Polymer Chemistry Commons^™

Synthesis And Characterization Of Degradable Polymers, Christopher Collins

Mahurin Honors College Capstone Experience/Thesis Projects

A degradable polymer with proposed applications in drug delivery was synthesized and characterized. This polymer was grown from a difunctional initiator, a "core" that is able to grow two polymer chains and able to degrade in the presence of oxidizing agents such as peroxides. During the first part of this project, poly(methyl methacrylate) was synthesized via atom transfer radical polymerization using commercially-available reagents in order to develop an optimal synthesis technique. This technique was then used to synthesize the degradable polymer. After introducing hydrogen peroxide, the molecular weight of the degradable polymer decreased in two different experiments, confirming its hypothesized …

Functional Polymers Through Mechanochemistry, Stephen Schrettl, Diedrik W.R. Balkenende, Céline Calvino, Marc Karman, Ana Lavrenova, Laura N. Neumann, Yoshimitsu Sagara, Ester Verde-Sesto, Michela Di Giannantonio, Yoan C. Simon, Katharina M. Fromm, Marco Lattuada, Christoph Weder

Faculty Publications

While coupling mechanical and chemical processes is widespread in living organisms, the idea to harness the mechanically induced dissociation of weak covalent and non-covalent bonds to create artificial materials that respond to mechanical stimulation has only recently gained attention. Here we summarize our activities that mainly revolve around the exploitation of non-covalent interactions in (supramolecular) polymeric materials with the goal to translate mechanical stresses into useful, pre-defined events. Focusing on mechano- chromic polymers that alter their optical absorption or fluorescence properties, several new operating principles, mechanosensitive entities, and materials systems were developed. Such materials are expected to be useful for …

Properties And Applications Of Tetraalkylphosphonium Alkylsulfate Ionic Liquids And 3d Printed Polymerized Ionic Liquids, Mustafa Mohammed Alhussain

Murray State Theses and Dissertations

Ionic liquids (ILs) are defined as pure salts with a melting temperature below 100 °C with a subset called room-temperature ILs (RTILs) with melting temperatures at or below room temperature. The sizes of the cation and anion play a critical role in determining the properties, with smaller ions forming stronger ionic forces and packing better, raising viscosity and lowering conductivity of the IL. At the same time, intermolecular forces such as van der Waals and hydrogen bonding can play a role in IL properties as well. Our research described herein is focused on three tetraalkylphosphonium-based cations coupled with three alkylsulfate …

Increased Utility Of Ph Sensitive Indicators As High Concentration Co2 Detectors Through The Use Of Polyelectrolyte Complexes As Stabilizing Media, Camden James Johnson

All Master's Theses

Development of plastic materials which produce visible color change when exposed to different environments has recently attracted attention for many biomedical applications.^1,2Many biomedical devices are packaged under high concentrations of carbon dioxide (CO₂) which can lower the pH of the packaging environment. This is similar to the CO₂ chemistry responsible for ocean acidification.³ Dye molecules that are sensitive to environmental changes in pH (known as pH indicators) can be encapsulated in plastics and produce a visible color change when a medical device is removed from the sterile CO₂ environment. Plastics made from large …

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated according to …

Mini‐Review: The Promise Of Piezoelectric Polymers, Timothy D. Usher, Kimberley R. Cousins, Renwu Zhang, Stephen Ducharme

Physics Faculty Publications

Recent advances provide new opportunities in the field of polymer piezoelectric materials. Piezoelectric materials provide unique insights to the fundamental understanding of the solid state. In addition, piezoelectric materials have a wide range of applications, representing billions of dollars of commercial applications. However, inorganic piezoelectric materials have limitations that polymer ferroelectric materials can overcome, if certain challenges can be addressed. This mini-review is a practical summary of the current research and future directions in the investigation and application of piezoelectric materials with an emphasis on polymeric piezoelectric materials. We will assume that the reader is well versed in the subject …

Investigations Into Ring-Opening Polymerization Of Functionalized Ε-Caprolactones, Danielle N. Coderre, Matthew K. Kiesewetter

Senior Honors Projects

Polymers are defined as large molecules constructed from small, repeating units (monomers) which make up everyday items, such as: plastic bags and bottles, waterproof coatings, pipes, etc. H-bonding urea (U) or thiourea (TU) catalysts paired with base cocatalysts used for organocatalytic ring-opening polymerization (ROP) of cyclic esters have been shown to exhibit fast rates of polymerization and result in polymers with controlled molecular weights (Mn) and low polydispersity indexes (PDI). Additionally, organocatalytic ring-opening polymerization (ROP) techniques have been shown to be tolerant of the incorporation of functional groups into the monomer feed, which is vital for the catalytic synthesis of …

Characterization Of Polymers Containing Ferrocene And Imidazole With Density Functional Theory, Eric Mullins

Electronic Theses & Dissertations

Electrochemical and UV-Vis studies on these polymers in the presence of aqueous solutions containing metal ions have revealed significant modifications in the electrochemical properties and absorption spectra. These modifications in electrochemical properties could be attributed to the ability of the imidazole to coordinate with metal ions, increasing its electron deficiency and enhancing oxidization of the nearby ferrocene moiety if it is in close proximity with imidazole. However, the mechanism of interaction between the imidazole and metal ions, as well as the equilibrium geometry of the resulting polymer-metal ion complex is unknown.

