Chemistry Commons^™

Understanding And Tuning Magnetism In Van Der Waals-Type Metal Thiophosphates, Rabindra Basnet, Jin Hu

Physics Faculty Publications and Presentations

Over the past two decades, significant progress in two-dimensional (2D) materials has invigorated research in condensed matter and material physics in low dimensions. While traditionally studied in three-dimensional systems, magnetism has now been extended to the 2D realm. Recent breakthroughs in 2D magnetism have attracted substantial interest from the scientific community, owing to the stable magnetic order achievable in atomically thin layers of the van der Waals (vdW)-type layered magnetic materials. These advances offer an exciting platform for investigating related phenomena in low dimensions and hold promise for spintronic applications. Consequently, vdW magnetic materials with tunable magnetism have attracted significant …

Synthesis And Characterization Of Medicinally Privileged Aza Heterocycles, Nneoma James

Theses and Dissertations

Four-membered cyclic amides, commonly known as β-lactams, have played a crucial role in drug discovery research since its discovery by Alexander Fleming in 1928 from Penicillium notatum. The β-lactam antibiotics are broadly effective against several bacterial infections through acylating the transpeptidase involved in cross-linking peptides to form peptidoglycan or periplasmic murein, which is a fundamental constituent of the bacterial cell wall for both the gram-positive (ten or more layers) and gram-negative (one or two layers) bacteria. Although for more than eight decades, β-lactams have been recognized as antibiotics, later, other medicinal activities of β-lactam derivatives have been reported, including lowering …

Chemical Investigation Of The Ethanol Extract Of Tillandsia Usneoides (Spanish Moss), Jakir Hossain

Theses and Dissertations

Tillandsia usneoides in epiphytic bromeliads takes up water through absorptive trichomes on the shoot surface under extreme environmental conditions. Although previous studies revealed the way by which T. usneoides absorbs water and prevents water loss, its water transport remains unclear. Uses of T. usneoides L. have been documented going back to pre-Columbian and late archaic societies. Between the 1800s and 1900s. T. usneoides was utilized in fruit packing and polish, among other industrial goods. In terms of medicine, tillandsia is well-known for treating leucorrhea, rheumatism, ulcers, hemorrhoids, and as an anti-diabetic, emetic, analgesic, purgative, antispasmodic, and diuretic. The chemical composition …

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 …

Developing Catalysts For The Hydrolysis Of Glycosidic Bonds In Oligosaccharides Using A Spectrophotometric Screening Assay, Susanna Striegler

Chemistry & Biochemistry Faculty Publications and Presentations

In a proof-of-concept study, a method for the empirical design of polyacrylate gel catalysts with the ability to cleave 1→4 α-glycosidic bonds in di- and trisaccharides was elaborated. The study included the synthesis of a 300-gel member library based on two different cross-linkers and 10 acrylate monomers, identification of monomodal gels by dynamic light scattering, and a 96-well plate spectrophotometric screening assay to monitor the hydrolysis of chromophore-free maltose into glucose units. The composition of the matrix of the most efficient catalysts in the library was found to enable CH−π, hydrophobic, and H-bond accepting interactions during the hydrolysis as typically …

Extraction Of Neutron-Gamma Irradiated Diffusion Pump Oils, Cooper L. Tillman

All Theses

This work successfully demonstrates solvent extraction methods for separation of oil from the by-products when two commercially available vacuum pump oils were exposed to an intense neutron and gamma-ray radiation environment. Nuclear fusion power at a commercial scale has accelerated the need for radiation resistant vacuum technology, such as oil-based diffusion pumps. Polyphenyl ether and aromatic silicone oils were irradiated at the Rhode Island Nuclear Science Center (RINSC) up to MGy absorbed doses with neutron and gamma-ray radiation. Solvent extractions were performed using hexane and isopropanol to characterize the oil extraction as a function of total absorbed dose. The by-products …

Electrocatalytic Reduction Of Hydrogen Peroxide At Paraffin-Sealed Nitrogen-Doped Carbon Fiber Ultramicroelectrodes, Yakubu Gausu Mohammed

Electronic Theses and Dissertations

Compared to unmodified carbons and even some metal materials, nitrogen-doped carbons have been found to exhibit better performance for reducing oxygen-oxygen bonds, a key step in electroreduction of both O₂ (an important reaction in energy applications) and H₂O₂ (an important reaction in sensing and biosensing). Previous studies from our lab revealed that thermal decomposition of urea in the presence of carbon fiber (CF) results in N-doped that exhibited good electrocatalytic properties for H₂O₂ reduction. However, previous methods of sealing ultramicroelectrodes (UMEs) made from N-doped CF using laser heating of borosilicate capillaries and epoxy …

