Projects

There has been a resurged interest in the synthesis of metal-organic frameworks because of their potential applications in energy production and drug delivery. Although diimides are insoluble in aqueous solutions, the addition of phosphonic acid allows the complex to be water soluble, which greatly increases their application. Therefore, the creation of a hybrid metal-organic complex by the addition of phosphonic groups to diimide ligands can result in a polar porous compound. In this project the ligand design included the use of dianhydrides including pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, and biphenyl-tetracarboxylic acid dianhydride. These dianhydride precursors were refluxed under argon …

Strategic Consideration And Recommendation On Development Of Chemistry In China, Yanlin Cheng, Shuxian Wu, Qing Dai, Chunying Chen, Yuliang Zhao

Bulletin of Chinese Academy of Sciences (Chinese Version)

Chemistry, as a central science linking all the other sciences, has played an influential role in promoting the development of the whole scientific and technological field and the prosperity of economy and society. Developed countries strongly support the development of chemistry and effectively promote the level of chemical research and chemical industry. Since the founding of the People's Republic of China, chemical research has been supported among the field of natural sciences, and its current level is at the forefront of the world. However, there are still problems in the field of chemistry research in China, such as insufficient major …

P3k14c, A Synthetic Global Database Of Archaeological Radiocarbon Dates, Erick Robinson

Anthropology Faculty Publications and Presentations

Archaeologists increasingly use large radiocarbon databases to model prehistoric human demography (also termed paleo-demography). Numerous independent projects, funded over the past decade, have assembled such databases from multiple regions of the world. These data provide unprecedented potential for comparative research on human population ecology and the evolution of social-ecological systems across the Earth. However, these databases have been developed using different sample selection criteria, which has resulted in interoperability issues for global-scale, comparative paleo-demographic research and integration with paleoclimate and paleoenvironmental data. We present a synthetic, global-scale archaeological radiocarbon database composed of 180,070 radiocarbon dates that have been cleaned according …

Fabrication And Characterization Of Novel Agnps Functionalized With Chlorothymol (C@Agnps), Lirim Sopaj

Browse all Theses and Dissertations

In this study, novel silver nanoparticles (AgNPs) were successfully synthesized and functionalized with an antibacterial agent, namely chlorothymol (denoted C@AgNPs). The resulting colloid (C@AgNPs) was purified by two comparative methods: ultrafiltration and ultracentrifugation. Ultrafiltration proved to be more efficient in purifying and size selecting (10 kD filter) and concentrating the C@AgNPs than ultracentrifugation. The physicochemical properties of the filtered C@AgNPs were then characterized by UV-Vis absorption spectroscopy, inductively coupled plasma optical emission spectroscopy (ICP-OES), Raman spectroscopy, Cytoviva hyperspectral imaging, and Scanning electron microscopy. These measurements confirmed the functionalization of the core AgNPs with chlorothymol and suggest the proposed mechanism of …

Harmful Algal Blooms In Caesar Creek Lake And Their Relationship To Riparian Cover, Morgan C. Grunden

Browse all Theses and Dissertations

Caesar Creek Lake (CCL) in Warren County, OH has recently been experiencing harmful algal blooms (HABs) which are most likely attributed to an excess of phosphorus (P) from fertilizers and manures applied to surrounding fields. Sediments act as a sink for P later supplying a source of P in lakes for HABs when waters become thermally stratified and anoxic. This study seeks to determine the relationship between HABs in CCL and riparian cover at the main tributaries, Anderson Fork and Caesar Creek. In order to do this, sediment samples were collected from four sample sites along Anderson Fork and three …

Detection And Identification Of Prevalent Cutting Agents In 'Street' Samples Utilizing Handheld And Benchtop Raman Spectroscopy And Surface-Enhanced Raman Spectroscopy (Sers), Nicole Kenny

Browse all Theses and Dissertations

Illicit and licit drugs continue to have a negative impact on the public’s health even with new regulations and laws. At local, state, and federal levels, crime laboratories analyze samples in a variety of mixtures and concentrations. Raman spectroscopy is a molecular fingerprinting, multiplex technique, which is considered a category A forensic characterization tool by the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG). The sensitivity of the Raman technique can be further enhanced down to the single-molecule detection level when analytes of interest are located at the interstitial sites of aggregated silver nanoparticles (i.e., the “hot spots” …

Detection Of Benzotriazole And Related Analogues In Surface Samples Collected Near An Ohio Airpark, Clara Leedy

Browse all Theses and Dissertations

Benzotriazoles are a class of contaminant of emerging concern which are commonly used as anticorrosive agents in aircraft deicer and anti-icing fluids (ADAFs). The analogues 1H-benzotriazole (BTZ), 4-methyl-1H-benzotrizole (4m-BTZ), and 5-methyl-1H-benzotriazole (5m-BTZ) are commonly found in environmental occurrence together. The two methylated isomers, collectively known as tolytriazole (TTZ), have different toxicity and stability. These contaminants are highly water soluble and resistant to biodegradation, making them persistent through water treatment. Benzotriazoles have been detected worldwide; this investigation focuses on monitoring three sites near a small airpark in Wilmington, Ohio. Two sites that receive runoff from the airpark, Lytle Creek and Indian …

Gene Vectors With Fluorescence Tracking Capabilities, Sophia Despina Angelopoulos

