Polymer Science Commons^™

Purifying Circular Rna Therapeutics, Karen Guillen-Cuevas

All Dissertations

Circular RNA (circRNA) has emerged as a promising therapeutic modality due to its enhanced stability and resistance to exonuclease degradation compared with linear mRNA. However, its stability and functionality depend strongly on achieving high purity, and current methods such as size-exclusion chromatography suffer from peak overlap, low yields, and poor scalability. This dissertation addresses these limitations by developing ultrafiltration-based strategies to purify circRNA directly from in vitro transcription (IVT) and self-splicing (circularization) reactions. First, the feasibility of ultrafiltration was demonstrated using polyethersulfone membranes, where sieving coefficients and critical flux values of circRNA, precursor RNA, and nicked RNA were measured to …

Design And Characterization Of Lignin-Based, Thermoresponsive Soft Composites With Improved Mechanical And Transport Properties, Missoury D. Wolff

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In an attempt to reduce reliance on petroleum-based polymers, lignin – an abundant biopolymer – has gained popularity as a sustainable alternative. However, research on lignin-containing soft composites – i.e., hydrogel (bio)composites – has largely been heuristic, providing limited insight into the fundamental structure-processing-property relationships that govern performance improvements in this emerging class of ‘green’ soft composites. As such, this dissertation presents a systematic investigation of how lignin molecular weight (MW), composite composition, and the concentrations of crosslinker and accelerator impact the mechanical and transport characteristics of soft composites composed of lignin, poly(N-isopropylacrylamide) (PNIPAm), and poly(vinyl alcohol) (PVA).

In the …

Magnetic Resonance Imaging Trackable Pathology-Triggered Polymersomes Toward Enzyme Replacement Theranostics For Gm1 Gangliosidosis, Dorian Foster

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This dissertation investigates the development and optimization of pathology-responsive polymersomes for simultaneous enhanced magnetic resonance imaging (MRI) and enzyme replacement therapy (ERT) in the treatment of GM1 gangliosidosis (GM1). While therapeutic strategies exist for similar, non-neuropathic lysosomal storage disorders, implementation towards GM1 faces significant challenges due to the blood-brain barrier.

Herein, we developed and characterized a range of low molecular weight hyaluronic acid-b-polylactic acid (HA-PLA) polymersomes (PSs) capable of encapsulating therapeutic enzymes in their hydrophilic core. These polymersomes exhibit pathophysiology-triggered responsiveness, degrading in the presence of acidic conditions, which is characteristic of lysosomes, and enzymes such as hexosaminidase A, which …

Isolation And Upgrading Of Lignin From Agricultural Sources Using Phase Equilibria, Bronson Lynn

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In the emerging bioeconomy, agricultural residues from our nationwide crop harvests are positioned to be a cornerstone of renewable and sustainable fuels, chemicals, and materials. However, to be economically viable, the basic constituents of this plant matter must be separated and funneled to the appropriate application to maximize value and overall usability.

This work focuses on the component that has, to this point, been largely left behind: lignin. Although it is the most abundant aromatic biopolymer on the planet, making up 15-40% of grasses, hardwoods, and softwoods, the processing involved to isolate usable lignins is too complex and expensive to …

Fabrication And Characterization Of Lignin–Pva Hydrogels With Tunable Network Structures, Keturah Bethel

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The ability to directly tune the crosslinked network structure of hydrogels is crucial for their functional applications in various fields, such as water filtration, protein separation, and tissue engineering. By controlling the crosslink density of the hydrogel, one can directly alter the mesh size – i.e., the end-to-end distance between crosslink junctions – and, subsequently, directly alter the hydrogel performance. This work discusses the fabrication and characterization of soft composites containing the biopolymer, lignin, are discussed. Precisely, physically-crosslinked composite lignin–Poly(vinyl alcohol) (PVA) hydrogels were fabricated via the freeze-thaw (F/T) pathway, whereby solutions containing specified amounts of PVA and lignin were …

Fundamental Study Of Nonlinear Electrophoresis, Joseph Armakan Bentor

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Classical electrophoretic theory describes the linear response of particles suspended in Newtonian fluids under weak electric fields. When the electric field exceeds this weak limit, a nonlinear response arises due to non-uniform surface conduction over the curved particles. This nonlinear behavior introduces dependencies on fluid and particle properties not considered in the classical theory, offering potential advantages for microfluidic particle manipulation. While this phenomenon has been extensively studied theoretically and numerically in Newtonian fluids, experimental investigations have been relatively limited.

