Polymer Chemistry Commons^™

N-Aryl Phenoxazines As Polymer Supported Photocatalysts, Mary Kathryn Hall

Master's Theses

In photosynthesis, the energy of sunlight is perfectly harnessed to facilitate the production of small molecules that are essential for plant life on earth. Inspired by this model of energy efficiency and simplicity, this work seeks to mimic that ability to use the energy in visible light to perform new and more efficient chemistries. Just like in photosynthesis, photocatalysts can act as chromophores absorbing light to excite electrons opening new pathways for previously untapped reactivity. Recent research has provided a wide range of small molecule reactions that are made possible or easier by the use of a photocatalyst. However, these …

Development And Characterization Of Polysaccharide-Based Controlled Drug Delivery Platforms, Amanda Pepler

Open Access Dissertations

Drug delivery research focuses on overcoming challenges in patient treatment. Most therapeutics are delivered systemically through oral or intravenous routes. However, these administration methods are often inefficient due to therapeutic hydrophobicity, poor bioavailability, and liver metabolic clearance, necessitating frequent dosing. When treatment plans require frequent dosing, patients experience significant fluctuations in therapeutic concentration in the bloodstream, which can increase adverse side effects. These factors contribute to low patient compliance. Therefore, the core focus of drug delivery research is to develop new administration routes for therapeutics. Drug delivery systems (DDS) that can target therapeutics to a localized region offer advantages over …

Bio-Based Rigid Polyurethane Foams Using Modified Hemp Seed Oil Combined With Flame Retardants, Sagar Jariwala

Electronic Theses & Dissertations

In today's world, the idea is to synthesize bio-based polyurethane (PU) goods, which reduces reliance on petroleum-based products. As a result, we produced polyol from hemp seed oil (HSO) and evaluated it using FTIR, GPC, hydroxyl value, and acid value. Hemp seed oil polyol (HSOP) was successfully synthesized and combined with additional ingredients such as catalysts, blowing agents, hardeners, and flame-retardant chemicals to produce stiff polyurethane foams. The focus of this research was to synthesize high-quality flame-retardant rigid polyurethane foams (RPUFs) through the addition of flame retardants. The test results revealed that the HSO-based PU without flame retardants has 47.04 …

Exploring Soybean Oil-Based Polyol And Effect Of Non-Halogenated Flame Retardants In Rigid Polyurethane Foam, Sahithi Kondaveeti

Electronic Theses & Dissertations

To address the increasing demand for sustainable biomaterials due to the depletion of fossil fuel resources and growing environmental concerns, a new type of biodegradable and environmentally friendly rigid polyurethane foam (RPUF) has been synthesized. These foams are derived from chemically modified soybean oil-based polyol obtained from soybean oil by epoxidation followed by a ring-opening reaction. Polyurethane foam is generally used in construction, furniture, and automobile industries but is highly flammable and releases toxic gases and smoke during combustion. In this study, a highly efficient synergistic effect halogen-free flame-retardant (FR) melamine salt, 2-carboxyethyl(phenyl)phosphinic acid melamine salt (CMA) was synthesized from …

Solubility, Reactivity And Diffusion In Polymeric Bilayer Thin Films, Jacob Sitterly

Legacy Theses & Dissertations (2009 - 2024)

Microelectronics manufacturing of modern devices has required the use of polymer photoresists in several essential steps. The traditional limitation in device capability has been dependent on the minimum feature size attainable by the wavelength of light and materials used in photolithography. In this thesis the study of polymer thin films in single and bilayer stacks is described. Three scientific concepts are fundamental to this study: (1) the diffusion and (2) reaction of acid and small molecules that change polymer (3) solubility. In this thesis, two chemical systems are designed and used to study these three scientific concepts.

