Physical Sciences and Mathematics Commons^™

Design And Modeling Of Bioinspired Polyelectrolytes With Controlled Architectures For Gene Delivery Applications, Kelli Stockmal

Dissertations

This dissertation focuses on the development of a range of bioinspired polyelectrolytes with controlled architectures for gene and drug delivery applications. Glycans are ubiquitous in biological systems, and understanding the role of saccharide stereochemistry, as well as cationic charge, on polymer behavior in aqueous solution and the interactions with nucleic acids can provide insight into how synthetic polyelectrolytes can be used for non-viral gene delivery and other biological applications. The first chapter provides an introductory overview on how cationic polyelectrolytes can be used to aid the delivery of RNA for controlling gene expression in a variety of cell types, how …

Atomic Oxygen Resistant Low Earth Orbit Stable Polymer Matrix Composites Employing Phenylphosphine Oxide Epoxy-Amines, Witold Fuchs

Dissertations

Atomic oxygen (AO) attacks polymer matrix composites (PMC’s) on the surfaces of spacecraft in low earth orbit (LEO) and threatens safe spacecraft operation and service life. Incorporating phenylphosphine oxide (PPO) groups into polymer chains offers a self-regenerating method of protection from AO but remains poorly understood. Herein, epoxies containing PPO groups were synthesized with increasing concentrations of phosphorus [P] from 0 to 8 wt % to investigate their AO resistance. Measurements confirmed the exposure of these materials to AO produces a passivation phosphate (POx) layer on the surface of the sample and the efficacy of the resultant layer was directly …

Water Elites’ Perceptions Of Water Security In The Middle East And North Africa Region, Ghaleb Akari

Dissertations

The Middle East and North African region continues to face significant water security challenges. The purpose of this dissertation is to gain a deeper understanding of water elites’ perceptions of water security in the MENA region. It is not meant to generalize the findings. Instead, the intention for the research is to identify, explain, and analyze by national elites' contrasting perceptions in Jordan, Iraq, Egypt, and Tunisia.

The study examines water elites’ perceptions in four areas: current knowledge level of water security, water resource management, water service delivery, and water-related risk mitigation. These elites’ perceptions of water security will help …

A Management Strategy Evaluation Of The Impacts Of Interspecific Competition And Recreational Fishery Dynamics On Vermilion Snapper (Rhomboplites Aurorubens) In The Gulf Of Mexico, Megumi C. Oshima

Dissertations

In the Gulf of Mexico (GOM), Vermilion Snapper (Rhomboplites auroruben), are believed to compete with Red Snapper directly for prey and habitat. The two species share similar diets and have significant spatial overlap in the Gulf. Red Snapper are thought to be the dominate competitor, forcing Vermilion Snapper to feed on less nutritious prey when local resources are depleted. In addition to ecological pressures, GOM Vermilion Snapper support substantial commercial and recreational fisheries. Over the past decade, recreational landings have steadily increased, reaching a historical high in 2018. One cause may be stricter regulations for similar target species such as …

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 …

Cost-Effective Gnss Hardware For High-Accuracy Surveys And Its Prospects For Post-Processed Kinematic (Ppk) And Precise Point Positioning (Ppp) Strategies, Johnson Olusegun Oguntuase

Dissertations

This dissertation determines for the first time the vertical accuracy achievable with low-cost mass-market multi-frequency, multi-GNSS (LM3GNSS) receivers, and antennas in the context of Ellipsoid Reference Survey (ERS), usually employed in bathymetric operations aboard survey platforms. LM3GNSS receivers are relatively new in the market, and their emergence is driven by the automobile industry and several mass-market applications requiring location-based solutions at high accuracies. It is foreseeable that emerging hydrographic survey platforms such as autonomous surface vehicles, small unmanned aircraft, crowd-sourced bathymetric platforms, and offshore GNSS buoy will find LM3GNSS receivers attractive since they are power- and cost-effective (often less than …

A Study Of Information Bots And Knowledge Bots, Amartya Hatua

Dissertations

In this dissertation, a study of different aspects of information bots and knowledge bots is done. The research contributes to a better understanding of the various characteristics of information bots as well as the different patterns and factors responsible for the information diffusion in a social network. This research also shows how these factors can be used to predict information diffusion for a particular topic in a social network. The second part of the research is focused on strategies for improving the knowledge base of knowledge bots, where two different approaches are studied. In the first approach, knowledge is transferred …

Variable Compact Multi-Point Upscaling Schemes For Anisotropic Diffusion Problems In Three-Dimensions, James Quinlan

Dissertations

Simulation is a useful tool to mitigate risk and uncertainty in subsurface flow models that contain geometrically complex features and in which the permeability field is highly heterogeneous. However, due to the level of detail in the underlying geocellular description, an upscaling procedure is needed to generate a coarsened model that is computationally feasible to perform simulations. These procedures require additional attention when coefficients in the system exhibit full-tensor anisotropy due to heterogeneity or not aligned with the computational grid. In this thesis, we generalize a multi-point finite volume scheme in several ways and benchmark it against the industry-standard routines. …