Assessing The Reactivity Of Amino Acids To Chlorination Using Capillary Electrophoresis, Pedro De Allende

Electronic Theses, Projects, and Dissertations

Amino acids (AA) are ubiquitous in wastewater systems. One of the most popular wastewater treatments is chlorination which is effective at eradicating bacteria and overall treating the wastewater, but it can also produce disinfection by-products (DBPs). Certain DBPs have been classified as Class B Carcinogens to humans and are therefore highly regulated and monitored. Past studies have shown that natural organic matter (NOM), specifically amino acids, can be precursors to DBPs if chlorinated to the correct dose. This thesis project explored AA chlorination's mechanism(s) to understand further which products arise. In particular, the investigation detailed which steps of the mechanism …

Effects Of Antifreeze Proteins On Lipid Membrane Stabilization At Cold Temperatures, Emily Vernon

Boise State University Theses and Dissertations

Cold-adapted organisms use antifreeze proteins (AFPs) and antifreeze glycoproteins (AFGPs) to enable survival in freezing habitats. AF(G)Ps have been proposed to prevent leakage of intracellular metabolites by stabilizing cellular membranes, a property that could be of great physiological and biomedical relevance. The generality of this effect is not understood, and for the known examples of membrane leakage prevention by AF(G)Ps, the mechanisms remain unclear. Here, we report a comprehensive evaluation of the effects of different AFPs on the leakage of ions and dyes from model membrane systems. We find that leakage is best prevented by AFGPs, while insect AFPs showed …

Characterizing Gsk3Β Interaction And Kinetics Via Isothermal Titration Calorimetry, W A Bhagya De Silva

UNLV Theses, Dissertations, Professional Papers, and Capstones

Glycogen synthase kinase 3β (GSK3β) is a multifunctional serine/threonine kinase involved in several key signaling pathways, including glycogen metabolism, WNT/β-catenin, and Hedgehog signaling. Hyperactivity of GSK3β has been linked to Alzheimer’s disease, bipolar disorder, type II diabetes, and some cancers. Therefore, GSK3β is of interest as a target for therapeutics. Lithium ion (Li+) is a classical inhibitor of GSK3β. Structurally similar beryllium ion (Be2+) is ~1000-fold more potent. Lithium and beryllium have demonstrated pathway-specific and cell type-specific inhibition of GSK3β, prompting an investigation into the inhibitory mechanisms and thermodynamic characteristics of the metal-enzyme interaction.Isothermal titration calorimetry (ITC) is a label-free …

Evaluation Of Electrochemical Corrosion, Electrodeposition, And Other Electroanalytical Methods As Investigative Forensic Techniques For Advancing Metal Substrate Analysis, Crystal C. Kitanovski

UNLV Theses, Dissertations, Professional Papers, and Capstones

Friction ridge skin, bearing unique patterns of epidermal ridges commonly known as fingerprints, has served as a crucial tool for identification since ancient times, with its utilization dating back to Chinese culture around 221 B.C. Today, friction ridge skin impressions remain vital evidence in forensic investigations, aiding in the identification of suspects. While fingerprints, palm prints, and footprints can all serve as identifying markers, this dissertation focuses specifically on fingerprints, broadly classified as visible or latent. Latent fingerprints, though invisible to the naked eye, constitute the majority of prints collected from crime scenes, necessitating physical, chemical, or physicochemical processing for …

Studying The Chemistry-Property Relationship In Magnetic And Optical Materials: Spin S = 3/2 Systems Of Neodymium, Manganese, And Cobalt Oxyanions, Xudong Huai

All Dissertations

This dissertation describes the design and tunability of new magnetic and optical materials, emphasizing the intricate relationship between their crystal structures and their optical, electronic, and magnetic properties.

Two new frustrated magnets, ANd(SO₄)₂ (A = Rb, Cs), were designed and synthesized to examine the influence of the the counter cation A site in Nd lanthanide materials featuring a distorted triangular magnetic lattice with S = 3/2. This work demonstrates how the tunability of magnetic and photoluminescent properties can be achieved through the A sites, with findings validated through density functional theory calculations.