Characterization Of Interlayer Laser Shock Peening During Fused Filament Fabrication Of Polylactic Acid (Pla), Fabien Denise

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

The field of additive manufacturing (AM) has gained a significant amount of popularity due to the increasing need for more sustainable manufacturing techniques and the adaptive development of complex product geometries. The problem is that AM parts routinely exhibit flaws or weaknesses that affect functionality or performance. Over the years, surface treatments have been developed to compensate certain flaws or weaknesses in manufactured products. Combining surface treatments with the modularity of additive manufacturing could lead to more adaptable and creative improvements of product functions in the future. The current work evaluates the feasibility of pursuing a new research axis in …

Gold(I)-Hydroarylation In Polymer Modification – Alkynes And Alkenes With Unexpected Reactivity, Samuel B. Hunt

Dissertations

Polymer modification is crucial for developing new properties and materials from recalcitrant waste polymers. Synthetically, polymers possess a chemical inertness that renders their functionalization challenging. Specifically, the omnipresence of C–H bonds in all commercial polymers endows their chemical resistance. Thus, developments in C–H activation chemistry are crucial to polymer diversification processes and allow for fundamental insight into the role of material processing conditions on novel chemical reactions. Au(I)-chemistry has recently come to the fore owing to a unique chemical reactivity nonexistent with other transition metals. The alkynophilicity of Au(I), in tandem with their insensitivity to common polymer processing conditions (air, …

Engineered Plga Nanofibers For Drug Delivery, Andrew Mancuso

Dissertations, Theses, and Capstone Projects

Poly-lactic-co-glycolic acid (PLGA) polymers are rapidly gaining momentum as a platform for next-generation drug delivery systems due to their ease and low cost of synthesis, favorable biocompatibility and biodegradability, and lack of toxicity. In particular, the application of drug-loaded PLGA nanofibers directly to a target tissue may represent a promising alternative to traditional routes of drug administration (e.g., oral, injectable) as they offer the potential to greatly improve bioavailability, increase efficacy, and reduce off-target toxicity. Furthermore, the use of such a system may potentially allow for greater flexibility in clinical drug development, by enabling the use of compounds which have …

Paek- And Pes-Like Perarylated Phosphonium Ionenes: Synthesis, Thermal Properties, And Conductivity, Samantha Sims

Murray State Theses and Dissertations

Ionic liquids (ILs) are useful for many applications due to the tunability of their characteristic properties making these salts ideal for many applications. To further increase possible areas of application for these materials, some ILs can be incorporated into polymer structures to form poly ionic liquids (PILs) or ionenes. The specific ions used within the material will determine the thermal, mechanical, and chemical stability properties exhibited by the polymer. Adjustments can be made to the ion structures during the synthetic process to influence these observed properties.

Fuel cells, batteries, solar cells, and capacitors, all require materials that can withstand high …

One-Step Synthesis Of Corn Oil-Based Polyol For Highly Flame-Retardant Rigid Polyurethane Foams, Tenzin Ingsel

Electronic Theses & Dissertations

Rigid polyurethane foams (RPUF), heavily utilized in construction, refrigeration, and the automotive industries, are a significant class of polyurethanes. They can substantially enhance energy efficiency by improving thermal insulation. However, the application of petrochemical sources in polyurethane has raised environmental concerns.

Such concerns call for the development and application of new bio-based polyurethanes to potentially reduce humanity's over-reliance on nonrenewable sources.

In this work, corn oil-based polyol was synthesized via popularized thiol-ene reaction. The obtained polyol was characterized by wet chemistry methods, spectroscopic evaluations, and chromatography. Non-halogenated flame retardants of cost-effective and environmentally friendly nature were incorporated into the polyurethane …

Synthesis Of Fluorinated Monomers And Polymers For Various Applications, Cassandra J. Hager

All Dissertations

The world of industry utilizes a variety of polymers for various applications in many prominent fields. From electronics to food storage, the versatility of this class of chemistry has been widely proven. The Thrasher research group undertook a program dedicated towards the development of a library of fluorinated materials that focused on the synthesis and characterization of perfluoroalkoxy (PFA) copolymers of tetrafluoroethylene (TFE) and perfluoroalkyl trifluorovinyl ethers. One aim of the project was to improve upon the mechanical strength and wearability of commercial PFA resins by incorporating bulkier perfluoroalkoxy trifluorovinyl ether monomers into these copolymers. In addition to focusing on …

Synthesis Of Functional Chalcone Library For Use In Aza- Dipyrromethene Dye Systems, Kendal Crawley