Fluid rheology can significantly alter particle dynamics under applied electric fields. Rheological properties like shear-thinning and elasticity which are not …

Green Chemistry Design Of Epoxies From Biomass For Circular Economy, Kavya Ganesan

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The commercial epoxies market in automobiles has been growing mainly in terms of usage as automotive coatings and lightweight composite structures manufacturing. Most of these commercial epoxies are bisphenol-based. Bisphenol-based epoxies are a class of high-performance polymer materials that, when cured, yield thermosets with high mechanical, thermal and chemical resistance properties. Roughly, North America produces around 123 billion pounds of these epoxies which are used in various industrial applications like coatings, composites, structural parts, automotive, electronics, construction etc. These epoxies are mainly manufactured from bisphenol-A (BPA) and epichlorohydrin (EPH). These raw materials are sourced from fossil fuel resources and are …

Sulfonated Ionomer Composite Membranes For Use In Vanadium Redox Flow Batteries, Xueting Wang

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While vanadium redox flow batteries (VRFBs) have garnered significant attention as a promising scalable energy storage technology, the current membrane material used in this technology, Nafion™, suffers from high cross mixing of vanadium ions in the liquid electrolytes, directly impacting battery performance properties such as the voltage and coulombic efficiencies, as well as resulting in a reduction in the overall battery lifetime. The use of ionomer nancomposites has proven to be one promising route of directly addressing the issue of high ion crossover, though the mechanism by which the nanoparticles act to reduce crossover remains in open question. Herein, the …

Activated Carbon Synthesis From Lignin-Rich Byproduct Streams Of Biorefineries, Chengjun Wu

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Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, it is necessary to add value to the “ligno-” components (up to 30% by mass) of the biomass. Instead of just burning it for heat and electricity generation, direct conversion of lignin carbon into a product provides a complementary path to carbon capture, promoting a more environmentally conscious approach. However, the utilization of these lignin-rich byproduct streams, which are separated from the biofuels production, for industrial products can be challenging. The use of specific …

Improving Lignin Recovery From Paper Mill And Biorefinery Waste Streams Via Liquid-Phase Splitting, Carter Fitzgerald

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Lignin is an abundant biopolymer with significant promise due to its aromaticity. It has been targeted as a replacement for a number of petroleum-based products including adhesives, coatings, polyurethane foams, activated carbon, and carbon fibers. However, commercially available bulk lignins are too polydisperse, and contain too many residual metals from the pulping process that are detrimental to the properties of the final product.

The Sequential Liquid-lignin Recovery and Purification (SLRP) process was developed by Michael Lake and John Blackburn, in collaboration with Clemson, with the intention of creating a continuous method for recovering lignin from paper-mill black liquors. Thies and …

Characterization Of Lignin And Cellulose Biopolymers Structure – Function Relationships, Zachariah Pittman

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Biomass is vital to ongoing efforts to secure a sustainable future. While many of our efforts focus on finding alternative forms of energy, biomass among them, only biomass has the potential to serve as a sustainable materials feedstock. However, biomass is heterogenous, complicating the upgrading processes needed to manufacture commodity and performance products. For example, plant biomass consists largely of cellulose, a crystalline polysaccharide, and lignin, a highly stable polyaromatic. The specific properties of cellulose and lignin depend greatly on the plant, harvesting conditions, and isolation procedures. Thus, accurate and reliable determination of the fundamental properties of biomass is crucial …

Elucidating The Mechanical And Transport Properties Of Lignin-Based Hydrogel Composites, Nicholas Gregorich