AMnTeO₆ (A = Ca, …

Assessment Of Tce And Chiral Pcb Dechlorination Rate, Congener Diversity, And Enantioselectivity In Town Creek, Sc, Usa Sediment Microcosms, Catherine P. Sumner

All Dissertations

Polychlorinated biphenyls (PCBs) and trichloroethene (TCE) are ubiquitous contaminants and are recognized as persistent organic pollutants due to their extreme chemical stability. PCBs were manufactured by chlorinating biphenyls that created 209 congeners with various structures, of which 19 are chiral and can exist as a pair of stable atropisomers. PCBs have been known to cause developmental and neurological toxicity in humans and wildlife; they can act as endocrine disrupters, carcinogens, and teratogens. Sangamo Weston Inc. was an industrial plant located near Town Creek in Pickens Country, South Carolina, that manufactured capacitors and used Aroclors 1016 and 1254 as dialectic fluids …

Proton-Coupled Electron Transfer To Drive Biomass Conversion, Cody Canote

Graduate Theses and Dissertations

Meeting rising demands for commodity chemicals while simultaneously easing reliance on fossil fuels presents one of the most substantial challenges for chemistry to date. Biomass has emerged as a sustainable precursor to commodity chemicals but requires substantial deoxygenation to displace petrochemicals. Development of efficient catalysts to achieve these transformations remains one of the central goals of inorganic and organometallic chemistry. Electrochemical strategies to propel biomass conversion are attractive, providing the driving force for reactivity and insights into catalyst mechanism. This work focuses on proton-coupled electron transfer (PCET) to facilitate redox catalysis in biomass up conversion and homolytic bond cleavage in …

Computational Models That Exploit Spatial, Temporal, And Voltage-Current Relationships In The Electrochemical Generation-Collection Of Redox-Active Molecules, Miguel Angel Abrego Tello

Graduate Theses and Dissertations

The numerical studies in this dissertation explore the application of redox cycling, an advanced electrochemical technique, for analyzing bioelectrochemical systems with a particular focus on small-volume samples and involves electrodes that can be activated to oxidize and reduce, separated by varying distances and featuring different geometries. The redox cycling approach facilitates the spatio-temporal interrogation of kinetics, mass transport, and the quantification and identification of chemical systems. We optimize a previously fabricated neural probe design on an SU-8 substrate, featuring coplanar arrays of nine microband electrodes suited for in vivo applications. Through comprehensive in situ and in silico redox cycling studies …

La1-Xsrxcoo3 Perovskite: Antimicrobial Properties And Pvdf Based Piezoelectric Nanogenerator For Energy Storage Through Self-Induced Polling, S M. Anyet Ullah Shohag

Theses and Dissertations

Piezoelectric Nanogenerators (PENGs), which can produce electrical energy from mechanical energy via ferroelectric effect, are one of the ambient sources of green energy. PENGs have gathered a huge attention due to cost-effectiveness, mechanical stability, and easy installation process. In this experiment, different weight percent of Sr2+ doped Lanthanum Cobaltite (La1- XSrXCoO3) perovskite, a ferroelectric material, was synthesizes by using a simple combination of sol-gel and molten-salt process and then characterization by X-ray diffraction, and scanning electron microscopy ensures the uniform morphology of nano cubes. Poly (vinylidene difluoride) (PVDF), N,N-dimethylformamide and acetone solution were used to make a flexible film using …

Use Of Computational Methods To Determine The Relative Thermodynamic Stability Of Myricetin, Quercetin And 4-Methylesculetin For Use As Spin Traps, Cole Walker

Electronic Theses and Dissertations

The research conducted focused on the oxidative intermediates of antioxidants known as Myricetin, Quercetin, and 4-Methylesutin by calculating the reaction mechanism. During this research, computational quantum chemistry on selected parts for the 3 antioxidants previously mentioned were performed to find the most stable intermediate to act as a spin trap. The hypothesis is that the intermediates found can act as spin traps which will allow longer preservation of a free radical to be identified using Electron Paramagnetic Resonance (EPR) spectroscopy. This may be because the buildup of excess free radicals in a system leads them to cause damage down to …

Di­Chlorido­Tetra­Kis­(3-Meth­­Oxy­Aniline)Nickel(Ii), Benjamin A. Mukda, Mark M. Turnbull

Chemistry

The reaction of nickel(II) chloride with 3-meth­oxy­aniline yielded di­chlorido­tetra­kis­(3-meth­oxy­aniline)nickel(II), [NiCl₂(C₇H₉NO)₄], as yellow crystals. The Ni^II ion is pseudo-octa­hedral with the chloride ions trans to each other. The four 3-meth­oxy­aniline ligands differ primarily due to different conformations about the Ni—N bond, which also affect the hydrogen bonding. Inter­molecular N—H⋯ Cl hydrogen bonds and short Cl⋯Cl contacts between mol­ecules link them into chains parallel to the b axis.

Evolution Mechanism Of Organic Macromolecular Structure During Lignite Pyrolysis, Ying Shi, Yanming Zhu, Zhenjiang You, Wu Li, Yang Wang, Yu Song

Research outputs 2022 to 2026

Understanding the mechanisms governing coal pyrolysis reactions, particularly in relation to the coal macromolecular structure, is crucial for improving energy efficiency and facilitating the transition of coal into a clean energy source. This study employs cutting-edge techniques, such as High-Resolution Transmission Electron Microscopy (HRTEM) and Thermogravimetric Analysis coupled with Fourier Transform Infrared Spectroscopy and Mass Spectrometry (TG–FTIR–MS), to analyze lignite and its residual solid samples subjected to pyrolysis across a range of temperatures from 300 °C to 1100 °C. The variational characteristics of the macromolecular structure during coal pyrolysis are examined. Utilizing molecular dynamics simulations, we analyze the evolution mechanism …

Phthalocyanine-Enabled Technologies For Water Treatment And Disinfection Strategies, Hooralain Bushnaq, Catherine Munro, Sisi Pu, Amir Razmjou, Masoumeh Zargar, Giovanni Palmisano, Srinivas Mettu, Ludovic F. Dumée

Research outputs 2022 to 2026

Water treatment and disinfection are critical factors in ensuring a safe and sustainable water supply. Phthalocyanines (Pcs), a class of versatile and robust organic compounds, have garnered significant attention for their application in various water treatment processes. This review paper offers a groundbreaking investigation of Pc-enabled technologies within the domain of water treatment applications. The core aim of this review is to meticulously analyze the chemical and optical properties of Pcs, elucidate their photosensitization mechanism and establish the crucial connection between their chemical structure and photodynamic efficacy. The various modes of Pcs application in water treatment processes - whether in …

Metal Assisted O2-Dependent Carbon-Carbon Bond Cleavage Of Β-Diketones And Flavonols, Stephen N. Anderson

All Graduate Theses and Dissertations, Fall 2023 to Present

Almost everything we interact with on a daily basis has been synthesized by chemists ranging from plastics, food preservatives, and medications. The diversity of synthetic molecules are achieved by the formation of new bonds between existing molecules and/or through the cleaving of bonds found in a molecule. There are uncountable amount of conditions reported to facilitate chemical reactions which all depend on the nature of molecules being used and the environment it is used in.

In recent years, more attention has been paid to identify chemical reactions that can use more environmentally favorable conditions and reduce the use of limited …

Functional Electrolytes Designing And Studying For Lithium Metal And Non-Aqueous Zinc Metal Batteries, Liping Zhang

All Graduate Theses and Dissertations, Fall 2023 to Present

Our current energy policy relies heavily on burning fossil fuels, raising serious concerns due to CO₂-related global warming. Consequently, significant progress is being made in pursuing renewable and green energy sources, such as solar, wind, and geothermal energy. These renewable energies require rechargeable batteries as energy storage systems to compensate for their intermittent nature.

Over the decades, lithium-ion batteries (LIBs) have become the dominant power sources for portable electronic devices. Current LIBs rely on graphite anodes with a limited theoretical capacity (372 mAh g^-1), which restricts their advanced applications. Li metal (Li⁰) anodes, with …

Studies Of Exotic Electronic, Optical, And Electrochemical Properties In Nanoparticle Assembly And Graphene, Jay Min Lim

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

It is well known that exotic properties and phenomena emerge as structural dimensions shrink to nanoscales. We self-assembled one-dimensional chains of gold nanoparticles in solution and quantified the growth process by monitoring the redshift of localized surface plasmon resonance (LSPR). Curiously, the redshift stopped while the chains continued to rearrange as manifested by gradual reduction in the LSPR peak. Using electromagnetic simulations, we quantitatively explained the phenomena as a rapid “addition-polymerization” followed by a sharp transition to “condensation-process.” Next, recognizing the significant electric field enhancement in the interparticle gap, a photoluminescent-active Eu³⁺ ion was used to probe Surface-Enhanced Photoluminescence …

Rotational State-To-State Transition Rate Coefficients For H2O + H2O Collisions At Nonequilibrium Conditions, Bikramaditya Mandal, Michal Zoltowski, Martin Cordiner, François Lique, Dmitri Babikov

Chemistry Faculty Research and Publications

Aims. The goal is to develop a database of rate coefficients for rotational state-to-state transitions in H₂O + H₂O collisions that is suitable for the modeling of energy transfer in nonequilibrium conditions, in which the distribution of rotational states of H₂O deviates from local thermodynamic equilibrium.