Murray State Theses and Dissertations

Over the past decade, Aza-Bodipy dyes (ADPs), a derivative of the extensively studied BF₂-dipyrromethene (BODIPY), have become a growing field of research due to their unique photophysical properties, high yielding synthesis, and relative stability. They possess a unique spectral window of 600 to 750 nm which is the red to near-IR region, evidenced by the blue color of many of these dyes. Increasing interest in these dyes is due to this near-IR window which is important for many applications.^1-4 ADP chromophores also have a common core motif to that of phthalocyanines which allow for coordination at their …

Poly(Β-Gal-Thr): A New Scalable Synthetic Mucin, Manuel A. Lema

Dissertations and Theses

A method for the preparation of glycosylated polypeptides via the nucleophilic ring-opening polymerization of a glycosylated N-carboxyanhydride (NCA) monomer is reported. The synthesis of 2,3,4,6-tetraacetyl-β-galactose-threonine N-carboxyanhydride (β-AcO-Gal-Thr-NCA) monomer in 5 steps with an 8 % overall yield is described, and the single-crystal X-ray structure is provided. The effect of a series of Ni⁰-based organometallic initiators, nucleophilic amine initiators, co-catalysts, and solvents on the polymerization were explored. The kinetics of the three most promising conditions were studied in greater detail. The conditions that provided the highest yield, low polydispersity (Ð), and …

Controlling Degradation With Force And Light, Brad Davis

Dissertations

Stimuli-responsive polymers respond to changes in their environment by altering their physical and chemical properties. Their responsiveness allows them to be used as sensors, mechanical actuators, delivery systems, and can yield either elongated lifetimes through healing mechanisms or shortened lifetimes through triggered degradation. Still a growing field in polymer science, researchers seek to expand the capabilities of these materials by improving their specificity, range, and mechanisms of both the stimuli and the response. The work presented explores stimuli-responsive materials, focusing on mechanical and light stimuli, and how to gain control of the response by specific changes in the polymeric material. …

Development Of Biomaterials For Drug Delivery, Raquel De Castro

Graduate Theses and Dissertations

Drug delivery systems (DDS) have highly evolved in the last decades with the development of hydrogels and nanoparticles. However, high systemic uptake, side effects, low bioavailability, and encapsulation efficiency continue to be a major hurdle faced by such DDSs.

Nanoparticles and hydrogels can be specifically designed for targeted DDSs to mitigate some of the problems. This dissertation aimed to design two DDSs for ocular drug delivery and one for cancer treatment. The first project sought to develop chitosan nanoparticles (Cs-NP) using PEGDA as a copolymer to encapsulate gentamicin (GtS) for ocular drug delivery. Cs-NPs contain positive charges that can interact …

A Conductivity Analysis Of A Newly Synthesized Poly(Ethylene Glycol) Methyl Ether Hydroxide Electrolyte, Sarah Marie Peterson

Honors Theses

This thesis investigates the synthesis and conductive properties of a Poly (ethylene glycol) methyl ether-based polymer electrolyte. The goal of the synthesis is to enhance the hydroxide ion conduction properties of the polymer with its cationic groups attached. The MePEG backbone contained seven ethylene glycol groups and was modified to substitute the hydroxide group in the MePEG with trimethylamine. In addition, the bromide added in the synthesis was exchanged for hydroxide ions to allow for the transportation of hydroxide ions in polymeric electrolytes that can be used in Anion Exchange Membrane Fuel Cells. The newly synthesized polymer was compared to …

Thermal, Mechanical, And Rehealing Properties Of Cross-Linked Ionene Networks, Katelyn Lindenmeyer

Honors College Theses

Polymers which contain ionic liquid groups have numerous applications in a wide variety of fields. Past research from our group has shown that IL-containing polymers which exist in covalently crosslinked networks can exhibit good ionic conductivities despite the hindrance in polymer chain mobility and relaxation. In part one of this thesis, efforts to create ionic networks which have the capability of being rehealed after exposure to an external stimulus are discussed. Thermoreversible maleimide-furan chemistry was incorporated into an imidazolium-containing ionene network. Maleimide-terminated, imidazolium-containing monomers were coupled with furan-functionalized monomers, prepared from commercially available multifunctional acrylates. Thermal, mechanical and rheological characterization …