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 …

Empirical Studies Of Deep Learning On Information Diffusion On Social Networks And Collective Task Learning For Swarm Robotics, Trung T. Nguyen

Dissertations

Researchers in multiple disciplines have recently adopted deep learning because of its ability of high accuracy representation learning from big and complex data. My research goal in this thesis is developing deep learning models for information diffusion analysis on social networks and collective tasks learning in swarm robotics. Firstly, the information diffusion on social networks is modeled as a multivariate time series in three dimensions with ten features. Then, we applied time-series clustering algorithms with Dynamic Time Warping to discover different patterns of our models. Then, we build a prediction model based on LSTM, which outperforms traditional time-series prediction methods. …

A 3d Image-Guided System To Improve Myocardial Revascularization Decision-Making For Patients With Coronary Artery Disease, Haipeng Tang

Dissertations

OBJECTIVES. Coronary artery disease (CAD) is the most common type of heart disease and kills over 360,000 people a year in the United States. Myocardial revascularization (MR) is a standard interventional treatment for patients with stable CAD. Fluoroscopy angiography is real-time anatomical imaging and routinely used to guide MR by visually estimating the percent stenosis of coronary arteries. However, a lot of patients do not benefit from the anatomical information-guided MR without functional testing. Single-photon emission computed tomography (SPECT) myocardial perfusion imaging (MPI) is a widely used functional testing for CAD evaluation but limits to the absence of anatomical information. …

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 …

A Dynamic F5 Algorithm, Candice Mitchell

Dissertations

Gröbner bases are a “nice” representation for nonlinear systems of polynomials, where by “nice” we mean they have good computation properties. They have many useful applications, including decidability (whether the system has a solution or not), ideal membership (whether a given polynomial is in the system or not), and cryptography. Traditional Gröbner basis algorithms require as input an ideal and an admissible term ordering. They then determine a Gröbner basis with respect to the given ordering. Some term orderings lead to a smaller basis, but finding them traditionally requires testing many orderings and hoping for better results. A dynamic algorithm …

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 …

Adsorption Of Polyisobutylene-Based Dispersants Onto Carbon Black, Travis Paul Holbrook

Dissertations

The formation of carbonaceous by-products (e.g. soot) during the operation of an internal combustion engine is unavoidable and the aggregation of this soot leads to deleterious effects including abrasive wear of the engine, increased oil viscosities, and sludge deposition. Dispersants, which are composed of a hydrophobic tail and a polar headgroup, are used as oil additives to aid in the suspension and stabilization of the soot particles. Polyisobutylene succinimide (PIBSI) is the most well-studied class of dispersants and is characterized by a linear architecture and polyamine headgroup that interacts with soot by acid-base and dipole-dipole interactions. As such, there remains …

The Antimicrobial Activity And Cellular Targets Of Plant Derived Aldehydes And Degradable Pro-Antimicrobial Networks In Pseudomonas Aeruginosa, Yetunde Adewunmi

Dissertations

Essential oils (EOs) are plant-derived products that have been long exploited for their antimicrobial activities in medicine, agriculture, and food preservation. EOs represent a promising alternative to conventional antibiotics due to the broad-range antimicrobial activity, low toxicity to human commensal bacteria, and the capacity to kill microorganisms without promoting resistance. Despite the progress in the understanding of the biological activity of EOs, many aspects of their mode of action remain inconclusive. The overarching aim of this work was to address these gaps by studying molecular interactions between antimicrobial plant aldehydes and the opportunistic human pathogen Pseudomonas aeruginosa. We initiated …

Developing A Computational Framework For A Construction Scheduling Decision Support Web Based Expert System, Feroz Ahmed

Dissertations

Decision-making is one of the basic cognitive processes of human behaviors by which a preferred option or a course of action is chosen from among a set of alternatives based on certain criteria. Decision-making is the thought process of selecting a logical choice from the available options. When trying to make a good decision, all the positives and negatives of each option should be evaluated. This decision-making process is particularly challenging during the preparation of a construction schedule, where it is difficult for a human to analyze all possible outcomes of each and every situation because, construction of a project …

Establishing The Role Of The Mississippi-Alabama Barrier Islands In Mississippi Sound And Bight Circulation Using Observational Data Analysis And A Coastal Model, Laura Hode

Dissertations

The Mississippi-Alabama barrier islands restrict exchange between the Mississippi Sound and Mississippi Bight in the northern Gulf of Mexico. The islands also act as storm breaks for tropical cyclones, so their continued existence sustains marine ecosystems and protects coastal communities. However, the chain has undergone extensive segmentation, erosion, and westward migration in the past two hundred years. The islands are now more susceptible to further erosion (Pendleton et al., 2013; Morton, 2007). Additional reduction in island subaerial land extent would alter circulation in the Mississippi Sound and Bight.

Consequently, this study targeted the two most vulnerable barrier islands in the …

Morphological Study Of Voids In Ultra-Large Models Of Amorphous Silicon, Durga Prasad Paudel

Dissertations

The microstructure of voids in pure and hydrogen-rich amorphous silicon (a:Si) network was studied in ultra-large models of amorphous silicon, using classical and quantum- mechanical simulations, on the nanometer length scale. The nanostructure, particularly voids of device grade ultra-large models of a:Si was studied, in which observed three-dimensional realistic voids were extended using geometrical approach within the experimental limit of void-volume fractions. In device-grade simulated models, the effect of void morphology; size, shape, number density, and distribution on simulated scattering intensities in small- angle region were investigated. The evolution of voids on annealing below the crystallization temperature …

Modifying Inhibited Primer Performance Via Control Of Epoxy-Amine Matrix Structure And Composition, Steven Wand

Dissertations

This research represents an effort to deliver a new fundamental understanding of how polymer matrix characteristics influence corrosion protection of organic coatings, in particular the performance of corrosion inhibitor-containing primers. By modifying the structure and composition features of epoxy-amine matrices which commonly serves as the binder for protective coatings, the thermal/mechanical, adhesion, and transport properties which govern coating performance and inhibitor release were altered in such a way that directly influenced protection efficacy. This research is composed of three distinct approaches towards systematically varying thermoset network characteristics and observing the resulting impact on transport behaviors and corrosion prevention, with an …

“Polysoaps” Via Raft Copolymerization To Form Well-Defined Micelles For Water Remediation And Targeted Drug Delivery Applications, Phillip Pickett

Dissertations

Amphiphilic copolymers have become increasingly important for environmental and biological applications due to their behavioral characteristics in aqueous solution. For example, structurally-tailored statistical amphiphilic copolymers or “polysoaps” can self-assemble into micelles or other architectures in water at various concentrations. Polysoaps may be differentiated from small molecule surfactant micelles in their capability to self-assemble into unimolecular associates (unimolecular micelles) with no dependence on concentration. Such micelles offer enormous potential for dispersion of hydrophobic species in water at high dilution. Importantly, each polymer chain forms its own micelle and upon dilution, these micelles remain intact and capable of dispersing hydrocarbon material in …

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Manipulation Of Noncovalent Interactions For The Synthesis And Use Of Natural Product Synthons, Alison P. Hart

Dissertations

Natural products are widely used in the pharmaceutical industry, in agriculture, and as specialty chemicals. Methodology development focuses on optimizing the key organic reactions to access these natural products while trying to limit the overall number of synthetic steps. Key bond forming strategies are sought to provide new ways to address carbon-carbon or carbon-heteroatom bonds. The advancement of new asymmetric reactions to generate enantiopure products from achiral starting materials is a vital area of research. The objectives addressed in this dissertation include: 1) the development of a general reductive conversion of esters to ethers with a broad substrate scope accessing …

Scalable Time-Stepping For Navier-Stokes Through High-Frequency Analysis Of Block Arnoldi Iteration, Brianna Bingham

Dissertations

Existing time-stepping methods for PDEs such as Navier-Stokes equations are not as efficient or scalable as they need to be for high-resolution simulation due to stiffness. The failure of existing time-stepping methods to adapt to changes in technology presents a dilemma that is becoming even more problematic over time. By rethinking approaches to time-stepping, dramatic gains in efficiency of simulation methods can be achieved. Krylov subspace spectral (KSS) methods have proven to be effective for solving time-dependent, variable-coefficient PDEs. The objective of this research is to continue the development of KSS methods to provide numerical solution methods that are far …

Enhancement Of Krylov Subspace Spectral Methods Through The Use Of The Residual, Haley Dozier

Dissertations

Depending on the type of equation, finding the solution of a time-dependent partial differential equation can be quite challenging. Although modern time-stepping methods for solving these equations have become more accurate for a small number of grid points, in a lot of cases the scalability of those methods leaves much to be desired. That is, unless the timestep is chosen to be sufficiently small, the computed solutions might exhibit unreasonable behavior with large input sizes. Therefore, to improve accuracy as the number of grid points increases, the time-steps must be chosen to be even smaller to reach a reasonable solution. …

Evaluating Corrosion Altering Properties Of Thiophene Based Copolymers, Robert Peterson

Dissertations

There is an important and ongoing debate on how or whether conductive polymers (CP) alter corrosion performance with some researchers reporting that CPs ultimately accelerate corrosion and others saying CPs, if understood could possibly replace the world’s best standard for corrosion prevention, i.e., chromium based inhibitors. The primary project goal was to improve our understanding of how CPs alter corrosion chemistry by 1) controlling the polymer structure and 2) in-turn the properties and then 3) targeting the best protocol for fast corrosion kinetic evaluation.

We detail the copolymer synthesis results and shift in corrosion protection properties for …