Physical Sciences and Mathematics Commons^™

Investigating The Role Of Topological Frustration On Morphology Of Novel Multiblock Copolymers, Rohit Gupta

Doctoral Dissertations

Multiblock copolymers have gained considerable attention due to their ability to offer immense potential for designing soft materials with complex architectures for diverse applications. The enlarged parameter space offered by these multiblock copolymers gives access to a wide variety of multiply continuous morphologies which can be used to produce highly ordered nanostructures. The investigation on multiblock copolymers has been subjected to two critical limitations: (i) A suitable synthetic strategy for accessing these structures and (ii) computational tools which can help in application driven design of these molecules. In this dissertation, the goal was to develop methodologies for the synthesis of …

Impact Of Chemical Doping On The Thermoelectric Charge Transport Of Organic Semiconductors, Connor J. Boyle

Doctoral Dissertations

The thermoelectric properties of organic semiconductors allow them to directly convert heat into electricity without the use of moving parts and to directly convert electricity into heat without the use of working fluids. These properties offer opportunities for the generation of electricity from non-conventional or renewable sources of heat and for refrigeration without the risk of leaking harmful working fluids at any length scale down to the nanoscale. Since organic materials are lightweight, flexible, and made from abundant resources, these opportunities could one day become affordable for widespread use and could be expanded to include specialized and otherwise difficult to …

The Electrochemical Study Of Simulated Spent Nuclear Fuel (Simfuel) Corrosion Under Permanent Disposal Conditions, Ziyan Zhu

Electronic Thesis and Dissertation Repository

The safety assessment of spent nuclear fuel under permanent disposal conditions requires examination of the corrosion of the spent fuel waste form (UO₂) inside a failed waste container. The objective of this research project was to develop a detailed mechanism of the UO₂ corrosion process when exposed to groundwater. The redox conditions within a failed container in a deep geologic repository will be complex. The oxidant, H₂O₂, produced by the α-radiolysis of groundwater, will be the main driving force for fuel corrosion. However, the efficiency of fuel dissolution will be determined by the …

Analysis And New Applications Of Metal Organic Frameworks (Mof): Thermal Conductivity Of A Perovskite-Type Mof And Incorporation Of A Lewis Pair Into A Mof., Wilarachchige D C B Gunatilleke

USF Tampa Graduate Theses and Dissertations

Metal organic frameworks have gained much attention due to their tunable pore sizes and very high surface areas. With the discovery many of these type materials the need has raised to look into new applications of theses porous frameworks. This thesis focuses on the synthesis of a new perovskite-type metal organic framework and measurement of its thermal conductivity in search of its applicability as a thermoelectric material. The second part of this work focuses on the synthesis of a metal organic framework incorporated with a Lewis pair for the first time. The optimum loading amount of the Lewis pair into …

Sequestration Effect On The Open-Cyclic Switchable Property Of Warfarin Induce By Cyclodextrin: Time-Resolved Fluorescence Study., Naji Saleh Ahmed Al-Dubaili.

Chemistry Theses

In this work, the photophysical properties of the fluorescent anticoagulant drug warfarin (W) were examined in water and inside methyl- β-cyclodextrins (Me- β-CD) through absorption and time-resolved fluorescence measurements at pH 3 and 9 and upon the selective excitation of different isomers of warfarin at 280 and 320 nm. The values of binding constants (2.9 x 10³ M^-1 and 4.2 x 10² M^-1 for protonated and deprotonated forms, respectively) were extracted from the spectrophotometric data. Both absorption and time-resolved fluorescence results established that the interior of the macromolecular host binds preferentially the open pronated form, redshifts …

Development, Characterization And Application Of Multi-Detector Flow Injection Systems Based On A Serial Flow Configuration For Simultaneous Multianalyte Determination, Aisha Rashed Al Hameidi Yammahi

Chemistry Theses

Oxidase enzymes have been used successfully in the analysis of several biochemical species such as glucose, lactate, pyruvate, creatine, creatinine, amino acids, cholesterol and sialic acid, by generating - in a single or consecutive reaction -hydrogen peroxide (H₂O₂) as a signal molecule which is commonly detected amperometrically. Some approaches have been also reported to use more than one enzyme in a given system to achieve multi-analyte determination. This study aims to evaluate a novel approach for n-analyte determination based on n-enzyme reactors (each is loaded with one or more oxidase enzyme) as well as n-1 catalase immobilized …