Effect Of Precise Control Of Crosslink Density On The Thermal, Mechanical, And Conductive Properties Of Covalently Crosslinked Ionene Networks, Alexander Thome

Honors College Theses

Ionic liquids (ILs), besides being well known as environmentally friendly solvents, have attracted attention for a wide variety of other applications, including gas separation, 3D-printing and electrochemical actuators. However, for many such applications, incorporation of the IL moiety into a polymeric material eliminates the use of mechanically unstable free ILs while maintaining many of their electrochemical benefits. Such polymers can take two basic forms: poly(ionic liquid)s are ion-containing polymers in which the IL group is attached pendant to the polymeric backbone, while ionenes are ion-containing polymers in which the IL group is anchored directly into the backbone of the repeating …

An Investigation Of Cross-Links On Crystallization And Degradation In A Novel, Photocross-Linkable Poly (Lactic Acid) System, Nicholas Baksh

USF Tampa Graduate Theses and Dissertations

Polymeric molecular structure consists of repeating units bonded together. Mechanicalproperties can be altered without affecting chemical makeup by altering the number of these units. Small molecules can be introduced and/or polymers can be modified to form bonds between molecular chains. Cross-linking, as this is called, also introduces mechanical variation with minimal effects on chemical composition. Lastly, polymer chains reorient themselves in response to intermolecular forces. This temperature dependent response is known as crystallization. Although chemistry is unaltered, mechanical properties can depend highly on the percent of the sample that is crystallized.

Cross-linking is known to enhance the mechanical properties of …

Polyesters With Main And Side Chain Phosphoesters As Structural Motives For Biocompatible Electrospun Fibres, André E. Polloni, Viviane Chiaradia, Ronaldo José F.C. Do Amaral, Cathal Kearney, Brian Gorey, Débora De Oliveira, José V. De Oliveira, Pedro H.H. De Araújo, Claudia Sayer, Andreas Heise

Articles

Phosphoester containing polymers are promising materials in biomedical applications due to their biocompatibility and biodegradability. Utilising thiol-ene chemistry, the synthesis of two novel structural polymer motives combining polyesters and phophoester groups was explored. The first polymer was obtained by coupling ene-functional poly(thioether-phosphoester) with thiol functional poly(pentadecalactone). While the coupling reaction was successful, yields remained low presumably due to inadequate endgroup stoichiometry. The second polymer comprised phosphoester side groups conjugated to unsaturated poly(globalide). Double bond conversions up to 84% were achieved depending of the type of phosphoester thiol and relative reactant ratios. The resulting polymers transitioned from solid semicrystaline to liquid …

Design, Synthesis And Applications Of Nanoparticles In Suppression Of Mosquito-Born Flaviviridae Viruses, Maria R. Blahove

College of Graduate Studies: Theses & Dissertations

Recently, nanoparticles have become an origin of exploration in the chemistry field due to their unique medical uses. The current drug delivery models of nanoparticles often include a metal base with a drug conjugated to its surface. However this raises concerns regarding toxicity. A novel approach to solving this dilemma is the development of nanosized biocompatible polymer-based micelles, created from PEG-PCL-PEG triblock polymer, and formed around a drug of choice. The goal is to create a drug carrier nanoparticle system that is labile at a specific intracellular pH, without undue toxicity to the cell. This creates a drug-loaded nanoparticle that …

Advancements In Bio-Based Novel (Co)Monomers For Polymeric Materials, Khristal Anne Monroe

College of Graduate Studies: Theses & Dissertations

Most current research in the area of sustainable and environmentally friendly materials relate to the use of renewable sources for the fabrication of bio-based polymers and composites. Using plant-based derivatives is a common strategy. Pine sap can be distilled into turpentines (light fraction) and pine rosin (heavy fraction). Pine rosin is obtained as a brittle solid and its major component is abietic acid. This project aims at investigating a synthetic approach for the synthesis of a pine rosin-based polymer that can be potentially used for manufacturing a collection device for pine sap. The synthetic strategy consisted in the preparation of …

Multi-Level Analysis Of Atomic Layer Deposition Barrier Coatings On Additively Manufactured Plastics For High Vacuum Applications, Nupur Bihari

Dissertations, Master's Theses and Master's Reports

While hardware innovations in micro/nano electronics and photonics are heavily patented, the rise of the open-source movement has significantly shifted focus to the importance of obtaining low-cost, functional and easily modifiable research equipment. This thesis provides a foundation of open source development of equipment to aid in the micro/nano electronics and photonics fields.

