Physical Sciences and Mathematics Commons^™

Molecular Mechanism Of Cyanobacteria Circadian Clock Oscillator And Effect Of Co Factors On Its Oscillation, Manpreet Kaur

Dissertations

The circadian rhythms arise as an adaptation to the environmental 24-hour day and night cycle due to Earth's rotation. These rhythms prepare organisms to align their internal biological activities and day to day behavior or events with the environmental change of the 24-hour day and night cycle. Circadian rhythms are found widely in all living kingdoms of life on Earth. Cyanobacteria are photosynthetic prokaryotes which first used to study these circadian rhythms. Among cyanobacterial species, Synechococcus elongatus PCC 7942 (henceforth, S. Elongatus) is the simplest organism with a durable and sturdy circadian clock and is study as a model organism. …

The Aging And Impacts Of Atmospheric Soot: Closing The Gap Between Experiments And Models, Ogochukwu Yvonne Enekwizu

Dissertations

The main goal of this dissertation is to generate data and parameterizations to accurately represent soot aerosols in atmospheric models. Soot from incomplete combustion of fossil fuels and biomass burning is a major air pollutant and a significant contributor to climate warming. The environmental impacts of soot are strongly dependent on the particle morphology and mixing state, which evolve continuously during atmospheric transport via a process known as aging. To make predictions of soot impacts on the environment, most atmospheric models adopt simplifications of particle structure and mixing state, which lead to substantial uncertainties. Using an experimentally constrained modeling approach, …

Modeling Mass Transfer And Chemical Reaction In Industrial Nitrocellulose Manufacturing Processes, Francis Patrick Sullivan

Dissertations

A series of models are proposed to describe the production of military grade nitrocellulose from dense cellulose materials in mixtures of nitric acid, sulfuric acid, and water. This effort is conducted to provide a predictive capability for analyzing the rate and extent of reaction achieved under a range of reaction conditions used in the industrial nitrocellulose manufacturing process for sheeted cellulose materials. Because this capability does not presently exist, nitrocellulose producers have historically relied on a very narrow range of cellulose raw materials and resorted to trial and error methods to develop processing conditions for new materials. This tool enables …

Novel Applications Of Mass Spectrometry For Quantitation And Reaction Mechanism Elucidation, Pengyi Zhao

Dissertations

Mass spectrometry (MS) has been growing as one of the most widely used tools in the field of analytical chemistry. Various applications have been developed to harness the high sensitivity and specificity of mass spectrometric analysis. In this dissertation, two major challenges are addressed. By developing mass spectrometric-based methods, absolute quantitation of proteins/peptides have been achieved. Elucidation of various reaction mechanisms are also enabled. These are the focuses of this dissertation.

In Chapters 2 to 4, a novel quantitation method is developed, titled as coulometric mass spectrometry (CMS). The strength of this method is that no reference standard or isotope-labeled …

Development Of Novel Membranes For Nanocarbon Enhanced Separation With Application In Biofuels And Solvent Recover, Oindrila Gupta

Dissertations

Pharmaceutical industries historically have had one of the highest amounts of solvent waste generated per unit of drug manufactured. Energy requirements and carbon footprint of current solvent recycling processes tend to be quite high, and the incineration of the solvents for waste disposal produces toxic air emissions. Also, rapidly increasing demand for energy and strict regulation on engine pollutant emissions have necessitated the use of alcohol as carbon-neutral fuels. Thermal distillation is one of the most common methods for the separation of alcohol-water mixtures. However, its application is limited due to energy requirements and high operating costs, and heating to …

A Library Of Low Molecular Weight Fluorescent Probes For The Detection Of Cu(Ii) And Fe(Iii) Ions, Ashley Johnson

Dissertations

This dissertation reports the synthesis and photophysical properties of a family of rhodamine dyes (compounds 3.9-3.13 and 4.6). The rhodamine dyes are prepared in two steps, and fully characterized by ESI-MS (Low and High resolution), X-Ray crystallography, NMR spectroscopy, and FT-IR spectroscopy. The coordination environment of the low molecular weight fluorescent probes (LMFPs) was systematically changed to investigate the thermodynamic behavior between the LMFPs and an array of metal ions (Cu²⁺, Fe²⁺, and Hg²⁺ ions) in protic and aprotic solvent systems. Upon coordinating to metal ions, the π-conjugation of the LMFPs changed, resulting in …

Practical Adhesion Measurements In Organic Coatings; Advancing Understanding And Mechanical Methods Development, Diana Gottschalk

Dissertations

“Adhesion” can be considered either a mechanical or chemical phenomenon. The mechanical interpretation describes the difficulty of separating surfaces and is useful for quantifying performance within applications that depend on bulk and interfacial properties. Chemical adhesion describes interfacial resistance to chemical attack and does not depend on bulk properties. Predicting chemical failure through mechanical measurement is confounded by the influence of bulk properties. However, the prospect is attractive because of the robust tolerance for sample geometries, allowing experiments to resemble an end-use system. The present work's primary goal was to elevate mechanical methods to provide a detailed interfacial characterization of …

Synthesis Of Biologically Active Phosphorus Heterocycles, Giri Gnawali

Dissertations

This dissertation work is divided into two parts. The first part is focused in the development of methodology for the synthesis of phostones and phosphonosugars and advancement thereof. The second part is focused in the development of affinity probes based on analogs of natural products cyclophostin and the cyclipostins.

Phostone (3) and phosphonosugars are cyclic phosphonates. The anomeric carbon of sugar is replaced by a phosphorus atom. The synthesis of phostones has been achieved starting form the key intermediate, γ,δ-epoxy vinyl phosphonate (1). The palladium catalyzed ring opening of γ,δ-epoxy vinyl phosphonates by a nucleophile results …

Embedded Gold Nanoparticles For Metal Enhanced Photoluminescence, Hasna Alali

Dissertations

Noble metal nanoparticles (MNPs) have attracted great attention in electronics, solar cells and catalysis. Their unique optical properties and biocompatibility makes them useful in biological applications like imaging, drug delivery, therapy and diagnostic. At the surface of MNPs the collective oscillation of free electrons resonates with a particular wavelength of incident light, generating the Localized Surface Plasmons Resonance (LSPR). LSPR results in absorption and scattering of incident light. Scattering results in reflecting photons and absorption leads to enhanced photoluminescence and quenching of fluorophores, if the fluorophore is in the vicinity of MNPs.

Most of the studies in this regard have …

Synthesis Of Alpha-Methylselenocysteine, Its Relevant Analogues, And An Unnatural Glutathione Disulfide Core, Robert J. Wehrle

Dissertations

Selenoproteins, such as glutathione peroxidase, have gained interest for their ability to act as antioxidants, and their potential to act as anti-cancer agents. Synthesizing and studying selenoproteins can be problematic, however, due to their propensity to degrade from over-oxidation. The degradation from over-oxidation can be avoided by the incorporation of the unnatural amino acid, alpha-methylselenocysteine. A synthesis utilizing methyl malonic esters was used to synthesize protected (R)-alpha-methylselenocysteine efficiently (46% over four steps) and in high enantio-purity (88% enantiomeric excess). Using similar procedures, the (S)-enantiomer was also synthesized as well as a beta-analogue.

The use of enzymes …

Machine Learning Approaches For Improving Prediction Performance Of Structure-Activity Relationship Models, Gabriel Idakwo

Dissertations

In silico bioactivity prediction studies are designed to complement in vivo and in vitro efforts to assess the activity and properties of small molecules. In silico methods such as Quantitative Structure-Activity/Property Relationship (QSAR) are used to correlate the structure of a molecule to its biological property in drug design and toxicological studies. In this body of work, I started with two in-depth reviews into the application of machine learning based approaches and feature reduction methods to QSAR, and then investigated solutions to three common challenges faced in machine learning based QSAR studies.

First, to improve the prediction accuracy of learning …

An Atomistic Study Of The Effects On Mechanical Properties And Bonding Interactions Of Carbon Nanofillers In Nylon 6 Nanocomposites, Michael Roth

Dissertations

Polymers have potential for a wide range of applications. The effectiveness of polymers can be further enhanced through the addition of nanofillers that improve thermal, mechanical, and electrical properties of the polymer. Carbon based nanofillers such as carbon nanotube (CNT), graphene, and carbon nanofibre (CNF) are of particular interest due to their high properties and high aspect ratios. However, limited understanding of the governing interactions of these nanofillers with polymers limits the effectiveness of the final nanocomposite.

The first facet of this dissertation focuses on determining the dominating interactions between pristine CNT and graphene with nylon 6 monomer and the …

Effect Of Selfsame Microparticles On Epoxide Amine Network Formation And Matrix Mechanics, Travis Palmer

Dissertations

Epoxide amine matrices are widely utilized in aerospace carbon fiber reinforced polymer (CFRP) composites having engendered significant reductions in weight and fuel consumption. This dissertation focuses on the effect of constrained space during network formation on the matrix mechanics of these highly complex composite systems. Precipitation polymerization conditions are developed to prepare epoxide amine microparticles (EMs) based on tetraglycidyl-4,4’-methylenedianiline (TGDDM) and isophorone diamine (IPDA). Surface functionality of EMs is tuned via control of epoxide to reactive amine hydrogen ratio, where unreactive, amine- and epoxide-functional EMs are prepared. We demonstrate that EMs are polydisperse, but can be filtered, yielding low dispersity …

Huisgen 1,3-Dipolar Azide-Alkyne Cycloaddition “Click” Reaction In Polymer Synthesis And Curing, Jie Wu

Dissertations

This dissertation’s key focus is on utilizing Huisgen 1,3-dipolar azide-alkyne cycloaddition (AAC) reaction in copolymer synthesis and modification, including thermoplastic block copolymer and commercially available two-component polyurethane system. It can be divided into two major projects, introduced as follows.

The first project involves the development of a modular synthetic approach toward polyisobutylene (PIB)-based triphasic pentablock thermoplastic elastomer with enhanced moisture permeability. This terpolymer consists of a poly(styrene-b-isobutylene-b-styrene) (SIBS) core and appended hydrophilic polymer blocks (HBs). The SIBS core was synthesized via living cationic polymerization (LCP) of isobutylene followed by sequential addition of styrene. AAC was utilized …

Geochemical Tracers Of Arctic Ocean Processes: A Study Of Gallium, Barium, And Vanadium, Laura M. Whitmore

Dissertations

The Arctic Ocean is linked to the global oceans and climate through its connectivity with the North Atlantic Ocean and the regional thermohaline deep water formation sites. It’s also a region undergoing rapid environmental change. To inform the community of potential changes in geochemical and biogeochemical cycles, this dissertation addresses three dissolved geochemical tracers (gallium, barium, and vanadium) as indicators of Arctic Ocean processes. Gallium is tested as a replacement for nutrient-type tracers in an effort to deconvolve Pacific and Atlantic derived waters in the Arctic Ocean basins. These water masses carry different heat and salt content and can influence …

New Catalytic Reactions In Carbohydrate Chemistry, Scott Geringer

Dissertations

Carbohydrates or sugars are some of the most diverse and abundant biological molecules. They are involved in a multitude of processes in the body such as fertilization, cell-cell communication, and cancer metathesis. Because of these vital functions, the study of sugars is rapidly growing field. The field however is limited due to the complex nature of sugars which results in difficulties in obtaining large quantities for study.

Protecting group manipulation is a large emphasis area in carbohydrate chemistry due to the need to selectively protect different functional groups of each molecule during synthesis. Catalytic and selective cleavage of protecting groups …

Metal Ions Impact On Shewanella Oneidensis Mr-1 Adhesion To Ito Electrode And The Enhancement Of Current Output, Aisha Awad Alshahrani

Dissertations

The goal of this study is to enhance the efficiency of bacterial extracellular electron transfer (EET) in Shewanella oneidensis MR-1 by enhancing adhesion to the electrode's surface. Our results clearly show a major difference in the attachment and behavior of Shewanella oneidensis MR-1 for Ca2+, Pb2+, Cd2+, and Mg2+, compared to the control. the final microbial coverage, as measured by confocal microscopy and cathodic peak charge in cyclic voltammetry (Qpc), increases with increasing metal ion concentrations. We found the cells attached to the electrode increased more with the addition of metal ion concentrations in the following order of metals: Ca2+ …

Optimization Of Microbial Fuel Cells, Norberto M. Gonzalez

Dissertations

Optimization of microbial fuel cells is investigated by utilizing Shewanella oneidensis as a model microorganism. the microbe's ability to grow and use glucose as a carbon source is explored under varying oxygen environments through an offline PMP derivatization method and HPLC analysis. Shewanella growth and glucose utilization is enhanced under aerobic environments; however, under microaerobic environments the addition of ferric iron results in a faster exponential growth initialization. a flavin mononucleotide modified indium tin oxide electrode is prepared and characterized for its usefulness in microbial fuel cells by controlled potential electrolysis, cyclic voltammetry, and electrochemical impedance spectroscopy studies. the electrode …

Lewis Acid-Carbonyl Solution Interactions And Their Implications In Catalytic Systems, Carly Soren Hanson

Dissertations

The utilization of Lewis acids to activate substrates containing carbonyls is ubiquitous in organic synthetic methods. in order to facilitate the development of novel reaction pathways and understand existing methods, it is necessary to determine the solution interactions between Lewis acids and Lewis bases. Historically, the characterization of the interactions of Lewis pairs has relied on solid state infrared (IR) spectroscopy and X-ray crystallography, as well as in situ NMR. I have developed a method utilizing in situ IR spectroscopy and solution conductivity towards the identification of the solution structures formed when a range of carbonyl compounds are combined with …

Development Of Methods For The Removal Of Selected Pollutants From Several Matrices And Identification Of Unknown Pollutants Adsorbed Onto Plastics Collected From Freshwater, Kathryn Marie Renyer

Dissertations

Plastic pollution represents one of greatest anthropogenic threats to the environment. Five to ten billion tons of plastic are manufactured every year. Currently, Earth's ecosystem is contaminated with billions of tons of plastic debris, much of which cannot be recycled. Over time, this plastic debris decomposes into small particles. Small plastic particles are known to adsorb toxic compounds in marine environments. My research is concerned with creating novel methods for the detection and quantification of selected persistent organic pollutants from several media. Specifically, I developed methods for the detection and quantification of endosulfan sulfate (ESS) from Lumbricus terrestris tissue and …

Electron Transfer Of Shewanella Oneidensis Mr-1 At Clay-Modified Ito Electrode, Reem Faez Alshehri

Dissertations

Various strategies have been established to enhance the extracellular electron transfer and energy output capability of microbial fuel cells, with the majority being aimed at anode modification. The anode has a significant impact on the electricity generation performance of MFCs because it is in direct contact with the microorganisms. The materials of the anode should be favorable for the bacterial cell and capable to facilitate the electron transfer. Developing of an electrode using low-cost and effective materials assists to enhance the bacterial cell attachment and extracellular electron transfer. This provides a significant improvement in MFC performance. In this study, clay …