Development And Characterization Of A Portable Apparatus For Continuous Measurement Of Hydrogen Sulfide In Gas Streams, Bashar Yousef Abu Hattab

Chemistry Theses

A novel detection scheme for the hydrogen sulfide (H₂S) was described and patented recently by researchers at UAE University. This detection scheme and the described bench-scale analyzer offered the advantage of low-cost solution for real-time monitoring of percentile levels of H₂S with excellent signal stability. However, this previous work suffered from two major limitations, which are the relatively low sensitivity and slow response time, which mainly hindered its commercial utilization. Therefore, the aims of the present work were to enhance the detection sensitivity, decrease the response time, and develop a portable prototype of the H₂S analyzer based on the improved …

Development Of Hydroxyapatite-Polymer Sorbents For The Removal Of Heavy Metal Ions From Waste Waters, Eleanora Charnetskaya

Chemistry Theses

Water pollution due to the presence of soluble metal ions is one of the greatest challenges to environmental scientists. Different methods have been explored to the removal of these soluble ions. Among these methods, elimination by sorption into/onto solid materials has been considered one of the successful approaches. Sorbent materials usually chemically interact with soluble ions and eliminate them by bond formation between the ions and the sorbent molecules. On the other hand, soluble ions can be also exchanged with inorganic sorbents in which other environmentally friendly ions can exchange with the soluble metal ions. In the current study, the …

Sequestration Effect On The Open-Cyclic Switchable Property Of Warfarin Induced By Cyclodextrin: Time-Resolved Fluoresence Study, Naji Saleh Ahmed Al-Dubaili

Chemistry Theses

In this work, the photophysical properties of the fluorescent anticoagulant drug warfarin (W) were examined in water and inside methyl-β-cyclodextrins (Me-β- CD) through absorption and time-resolved fluorescence measurements at pH 3 and 9 and upon the selective excitation of different isomers of warfarin at 280 and 320 nm. The values of binding constants (2.9 × 103 M–1 and 4.2 × 102 M–1 for protonated and deprotonated forms, respectively) were extracted from the spectrophotometric data. Both absorption and time-resolved fluorescence results established that the interior of the macromolecular host binds preferentially the open protonated form, red shifts the maximum of its …

Optimizing Peptide Fractionation To Maximize Content In Cancer Proteomics, Victoria Izumi

USF Tampa Graduate Theses and Dissertations

The purpose of the studies included in this thesis is to develop an effective an efficient method to study the proteome using separation and detection of peptides, when only a limited amount of sample, 10 micrograms of total protein or less, is available. The analysis will be applied to multiple myeloma cancer cells using ultra high-performance liquid chromatography-mass spectrometry for expression proteomics to illustrate utility. To detect low abundance peptides in a complex proteome, we use different strategies, including basic pH reversed-phase liquid chromatography (bRPLC), mass-to-charge fractionation in the mass spectrometer, and various liquid chromatography gradients to increase peptide separation …

Lc-Ms/Ms Based Analysis Of Vitamins B3 And B6 In Healthy And Obese Emirati Population, Ghada Rashad Mohamed Shafiek Ibrahim

Theses

Water-soluble vitamins like Vitamin B3, B6, and B9 are of utmost importance in human health and disease, as they are involved in numerous critical metabolic reactions. Not surprisingly, deficiencies of these vitamins have been linked to various disease states. For example, Vitamin B6 deficiency has been related to many diseases in humans especially in women with type 1 diabetes and in patients with systemic inflammation, liver disease, rheumatoid arthritis, and those infected with HIV. Similarly, derivatives of Vitamin B9 (such as folates), are needed to synthesize, repair, and methylate DNA as well as to act as a cofactor in certain …

Synthesis, Characterization And Application Of Structurally Diverse Poly(Chalcogenylene Vinylene)S, Zhen Zhang

Chemistry and Chemical Biology ETDs

Conjugated polymers have found widespread applications in flexible and printable electronic devices, among which poly(thienylene vinylene) (PTV) displays outstanding optoelectronic properties and promising applications. However, further studies of its structure-property-function relationship have been greatly impeded mainly due to the synthetic difficulty of generating new structures beyond its rudimentary form.

To further investigate this class of material, I have developed a facile methodology for the preparation of structurally diverse poly(chalcogenylene vinylene)s (PCVs) through a combination of acyclic diene metathesis (ADMET) polymerization and post-polymerization modification techniques. Specifically, a series of halogenated and cross-conjugated PCVs have been designed and synthesized, followed by complete …

Development Of Betulinic Acid Triazole Conjugates As Potential Anti-Cancer Agents, Gayathri Jampana

Theses and Dissertations

Betulin and betulinic acid are pentacyclic triterpenoid natural product isolated from the bark of birch trees. While betulin is abundantly available in the bark, betulinic acid is present in scarce quantities in nature. However, betulinic acid can be conveniently synthesized from betulin via simple redox manipulations. Betulinic acid shows selective cytotoxicity profile against cancer cells in vitro while being relatively safe for normal cells. One of the challenges for the clinical development of betulinic acid is its lack of aqueous solubility. The three key structural features of betulin/betulinic acid that have been routinely exploited for structural modifications to enhance their …

Synthesis And Characterization Of A Series Of Vanadium ( Iv ) Complexes With The Kläui Ligand, Xiao Wu

Theses and Dissertations

Cyclopentadienyltris (dibutyl phosphito-P) cobaltate, {(C5H5)Co[(OR)2PO]3}– (R=Bu), is a tripodal ligand and also called Kläui ligand (R=Bu). The synthesis and characterization of several vanadium(III) and vanadium(IV) complexes containing Kläui ligand (R=Bu) as the catalytic models to catalyst the oxidation reaction of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-benzoquinone (3,5-DTBQ) are detailed here. Chapter II details the synthesis of the supersandwiches and Kläui ligand (R=Bu). Chapter III details the synthesis of vanadium monomeric complexes containing Kläui ligand (R=Bu). Chapter IV details the vanadium dimeric bridging complexes synthesized by different vanadium monomers from Chapter III. Chapter V details the catalytic activities of these vanadium complexes.

Pressure Tuning Of Energy Storage Materials Probed By In-Situ Vibrational Spectroscopy And Synchrotron Radiation, Pan Wang

Electronic Thesis and Dissertation Repository

Clean and renewable energy has drawn much attention recently due to the increasing demand for more energy and environmental issues. New materials have been developed and the improved performance of such materials have been achieved in the past decades. It has been proved that application of external high pressure can significantly tune the structure of materials. Consequently, the properties of the materials could also be modified. Therefore, in this thesis, we focused on the high-pressure studies of two classes of energy storage materials, hydrogen storage materials and solar cell materials. Ammonia borane (AB) has been extensively investigated as an excellent …

From The River To The Gulf: An Investigation Of Biogeochemical Cycling In Wetland Soils And Coastal Shelf Sediments, Katie Bowes

LSU Master's Theses

Louisiana is home to 40% of the coastal wetlands in the lower 48 states, yet accounts for 80% of the coastal wetland loss in this region. This loss is attributed to decreased sediment supply, levee alteration, sea level rise, channelization, and subsidence. The levee system in Louisiana disconnected coastal wetlands from the main stem of the Mississippi River (MSR), reducing the amount of land-building sediment that reaches coastal wetlands. This disconnection also allows a greater percentage of river discharge, including agricultural contaminants and runoff, to flow into the northern Gulf of Mexico (NGOM).

The 2012 Coastal Master Plan proposed eight …

Voltage-Driven Polyelectrolyte Complexation Inside A Nanopore, Prabhat Tripathi

Doctoral Dissertations

This thesis investigates how a pair of oppositely charged macromolecules can be driven by an electric field to form a polyelectrolyte complex inside a nanopore. To observe and isolate an individual complex pair, a model protein nanopore, embedded in artificial phospholipid membrane, allowing compartmentalization (cis/trans) is employed. A polyanion in the cis and a polycation in the trans compartments are subjected to electrophoretic capture by the pore. We find that the measured ionic current across the pore has a distinguishable signature of complex formation, which is different from the signature of the passage of individual molecules …

The Balance Between Dipole-Dipole Interactions And Steric Exclusion On Ordering In Cationic Polymers, Chinomso Nwosu

Doctoral Dissertations

Structure-property correlations in charged polymers is an interesting facet of polymer science. Understanding the effects of intermolecular forces on the morphologies of polymers can lead to the design of membranes with desired structures to improve properties, for example ion conductivity. In random, comb-shaped polycations, competing intermolecular forces result in two different short-range orderings. Side-chain steric repulsion results in backbone-backbone morphology characterized by periodic spacing between polymer backbones. However, dipole - dipole attraction in these polycations can facilitate the formation of ionomer cluster morphology characterized by a spacing between clustered dipoles. Although both of these short-range orderings have disparate origins, their …

The Dissociative Chemisorption Of Methane And Its Isotopologues On Metal Surfaces, Han Guo

Doctoral Dissertations

The dissociative chemisorption of small molecules on metal surfaces is an important step in many heterogeneous catalytic processes, and has received considerable scientific attention. In this thesis, a quantum approach based on the reaction path Hamiltonian is used to explore the dissociative chemisorption of methane and its deuterated isotopologues on several metal surfaces. The theoretical approach is described in Chapter 2. This approach treats all 15 degrees of freedom of the methane molecule, and includes the effects of lattice motion, allowing us to examine the translational and vibrational enhancements, mode- and bond-selectivity and the surface temperature dependence observed in experiments. …

Surface Functionalization Of Fabrics And Threads For Smart Textiles, Morgan Baima

Doctoral Dissertations

The future of electronics is moving toward wearable devices and therefore requires a shift away from hard, inflexible materials towards fibers, threads, and fabrics that conform to the shape of the body. Therefore new methods for incorporating textiles as electronic components are needed to replace conventional processing techniques used with smooth, flat substrates like glass, silicon, and many polymers. Toward this end, this work investigates different methods that can be used to tune textile surfaces for electronic functionality, including weaving, solution grafting, and initiated chemical vapor deposition (iCVD). While all of these methods were used to make triboelectrically-active textiles, iCVD …

Calculation Guided Rational Design And Synthesis Of Novel Cationic Fluorescent Meso–Pyridinium Bodipys For Bio-Imaging, Daniel J. Lamaster

LSU Doctoral Dissertations

Chapter 1 contains a brief overview of the history, synthesis, and properties of BODIPY dyes as well as that of the biomedical applications of bio-imaging and photodynamic therapy. Additionally, an overview of the theoretical framework of density functional theory and its time-dependent variant are provided. In Chapter 2, the effects of structural modification on the electronic structure and electron dynamics of cationic meso-(4-pyridyl)-BODIPYs were investigated. A library of 2,6-difunctionalized meso-(4-pyridyl)-BODIPYs bearing various electron-withdrawing substituents was designed and DFT calculations were used to model the redox properties, while TDDFT was used to determine the effects of functionalization on the excited …

Influence Of Salinity, Sunlight, And Sediment On The Toxicity Of Pesticides In Three Non-Target Organisms, Emily Noelle Vebrosky

LSU Doctoral Dissertations

Pesticides used in the United States must undergo registration by the United States Environmental Protection Agency (USEPA), after a multitude of analyses ranging from environmental fate to aquatic toxicological impacts to human risk exposure. Testing varies for each chemical, some requiring more testing than others. In many cases, environmental factors are restricted in the analysis of chemical behavior and organismal testing is limited to larvae. Many pesticides are formulated to breakdown in the environment by means of photolysis, hydrolysis, or oxidation, either to ensure low-persistence, limited transport, or to form the active ingredient (pro-pesticides). Environmental influences on chemical behaviors include …

Computational Studies On Nucleic Acid-Ion Interactions In Droplets And Bulk Solution, Mahmoud Sharawy

Electronic Thesis and Dissertation Repository

Interactions of macromolecules with ions in solution have a long history of study because of their ubiquitous nature. These interactions are essential for the stability and function of macromolecules such as nucleic acids. Nucleic acids are involved in many natural biochemical processes. For example, deoxyribonucleic acid (DNA) provides more than storage of genetic information. The guanine-rich structures, at the ends of the DNA, participate in regulating the gene expression in the living cell by forming guanine quadruplex (G-quadruplex) structures. These structures provide a possible drug target for the treatment of cancer. Nucleic acids are polyions under physiological pH of 7.4. …

Electro- And Photocatalytic Carbon Dioxide Reduction With Mononuclear And Dinuclear Rhenium Polypyridyl Complexes, Eva Amatya

Honors Theses

The main challenge of reducing carbon dioxide (CO2) to value-added products lies in designing more efficient catalysts that are long-lived, selective, and operate near the thermodynamic potential for the reaction. In this work, mononuclear and dinuclear Re complexes containing diamine ligands linked to a pendant anthracene moiety have been synthesized and studied for both electrocatalytic and photocatalytic CO2 reduction. Electrocatalytically, the performances of both catalysts were studied in N,N-dimethylformamide (DMF) and acetonitrile (MeCN) solutions to determine their turnover frequencies (TOFs) for CO2 reduction. Catalyst performance was compared to previously reported rhenium systems, and both systems studied here were shown to …

Development Of Bioactive Peptidomimetics, Fengyu She

USF Tampa Graduate Theses and Dissertations

Peptidomimetics are synthetic foldamers that expected more resistant to proteolytic degradation and enormous chemodiversity when compared with peptides. To date, the functional peptidomimetics such as β-peptides, peptoids, oligoureas, etc have been developed in many science fields. In order to explore the unnatural foldameric architectures, it’s necessary to discover the novel frameworks and molecular scaffolds. γ-AApeptides were reported to be a new class of peptidomimetics that showed its potential applications in drug discovery and chemical biology. However, a wide function and property of γ-AApeptides need to be further explored. To expand the potential application of γ-AApeptides in biochemistry, I have been …

Development Of A Fluorescence Imaging Photometer-Based Method For Characterization Of Phytoplankton Communities, Cameron Maxwell Rekully

Theses and Dissertations

The development of methods for real-time characterization of phytoplankton community structure has important implications for environmental monitoring and the prediction of harmful algal blooms. Our research group has developed an instrument, the Fluorescence Imaging Photometer (FIP), which is capable of rapid classification of phytoplankton via imaging single-cell chlorophyll a fluorescence under different excitation conditions. Discrimination of cells from different taxonomic groups is achieved using optical bandpass filters that have been chosen to selectively excite pigments which occur in characteristic ratios that vary from one group to the next. The relative fluorescence intensity emitted by cells under these different excitation conditions …

Hierarchical Corannulene-Based Materials, Allison M. Rice

Theses and Dissertations

Merging the intrinsic properties of fullerene (buckyball) and corannulene (buckybowl) derivatives with the inherent properties of crystalline metal- and covalent- organic frameworks (MOFs and COFs), including their modularity, porosity, versatility, high surface area, and structural tunability, opens a pathway to unlock a novel class of fulleretic materials. Despite the great interest in MOFs and COFs, as well as fullerene derivatives, this dissertation is focused on crystalline fullerene- and corannulene- containing frameworks, highlighting their potential contributions in the fields of optoelectronic devices, electrodes, and photosensitizers. We have revealed a dual role of fullerene- and corannulene-containing building blocks showing their versatility to …

Layer-By-Layer Construction Strategies Towards Efficient Czts Solar Cells, Matthew J. Turnbull

Electronic Thesis and Dissertation Repository

Solar energy has very high potential for ensuring the world’s energy requirements for the long-term future. Earth-abundant materials like Cu₂ZnSnS₄ (CZTS) are especially desirable, with a non-toxic, low-cost nature, though the quaternary nature allows for a lot of crystal structure variability, and thus underwhelming performance. This Ph.D. thesis is devoted to deepening the understanding of the CZTS material formation, and the processes that can be used to control it, to construct a low-cost, high efficiency CZTS-based solar cell. The layer-by-layer approach presented within this thesis shows great potential for rectifying the problem. CZTS nanocrystal (NC) stoichiometric control …

Efforts Towards The Discovery Of Novel Methods For The Synthesis Of Pharmacologically Relevant Molecular Scaffolds, Graham Joseph Haun

Theses and Dissertations

With the introductions of pharmaceuticals into modern day society many people have been using them to improve their lives. Due to this high increase in demand along with the ever-growing concern of environmental impact pharmaceutical companies have been pressed to synthesis new and existing drugs at a higher rate. This increased rate can cause low yield drugs or have a heavy environmental impact. As the use of pharmaceuticals becomes more widespread the need for greener and simpler organic synthesis methods to make these pharmaceuticals becomes more needed.

Herein is reported the methodological development of different pharmacologically relevant scaffolds. This work …

Coupling Scanning Electrochemical Microscopy And 3d Modelling To Probe Membrane Permeability Of Human Bladder Cancer (T24) Cells, Fraser Filice

Electronic Thesis and Dissertation Repository

Scanning electrochemical microscopy (SECM) scans a biased ultramicroelectrode (≤ 25 µm) probe over a sample to characterize topography, physical properties and chemical reactivity. In this dissertation, SECM was used to investigate the metal-induced changes in membrane response of single live human bladder cancer cells (T24). SECM imaging was coupled to 3D finite element method (FEM) simulations which were the first of their kind, providing advanced quantification of sample traits under conditions not previously usable.

The effects of Cd²⁺ on T24 cell membrane permeability were examined. Experimental depth-scan imaging was coupled with full 3D FEM simulations, eliminating many limitations of …