First, the massive acceptance of the open source Arduino microcontroller has aided in the development of control systems with a wide variety of uses. Here it is used for the development of an open-source dual axis gimbal system. This system is used to characterize optoelectronic properties of …

Proto-Rna Synthesis Using Glycerol And Phosphate Anion, Noah Parker

Williams Honors College, Honors Research Projects

Nucleic acids are important molecules for all life, serving as the primary molecules for information storage and reproduction. RNA has long been thought to be the molecule that initiated protein synthesis. However, RNA has recently been thought to be too complex to synthesize prebiotically. Through a 1:1 mole ratio condensation of glycerol and phosphoric acid, I generated glycerol-phosphate oligomers that resemble a primitive form of the carbon-phosphate backbone of RNA. 75 mmol MgCl2 was added to some samples to see if the Mg cation could stabilize the reaction intermediates and further promote longer proto-RNA oligomers. These samples were all heated …

Reversible Addition-Fragmentation Chain-Transfer Emulsion Polymerization And Its Application To Waterborne Coatings, Andrew Balgeman

Graduate Research Theses & Dissertations

Waterborne acrylic latex makes up a vast majority of the architectural coatings market, including most of the paints sold in retail stores. Most, if not all, of these latex formulations are prepared using radical polymerization of acrylic monomers. Reversible addition-fragmentation chain-transfer (RAFT) polymerization has been researched for over two decades, but to this point has made very little progress finding success in commercial applications. Indeed, a majority of RAFT research has been dedicated to successfully polymerizing different monomers with good degree of polymerization control, and very little research has been directed toward actual coating applications. In this study, we focused …

Effect Of Polymer Design And Coating Formulation On The Water Uptake And Sensitivity Of Acrylic Water-Borne Films, William Z. Thompson

Master's Theses

Water-borne latex coatings represent a safer, more user-friendly, and environmentally responsible alternative to solvent-borne coatings, and are growing in popularity each year. However, these coatings often exhibit unfavorable performance when exposed to water for extended periods of time. This prolonged exposure often results in water uptake, which may give rise to other detrimental effects such as a decrease in modulus, blushing or water-whitening, reduced serviceable life, and softening of the film. In this study, various polymer composition latex design spaces are studied to develop an understanding of how water uptake can be modulated and minimized using common synthetic approaches. Factors …

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 …

Research And Review Of Polymethyl-Methacrylate Copolymers In The Development Of Enhanced Pharmaceutical Delivery Systems, Jake Dyess

Senior Honors Theses

The following thesis shall primarily explore the current research regarding the implementation of modifiable microscopic and nanoscopic polymer particles as novel pharmaceutical delivery systems. Polymethacrylate-based copolymers, such as Eudragit^TM, are sensitive to alterations in pH levels, becoming increasingly more soluble in response to an increase in pH. The selective solubility and modifiable nature of these polymers allows for greater flexibility of treatment options for patients (Patra et al., 2017). The wide range of functionality of polymethacrylate (PMA) may provide solutions to challenges relating to the current treatment and therapy of certain conditions. Research indicates that PMA based micro- …

Filtration Apparatus Design For Oil-Water Separation Using Membranes And Sponges, Alec Jerger

Williams Honors College, Honors Research Projects

It can be difficult to separate water and oil emulsions through traditional filtration. Therefore, investigations of filtering using thermo-responsive (TR) polymers, in this case poly(vinyl methyl ether) (PVME), was conducted. It’s hypothesized that below its lower critical solution temperature (LCST), PVME has an affinity for water while oil substances do not. Above the LCST the opposite will be true. To verify this hypothesis, iterations of filtration designs were created to provide optimum control over the parameters to measure flow. The final optimized experimental apparatus was a Chromaflex glass column which was air tight and controlled all parameters besides fluid flow. …

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …