Chemistry Commons^™

Investigations Of Prokaryotic Defense Systems, Hannah Domgaard

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Bacteria are constantly threatened with infection by mobile genetic elements (MGE) such as bacteriophage and plasmids. Bacteriophage and plasmids require the bacteria's cellular infrastructure to replicate their genomes. Rampant replication can lead to cell death which is one reason why bacteria have developed a diverse array of immune systems to prevent or limit infection. This thesis studies three types of bacterial immune systems, type IV-A CRISPR-Cas (Clustered Regularly Interspaced Short Palindromic Repeat –CRISPR associated), type V-A2 CRISPR-Cas systems, and Wadjet systems.

The type IV-A system lies adjacent to a dinG-like helicase gene. Research has shown that this system can target …

Elucidation Of Active Site And Mechanism Of Metal Catalysts Supported In Nu-1000, Hafeera Shabbir

All Dissertations

Advances in extraction of shale oil and gas has increased the production of geographically stranded natural gas (primarily consisting of methane (C1) and ethane (C2)) that is burned on site. A potential utilization strategy for shale gas is to convert it into fuel range hydrocarbons by catalytic dehydrogenation followed by oligomerization by direct efficient catalysts. This work focuses on understanding metal cation catalysts supported on metal-organic framework (MOF) NU-1000 that will actively and selectively do this transformation under mild reaction conditions, while remaining stable to deactivation (via metal agglomeration or sintering). I built computational models validated by experimental methods to …

Exploring The Biomedical Applications Of Polyurethane-Based Foams, Films, And Hydrogels, Anand Utpal Vakil

Dissertations - ALL

Shape memory polymers (SMPs) are a class of smart materials that can be temporarily stored in a deformed shape and can actively recover their original shape upon exposure to an external stimulus, such as heat, magnetic field, moisture, pH, light, or electric field. The ability of SMPs to change shape when required can be used for a wide range of applications, especially in the case of minimally invasive biomedical applications. In this work, polyurethane-based SMPs were explored for their use in tissue engineering, drug delivery, and wound healing applications.

In the second chapter, low density porous foams with tunable degradability …

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …

Intersections Of Environmentalism, Chemistry, And Racism: An Experimental Study Of Halobenzene Hydrogenolysis And Critical Communication Studies Of Equitable Learning Practices Rooted In Black Feminism, Lauren O. Babb

Electronic Theses and Dissertations

Increasing concentrations of fluorinated aromatic compounds in surface water, groundwater, and soil pose threats to the environment. Fundamental studies that elucidate mechanisms of dehalogenation for C-X compounds (where X represents a halide) are required to develop effective remediation strategies. For halogenated benzenes, previously published research has suggested that the strength of the C-X bond is not rate-determining in the overall rate of dehalogenation. Instead, the rate-determining step has been hypothesized to be adsorption of the C-X compound onto the surface of a catalyst. Building on this hypothesis, in this work, we examine the reaction kinetics of fluorobenzene conversion to benzene, …

Functional Bottlebrush Polymer Additives For Thin Films And Coatings, Travis S. Laws

Doctoral Dissertations

Bottlebrush polymers are a class of highly branched polymers consisting of polymeric side chains that are densely grafted to a linear backbone. Their highly branched architecture results in surface enrichment across a broad range of materials. The goal of my research has been centered around the design of functional bottlebrush polymers and their use as surface active additives in blend films and coatings.

In the first chapter, we examine the segregation behavior of polystyrene bottlebrushes that are blended with linear polystyrene. We systematically vary the lengths of the bottlebrush backbone (Nb), side-chain (Nsc), and the linear matrix (Nm) in order …

Development Of High Quantum Efficiency Strained Superlattice Spin Polarized Photocathodes Via Metal Organic Chemical Vapor Deposition, Benjamin Belfore

Electrical & Computer Engineering Theses & Dissertations

Spin polarized photocathodes are necessary to examine parity violations and other fundamental phenomena in the field of high energy physics. To create these devices, expensive and complicated growth processes are necessary. While integral to accelerator physics, spin polarized electrons could have other exciting applications in materials science and other fields of physics. In order to explore these other applications feasibly, the relative supply of spin polarized photocathodes with a high rate of both polarization and photoemission needs to be increased. One such way to increase this supply is to develop the means to grow them faster and at a larger …

Chromatographic Dynamic Chemisorption, Shreya Thakkar

Masters Theses

Reaction rates of catalytic cycles over supported metal catalysts are normalized by the exposed metal atoms on the catalyst surface, reported as site time yields which provide a rigorous standard to compare distinct metal surfaces. Defined as the fraction of exposed metal surface atoms to the total number of metal atoms, it is important to measure the dispersion of supported metal catalysts to report standardized rates for kinetic investigations. Multiple characterization techniques such as electron microscopy, spectroscopy and chemisorption are exploited for catalyst dispersion measurements. While effective, electron microscopy and spectroscopy are not readily accessible due to cost and maintenance …

Atmospheric Mercury Chemistry: Detection, Kinetics, And Mechanism, Na Mao

Dissertations

The presence of mercury in the environment is of global concern due to its toxicity. The atmosphere is an important transient reservoir for mercury released by human activities and natural sources. The knowledge of atmospheric mercury chemistry is critical for understanding the global biogeochemical cycle. In the atmosphere, mercury primarily exists in three forms: gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM). Over the last decade, the existing knowledge of mercury cycle has dramatically changed: (1) There has been increasing evidence that current detection methods do not accurately quantify gaseous oxidized mercury and a technique which …

Extractive Membranes For The Detection And Screening Of Waterborne Plutonium, James Foster

All Dissertations

The development of rapid screening tools for special nuclear materials remains a crucial focus for nonproliferation efforts. Traditional approaches for the analysis of trace-level Pu isotopes in water requires tedious and time-consuming sample preparation steps that do not lend well to expeditious screening. Therefore, a novel analytical method that combines both Pu concentration and source preparation into a single detection system would make for an invaluable tool for nuclear security applications. Extractive membranes absorbers can help to fulfill this role as they are capable of concentrating Pu to detectable limits while subsequently serving as alpha spectrometry sample sources. In Chapter …

Diffusion Of A Salt In An Aqueous Media, Aldaly Pineda Hernandez

Chemical Engineering Undergraduate Honors Theses

Diffusion is defined as the net transfer of a molecule from a high concentration region to a low concentration region. The concept of diffusion is used in a very important process called "desalination." Desalination is a separation process used to reduce the salt content dissolved in brackish water to make it suitable for human consumption, irrigation, and industrial use.

In desalination plants, it is important to monitor the constantly changing salt content of water, partly due to the diffusive effect. The main purpose of this experiment was to study the diffusion of NaCl in water at two NaCl concentrations. The …

Surface-Functionalized Chemiresistive Films That Exploit H-Bonding, Cation-Pi, And Metal-Halide Interactions., Prasadanie Karunarathna Adhihetty

Electronic Theses and Dissertations

The development of gas sensors for detection of volatile organic compounds (VOCs) has been of interest in the sensing field for decades. To date, the use of metal nanoparticle-based chemiresistors for trace VOC detection, particularly gold nanoparticle-based sensors, is of great interest due to their high chemical stability, ease of synthesis, unique optical properties, large surface to volume ratio, and high level of conductivity. Much effort has been devoted towards gold monolayer protected clusters (Au MPCs) as chemiresistors to detect harmful VOCs. The present thesis documents the results of our efforts to exploit the advantages of functionalized Au MPCs chemiresistors …

Structural, Charge Transport, Gas Sensing, Magnetic, Pseudocapacitive, And Electrocatalytic Properties Of Perovskite Oxides., Surendra Bahadur Karki

Electronic Theses and Dissertations

Perovskites are functional materials with the general formula ABO₃ (A = alkali, alkaline earth or lanthanoid cations and B = transition metal or main group cations). These materials are marked by a variety of crystal structures and interesting properties such as colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, pseudocapacitance, gas sensing, charge transport, and electrocatalytic properties. The formula of perovskite can be written as AA’BB’O₆, when there is ordering between two cations over A and B-sites. Such compounds are called double perovskite oxides. Some amount of oxygen could be lost from crystal structure without decomposition of the phase. Such …

Computational Study Of The Reactions Of Heteroatomic Compounds On Ceo2, Suman Bhasker Ranganath

LSU Doctoral Dissertations

The mechanisms of ambient-temperature reactions of heteroatomic compounds catalyzed by ceria (CeO₂), an archetypical reducible oxide, for enzyme mimetics, environmental protection, and chemical synthesis are investigated in this dissertation using theoretical methods. CeO₂ is modeled with thermodynamically stable low-index surfaces exposed by commonly studied ceria thin films and nano particles. To understand phosphatase-like dephosphorylation activity, stable adsorption states and surface reactions of model phosphates are examined. Binding of the central P-atom to surface lattice oxygen (O_latt) supplemented by phosphoryl O-Ce interaction is the only stable adsorption state for the un-dissociated molecule. Deprotonation of phosphate monoesters, …

Charged-Particle Interactions To Generate Novel Coatings And Materials, Pradnya D. Rao

Electronic Theses and Dissertations

A typical paper coating formulation contains anionically charged pigments and latex to provide a high-quality surface for printing. However, during application and drying, the latex can migrate to the surface or deep into the paper, resulting in weak coating layers or the need to use a high latex content to obtain the same strength properties. In this thesis, we have explored the introduction of cationically charged particles into the suspension as a way to reduce the amount of binder in the coatings, improve coating strength and reduce binder migration. With these aims in mind, we have generated cationic precipitated calcium …

Design And Fabrication Of Nanostructured Electrodes For Complementary Electrochemical And Photoelectrochemical Water Splitting, Kholoud El Sayed Abousalem

Theses and Dissertations

Designing highly active, durable, and nonprecious electrodes for overall water splitting is of urgent scientific importance to realize sustainable hydrogen production. Accordingly, the need to search efficient energy production systems is of crucial necessity. In this thesis, two various systems for sustainable hydrogen production have been reported using electrochemical and photoelectrochemical pathways. In the first part of the thesis, electrochemical water splitting involving both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been established. To this end, an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn, Ni, Co phosphide catalysts directly on nickel foam via …

Photocatalytic Degradation Of Lignin By Supported Silver Nanoparticles, Ning Wei

Theses and Dissertations--Chemical and Materials Engineering

Lignin is the second most abundant form of biomass on earth. The phenolic structure and high carbon to oxygen ratio make lignin an attractive renewable source of fuel and chemicals. However, its recalcitrance and heterogeneous nature prove difficult for decomposing lignin’s polymer structure and separation of the products. This work has focused on the use of low-energy catalytic approaches to overcome these barriers. A mimic of the lignin degrading enzyme laccase, consisting of a copper cluster Cu4Py4I4 modified with AgNO3, was developed to function similarly to the laccase active site. The prepared copper complex solution was found to be active …

Calcite Depression In Bastnaesite-Calcite Flotation System Using Organic Acids, Emmy Muhoza

Graduate Theses, Dissertations, and Problem Reports

Bastnaesite is the primary source of light REEs, namely cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), to name a few. Bastnaesite is typically concentrated using the froth flotation beneficiation method. Flotation of bastnaesite suffers from high reagent consumption due to the similar surface characteristics of bastnaesite and associated gangue minerals, including calcite. Additionally, complex stages of high-temperature conditioning are often required to suppress the detrimental impact of dissolved calcium ions on the flotation of bastnaesite. This research seeks to investigate the capabilities of organic acids in the bastnaesite-calcite flotation systems to selectively depress calcite minerals and effectively chelate calcium …

Scale-Up Of Flow-Electrode Capacitive Deionization Method For Hard Water Softening, Noah Henry

Williams Honors College, Honors Research Projects

This study’s purpose is to further document a capacitive deionization design that could be capable of purifying H₂O at a household scale where clean water is otherwise unobtainable in applicable regions of the world. The hypothesis behind this study was continuously larger scaled electrochemical cell-units would increase their water softening capabilities in sustainable fashion. The trend at which performance will scale is currently unknown. The units studied were constructed using graphite plates, anion exchange membranes, cation exchange membranes, and Teflon channels. Three streams, two being CaCl₂ solutions in DI H₂O (one being concentrated with CaCl …

Reinforcement Of Elastomers By Reactive Ionic Surfactant, Nicole Vickerman

Williams Honors College, Honors Research Projects

Elastomers without cross-linking agents or fillers do not have the necessary properties for practical applications in the rubber industry. Elastomers must be reinforced with fillers and/or cross-linking agents to achieve the needs of physical and mechanical properties for commercial products. Sodium octyl 6-mercaptohexyl phosphate (SOMP) and sodium ethyl (6-mercaptohexyl) phosphate (SEMP) were used to investigate the influence of a reactive ionic surfactant and its influence on the physical properties of peroxide crosslinked styrene butadiene rubber (SBR). SEMP and SOMP were both found to be able to be grafted successfully on to the SBR chains within the rubber using extraction testing …