Browse all Theses and Dissertations

This project focuses on the optimization of benzothiazole-based chromophores to utilize them as fluorescent tags functionalized onto stimuli-responsive, or “smart,” polymers as non-viral gene delivery vectors for gene therapy applications. Blue-fluorescent emissive chromophores will allow tracking capabilities for the transfection pathway of the vector to be monitored as it delivers the DNA payload within intercellular space. The most appropriate chromophore must be covalently bound to a free amine within the vector, which is accomplished through NAS chemistry from fluorophenyl-benzothiazoles (F-BTZ-CBz) derivatives to amidated hyperbranched poly(ethyleneimine)(HPEI-IBAm0.61). HPEI is considered to be a synthetic polycation, which promotes tunable solubility through characteristics of …

Dirhenium Compounds Containing The Diphosphine Ligands Ph2pch2pph2, Ph2pch(Cn)Pph2, Or Ph2pch(Ch3)Pph2: A Comparative Study, Hannah C. Arthur

Undergraduate Honors Theses

When M₂L₁₀ complexes containing two rhenium(III) atoms in a quadruple bond react with an excess of the diphosphine ligand Ph₂PCH₂PPh₂, the bond order decreases, and the rhenium is reduced to rhenium(II). When two diphosphine ligands are bonded to the dirhenium center, they can adopt a trans-trans, trans-cis, or cis-cis configuration. NMR spectra of compounds that adopt the cis-cis arrangement show unusually large downfield shifts for one of the bridgehead methylene hydrogens (P-CH₂-P). To understand the unusual chemical shift, the hydrogens first have to be assigned. The strategy for …

The Vagabond Flourine Atom Revisited: Dissociative Photoionization Of Tri- And Pentafluoropropene, Jessica K. De La Cruz

University of the Pacific Theses and Dissertations

Photoelectron Photoion Coincidence (PEPICO) Spectroscopy studies on two unsaturated hydrofluorocarbons (HFCs), also known as hydrofluoroolefines (HFOs), are presented here. Previously, the Sztáray group has studied the dissociation of trans-1,3,3,3-tetrafluoroprop-1-ene (ElixClean), which is a fourth-generation refrigerant and propellant and has lower global warming potential than its precursors. My study is an extension of the ElixClean study as it aims to explore how the different number of fluorine atoms impact the dissociation reactions of these molecules. Both 3,3,3-trifluoropropene (TFP) and cis-1,2,3,3,3- pentafluoropropene (PFP) are also utilized as propellants and refrigerants.Measurements were carried out with remote access to the CRF-PEPICO (combustion reactions followed …

Gas-Phase Acid-Base Properties And Conformations Of Oligopeptides Through Mass Spectrometry And Computational Studies, Yuntao Zhang

University of the Pacific Theses and Dissertations

This dissertation presents a comprehensive study of the peptides of interest to deeper understand the gas-phase acid-base properties in relation to their conformations and chirality. In the first part of the study, two pairs of alanine (A)-based isomeric peptides consisting of a basic probe, lysine (Lys) or 2,3-diaminopropionic acid (Dap), were investigated to understand the nature of the enhanced basicity when the basic probe was moved from the N-terminus to the C-terminus. In the second part of the study, alanine-based peptides containing a cysteine (C) as the acidic probe were investigated to understand the chirality effects on the gas-phase acidity …

Measurements Of Atmospheric Radicals, Heather L. Runberg

Electronic Theses and Dissertations

Atmospheric particulate matter (PM) is a global health concern. PM_2.5 is formed primarily through combustion processes such as automobile use and industrial activity. Natural sources of PM_2.5 result from events like volcanos and wildfires. Upon inhalation, PM_2.5 is small enough to travel deep into the lungs where it can form reactive oxygen species (ROS), such as hydroxyl radical (OH), causing oxidative damage to pulmonary tissues. PM_2.5 has been linked to cardiopulmonary diseases such as asthma, chronic obstructive pulmonary disease (COPD), and high blood pressure.

PM_2.5 is small enough to remain aloft and travel many hundreds …

Heterogenous Reduction Of Co2 Over Boron-Rich Alb2, Jose C. Berger

Honors Undergraduate Theses

Evidence suggests that the recent drastic changes in the global climate have been caused by greenhouse gases, especially CO­₂. As a result, scientists are aiming to develop processes that either minimize the production of these gases or convert them into products of higher value. To that end, the catalytic properties of a two-dimensional boron-rich material were investigated. Herein is reported that such a material can reduce CO₂ into benzene, C₃ species, and C₄ species at relatively low temperatures (225-450 ℃) and pressures (0.38 MPa). Current data suggest that a low-temperature induction period (e.g., 225 ℃) …

Protocol For Fabricating Electroless Nickel Immersion Gold Strain Sensors On Nitrile Butadiene Rubber Gloves For Wearable Electronics, Sara S. Mechael, Yunyun Wu, Yiting Chen, Tricia Breen Carmichael

Chemistry and Biochemistry Publications

This protocol describes the fabrication of patterned conductive gold films on nitrile butadiene rubber (NBR) gloves for wearable strain sensors using electroless nickel immersion gold (ENIG) plating, a solution-based metallization technique. The resulting NBR/ENIG films are strain sensitive; resistance measurements of a patterned sensing array can be used to map human hand motions. This protocol also describes challenges related to the ENIG process and troubleshooting steps to achieve conformal gold films for strain sensing over a large working range. For complete details on the use and execution of this protocol, please refer to Mechael et al. (2021).