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The use of lignin in the fabrication of soft composites has become an emerging area of research in polymer science and polymer chemistry. These lignin-based materials present numerous benefits, notably, a reduction in the use of petroleum-based precursor, improved structural benefits to otherwise soft host polymers, as well as the inherent antimicrobial and antioxidant properties of lignin, making it suitable for biomaterials. Herein, we present two chemical reaction pathways of incorporating lignin that was fractionated and cleaned using the Aqueous Lignin Purification with Hot Agents (ALPHA) process into poly(vinyl alcohol) (PVA) hydrogel composites for aqueous-based separations. By leveraging the ALPHA …

Bridging The Gap Between Phase Behavior And Processing For Renewable And Refinable Carbonaceous Precursors, Graham Tindall

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As a category of materials, engineered carbons, specifically carbon fibers, are first-in-class for properties such as modulus, specific strength, and thermal resilience; however, the inability to directly process atomic carbon necessitates the development and optimization of carbonaceous precursors. Because the structure and properties of carbon are highly dependent on the precursors and requisite processing, numerous materials have been investigated as feedstocks for large-scale production. Although cellulose and rayon were among the first investigated, polyacrylonitrile (PAN) is the current hegemon of carbon fiber precursors. PAN feeds 90% of this market, but it is neither inexpensive nor renewable. Because a significant fraction …

Carbon Fibers From Bio-Based Precursors Derived From Renewable Sources, Sagar Kanhere

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Carbon fibers have the highest strength and modulus among all known fibers and are used as reinforcements in high-performance composites [1]. Carbon fibers also have a very low density relative to metals. Therefore, carbon fibers possess ultrahigh specific strength and modulus, which make them desirable for high-performance light-weight composites. A vast majority of commercial carbon fibers are produced from PAN precursors that are expensive, which limits the use of PAN-derived carbon fibers to aerospace applications (e.g., airplanes). However, for costsensitive applications, there is a need for low-cost, moderate performance carbon fibers. Lignin is a low-cost by-product of pulping and biorefining …

Reactive Thin Film Polymers And Thin Film Composite Membranes For The Rapid Screening Of Uranium Isotopes, Abenazer W. Darge

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Traditional radiochemistry approaches for the detection of trace-level alpha-emitting radioisotopes in water require lengthy offsite sample preparations and do not lend themselves to rapid quantification. Therefore, a novel platform is needed that combines onsite purification, concentration, and isotopic screening with a fieldable detection system. My dissertation research objective was to develop novel reactive thin polymer films and thin film composite membranes for the selective separation of uranium from environmental water followed by direct isotopic analysis by alpha spectroscopy. Chapter 1 reviews progress made on uranium separation from aqueous matrices and discusses methods used for the determination of isotopic composition.

Chapter …

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

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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 …

Investigating Polymer Based Scaffolds For Urinary Bladder Tissue Engineering, Srikanth Sivaraman

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Current surgical treatments for urinary bladder disorders rely on the use of autologous intestinal segments and xenografts such as small intestinal submucosa, which suffer from various complications including mechanical mismatch and graft shrinkage. Despite early promises of bladder tissue engineering, a recent report of unsuccessful clinical trials suggests that the technology needs further improvement and evaluation through animal models of bladder dysfunction. Therefore, the objective of this doctoral dissertation was to characterize a viable bladder tissue scaffold (patch) which mimics the mechanical properties of the bladder, maintains the phenotype of the BSMC seeded in it and finally, tested in vivo …

Synthesis And Characterization Of Chemically Functionalized Shape Memory Nanofoams For Unattended Sensing Applications, Anna Paola Soliani

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The work in this dissertation is devoted to the synthesis and characterization of novel materials for off-line unattended sensing: shape-memory grafted nanofoams. The fabrication process and characterization of highly efficient, polymeric nanosensor element with the ability to selectively detect analytes and retain memory of specific exposure events is reported. These shape memory nanofoams could potentially act as efficient and highly sensitive coatings for evanescent waveguide-based optical monitoring systems. On exposure to specific analytes, the polymeric coatings locally change their internal structure irreversibly at the nanolevel, affecting the local optical properties such as refractive index. Currently, enrichment polymer layers (EPLs) are …

Thermally Responsive Polymer Electrolytes For Inherently Safe Electrochemical Energy Storage, Jesse Kelly

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Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in …

High-Productivity Membrane Adsorbers: Polymer Surface-Modification Studies For Ion-Exchange And Affinity Bioseparations, Heather Chenette

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This Dissertation centers on the surface-modification of macroporous membranes to make them selective adsorbers for different proteins, and the analysis of the performance of these membranes relative to existing technology. Traditional chromatographic separations for the isolation and purification of proteins implement a column packed with resin beads or gel media that contain specific binding ligands on their exposed surface area. The productivity of this process is balanced by the effective use of the binding sites within the column and the speed at which the separation can take place, in addition to the need to maintain sufficient protein purity and bioactivity. …

Sulfonated Perfluorocyclobutyl (Pfcb) Aryl Ether Polymers: Synthesis, Reactivity, And Characterization For Polymer Electrolyte Applications, Jiyoung Park

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Perfluorocyclobutyl (PFCB) aryl ether copolymers are excellent candidates for proton exchange membrane (PEM) component in PEM fuel cells. Sulfonated PFCB copolymer membranes exhibit not only high chemical/thermal/mechanical stability but also high proton conductivity. In this regard, PFCB aryl ether copolymers were synthesized via thermal step-growth [2 + 2] cyclopolymerization from aryl bis-(trifluorovinyl ether) (TFVE) monomers and oligomers. Experimental and computational studies confirmed that copolymerization of relatively electron-rich and electron-poor TFVE monomers gave selective-segmented copolymers in an one-pot polymerization. After sulfonation, the PFCB copolymers comprising hydrophilic and hydrophobic segments gave membranes with high proton conductivity. Cross-linked membranes of the sulfonated PFCB …

A Localized Controlled Delivery System Utilizing A Block Copolymer To Improve The Current Paradigm Of Chemotherapy, Jason Olbrich

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The goal of the field of Bioengineering has always been to bring about a better standard of care for patients. As a field encompassing a broad array of researchers and talents, such improvements often are brought about through the integration of different fields. This work advances the integration of controlled delivery and chemotherapy. The use of cytotoxic chemotherapy has become and will continue to be a powerful tool for the treatment of solid malignancies. Conventional dose scheduling of cytotoxic agents and newer biological response modifiers are investigated under a clinical paradigm initially designed to identify a drug dose that elicits …

Aqueous Suspensions Of Polymer Coated Magnetite Nanoparticles: Colloidal Stability, Specific Absorption Rate, And Transverse Relaxivity, Steven Saville

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The design, functionalization, characterization, and applications of magnetic nanoparticles have garnered significant interest over the past several decades. While this area has garnered increasing attention, several questions remain unanswered about the stability of these systems and it's influence on their biomedical applications. To help answer these questions about the stability of these, a novel tri(nitroDOPA) terminated polymer based ligand has been developed for the stabilization of magnetite nanoparticles. The synthesis involves a process in which ethylene oxide is polymerized using a trivinyl initiator, modified with carboxylic acid using a free radical addition of mercaptoundecanoic acid, and then functionalized with nitroDOPA …

Light-Emitting Nanocomposites And Novel Amorphous Polymers For Optical Applications, Kyle Gipson

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Polymeric optical materials generally are comprised of amorphous polymers that are transparent in at visible wavelengths but exhibit strong absorption bands in the near-infrared making them less useful for many optical applications. Attenuation, which is the absorption per unit length, largely results from the high vibrational energy associated with carbon-hydrogen bonds contained in the polymer backbone. Attenuation can be mitigated by optical amplification utilizing light emitting additives. Investigated in this dissertation are synthesis techniques for the fabrication of light-emitting polymer nanocomposites and their resultant thermal and rheological characteristics for potential use as polymer optical fibers or films.
Inorganic nanocrystals doped …