Methods. A two-temperature model was employed that assumed that although there is no equilibrium between all possible degrees of freedom in the system, the translational and rotational degrees of freedom can be expected to achieve their own equilibria independently, and that they can be approximately characterized by Boltzmann …

Chemical Recycling Of Bio-Based Polyurethane Foams: Evaluating Bio-Based Glycols In Comparison To Petroleum-Based Glycols, Anirudh Thorbole Mr.

Electronic Theses & Dissertations

The paradigm shift towards bio-based polyurethane foams (bio-PUF) has significantly increased post-consumer waste. To address this issue, this research represents a novel approach to enhance sustainable development in the recycling industry by replacing traditional petroleum-based glycols with sustainable bio-based alternatives. This study explores the glycolysis of bio-PUF using bio-based SG-522 glycol and polyethylene glycol (PEG) for comparison. The findings from this research as outlined, reveal no significant differences in depolymerization time between the two glycols, achieving proper depolymerization and high recovery yields of over 95% after solvent purification. Comprehensive FT-IR and NMR analyses confirmed the successful degradation of bio-PUF and …

Castor Oil-Based Polyurethane Adhesives: Effect Of Cross-Linker On The Bond Strength, Mayankkumar Chaudhary

Electronic Theses & Dissertations

Adhesives are important for binding diverse materials, promoting structural integrity and functional versatility in countless daily life applications. An enormous obstacle remains in the development of polyurethane (PU) adhesives exhibiting excellent bonding strength. Designing a chain extender with appropriate molecular structures is critical to improving the bonding strength of PU-based adhesives. In this work, PU-based adhesive was prepared using castor-oil-based polyol (COP) and diisocyanate. The bonding strength of the adhesive was improved by adding chain extenders such as N, N-bis(2-hydroxyethyl) thiophene-2,5-dicarboxamide (ETP) and N, N-Bis(2-hydroxyethyl)-terephthalamide (ETAM). The modified adhesive showed high bonding strength after the addition of chain extenders due …

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 …

Secondary Electron Yield Of Metals, Alloys, And Metal Oxides From First Principles Based Monte Carlo Simulations, Raul E. Gutierrez

Electrical and Computer Engineering ETDs

Density Functional Theory (DFT) based Monte Carlo (MC) simulations of the Sec-
ondary Electron Yield (SEY) of metals, alloys, and metal oxides are performed to
find material properties that could help reduce or influence the multipactor effect.
In order to accurately model the SEY of materials, knowledge of the frequency- and
momentum-dependent Energy Loss Function (qDepELF) is required. The qDepELF
is difficult to determine from experiment; however, it can be calculated from first
principles. The DFT-MC approach for simulating the secondary electron genera-
tion, propagation, and emission processes is described herein. Material properties,
which are calculated using DFT and used …

Cross-Correlation Increases Sampling In Diffusion-Based Super-Resolution Optical Fluctuation Imaging, Jeanpun Antarasen, Benjamin Wellnitz, Stephanie N. Kramer, Surajit Chatterjee, Lydia Kisley

Faculty Scholarship

Correlation signal processing of optical three-dimensional (x, y, t) data can produce super-resolution images. The second-order cross-correlation function XC2 has been documented to produce super-resolution imaging with static and blinking emitters but not for diffusing emitters. Here, we both analytically and numerically demonstrate cross-correlation analysis for diffusing particles. We then expand our fluorescence correlation spectroscopy super-resolution optical fluctuation imaging (fcsSOFI) analysis to use cross-correlation as a postprocessing computational technique to extract both dynamic and structural information on particle diffusion in nanoscale structures simultaneously. Cross-correlation maintains the same super-resolution as auto-correlation while also increasing the sampling rates to reduce aliasing for …

We Think, We Smell, We Remember: The Effect Of Smell On Memory For Chemistry Lab Learning, Michael A. Marino, Francine Wisnewski, Catherine Reilly, Andre Alexis

BCES: Faculty Presentations

The traditional five senses are the primary receptors of external stimuli for the brain. While tactile learning and visual observations are integral to the chemistry laboratory, olfaction is a sense that should be considered part of an educator's repertoire. Previous studies have discovered that our sense of smell plays a significant role in triggering memories. Moreover, specific scents like vanillin can prompt anamneses to recall previous experiences. A sample of 61 college students was employed for a three-week pretest-posttest control group experimental design. In the first week, participants conducted a chemical reaction to synthesize isoamyl acetate, the familiar and nontoxic …