In this thesis, density functional theory (DFT) was used …

End-Capping Strategies For Triggering End-To-End Depolymerization Of Polyglyoxylates, Bo Fan, John Trant, Elizabeth Gillies

Chemistry Publications

Polymers that undergo end-to-end depolymerization in response to the cleavage of a stimuli-responsive end-cap are promising for diverse applications from drug delivery to responsive coatings and plastics. It is critical that the end-cap is designed to respond to an appropriate stimulus for the application. In the current work, end-caps for triggering the depolymerization of poly(ethyl glyoxylate) (PEtG) were explored. First, a phenylboronate, a disulfi de, and an azobenzene were utilized to impart redox-responsive properties to PEtG. Then, methoxy-substituted trityl groups were used to provide sensitivity to mild acid. A multiresponsive platform was also introduced, allowing PEtG to respond to multiple …

Synthesis, Properties, And Antibacterial Activity Of Polyphosphonium Semi-Interpenetrating Networks, Tyler John Cuthbert, Tristan Harrison, Paul J. Ragogna, Elizabeth Gillies

Chemistry Publications

The development of new approaches to antibacterial surfaces is of growing interest to combat the spread of harmful bacterial infections. Relative to polyammoniums, polyphosphoniums can exhibit enhanced chemical and thermal stability, but have not yet been widely explored for the preparation of antibacterial surfaces. In this work, polyphosphoniums of varying chain lengths were synthesized by reversible addition-fragmentation chain-transfer polymerization of 4-vinylbenzyl derivatives of triethyl, tributyl, and trioctylphosphonium. These polyphosphoniums were then incorporated into semi-interpenetrating networks (SIPNs) based on tetra(ethylene glycol) diacrylate (TEGDA) via a UV light-initiated curing process. Measurements of cure percentage, gel content, water contact angle, and surface charge …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

Synthesis And Properties Of Bisimidazolium And Poly(Ethylene Glycol)-Containing Michael Addition Polyester Networks, Joshua Allan Dippie

Murray State Theses and Dissertations

Poly(ionic liquid)s (PILs) have been examined in recent years for applications in various technologies, including solid-state lithium ion batteries and gas separation membranes. In this work, a series of bisimidazolium-containing, Michael addition donors were synthesized and used to produce a series of covalently crosslinked PIL polyester networks containing bis(trifluoromethylsulfonyl)imide as the counteranion. Within the series, the length of alkyl spacer between the two imidazolium cations and the diacrylate to acetoacetate monomer ratio were varied in an attempt to correlate structural variations with the thermal, mechanical, and conductive properties of the PILs. Keeping the diacrylate to acetoacetate ratio constant, increasing the …

Polymerization Of Blocked Isocyanate Functional Polymer Surfaces And Post-Polymerization Modification By Thiol-Isocyanate Reactions, Chase A. Tretbar

Honors Theses

Direct polymerization of isocyanate-functional monomers has been achieved with controlled radical polymerizations (CRP) for precisely engineered modification platforms with highly reactive side chains. However, despite the success of these strategies, the inherent reactivity of isocyanates still leads to adverse side reactions, such as hydrolysis, that are difficult to suppress. Phenol, lactam, and oxime-based blocking agents have been used to limit the reactivity of isocyanates in applications such as multicomponent urethane coating systems. The reactivity of these blocked isocyanates can be restored by thermal deprotection of the blocking agent to achieve the desired reactions. In this work, we use blocked isocyanate-functional …

Multi-Mode And Single Mode Polymer Waveguides And Structures For Short-Haul Optical Interconnects, Kevin L. Kruse

Dissertations, Master's Theses and Master's Reports - Open

Single mode and multi-mode polymer optical waveguides are a viable solution for replacing copper interconnects as high speed and large bandwidth short-haul optical interconnects in next-generation supercomputers and data servers. A precision laser direct writing method is implemented for producing various single mode and multi-mode polymer waveguide structures and their performance is evaluated experimentally showing agreement with theoretically developed models. The laser direct writing method is the optimal solution for low-rate cost-effective prototyping and large area panel production.

A single mode polymer waveguide bridge module for silicon to glass optical fibers is designed, modeled, fabricated, and measured. The bridge module …

Biodegradable Poly(Ester Urea's) Scaffold Sponges Containing Platelet-Rich Plasma For Targeted Tendon-Bone Fixation, Alex B. Ellenberger Mr.

Williams Honors College, Honors Research Projects

In this report the synthesis and characterization of L-valine and L-isoleucine poly(ester ureas) (PEUs) for future use in the synthesis of biodegradable PEUs sponges will be discussed. The method of monomer and polymer synthesis will be explained along with the characterization of the monomer and polymer products. This characterization will be done by the use of Nuclear Magnetic Resonance (NMR) and Size Exclusion Chromatography (SEC). NMR is a quick and convenient method for determining structure and purity of the monomer and polymer products. SEC gives the number average molecular weight, which is the statistical average molecular weight of all the …

Surgical Adhesive From Mussel Mimetic Polymer, Jenna Desousa, Cori Jenkins, Jonathan Wilker

The Summer Undergraduate Research Fellowship (SURF) Symposium

Injuries involving damaged tissues are currently repaired through an invasive technique involving the use of screws, plates and sutures as support, which can damage these tissues. The biomedical field currently lacks an adhesive that can replace harmful implants. A surgical adhesive can provide a quick and easy alternative, which will minimize the risk of damaging healthy tissue in surgery. Inspiration for such materials can be found by looking at marine mussels as they are able to stick to nearly any surface, even in wet environments. Marine mussels affix themselves to different surfaces using adhesive plaques consisting of various proteins. Polymer …

Effects Of Varying The Cure Profiles Of An Epoxy-Amine System, Patrick W. Hollingsworth

Honors Theses

The cure of an epoxy prepolymer with an amine hardener induces stress in thermosetting systems. The extent of residual stresses in the cured epoxy-amine thermosets are dependent on several factors; one of which is the cure profile utilized. The effect of cure profile on cure induced stresses of an epoxy-amine thermoset was examined in the current study. A difunctional epoxide based on diglycidyl ether of bisphenol-A (DGEBA) and a tetrafunctional amine curative were used to conduct this study. Two cure profiles were selected to prepare samples of varying degrees of stress in the cured thermosets. The first was constant heating …

Nanoparticles And Polymer Crystallization Kinetics In Hybrid Electronic Devices, Taylor William Wagner

Master's Theses

Conjugated semi-conducting polymers have become well known for their potential applications in hybrid electronic devices like solar cells, LEDs, and organic displays. These hybrid devices also contain inorganic nanoparticles, which complement the polymer when they are combined into the same layer. Control over the conformation and crystallinity of the polymer is critical for device performance, yet not much is known about the effect that these nanoparticles have on the polymer. Here, zinc oxide nanowire was surface modified with mono-substituted-carboxylic acid tetraphenylporphyrin and dodecanethiol, and introduced to poly(3-hexyl thiophene) in solution. The electron transfer, kinetics, and thermodynamics of this system were …

Formulation Development Of A Polymer-Drug Matrix With A Controlled Release Profile For The Treatment Of Glaucoma, Eric W. Tsoi

Master's Theses

Glaucoma is the leading cause of blindness in the United States accounting for 9-12% of all cases of blindness. Currently, the front line treatment for glaucoma are prostaglandins that may have to be taken up to several times a day. Even with proper treatment, roughly 11% of the patients using the treatment are non-compliant and lose their vision. In this project, ForSight Laboratories has developed a pharmaceutical drug delivering implant with the capability of sustaining long-term release of a prostaglandin as a new way to treat the condition. This project reports the product development of a polymer drug matrix with …

Development Of Quantitative Ft- Ir Methods For Analyzing The Cure Kinetics Of Epoxy Resins, Sang Ha Son

Open Access Dissertations

Epoxy thermosets are important engineering materials with applications in coating, adhesives, packaging and as structural components in a variety of advanced engineering products. The ultimate performance of polymer critically depends upon the details of the cure chemistry used to produce the thermoset. In order to better understand and monitor the cure chemistry, quantitative analysis of the FT-IR response has been developed for describing the epoxy-amine curing reaction as well as monitoring the hydrogen bonding that occurs in these systems The FT-IR analysis includes (i) quantitative deconvolution of complex peaks into individual spectral contributions, (ii) peak identification via DFT analysis and …

Latent Cysteine Residues From Polymers Prepared Via Free And Controlled Radical Polymerizations, Douglas Vincent Amato

Master's Theses

One less commonly used “click” reaction is thiazolidine chemistry. Thiazolidine chemistry is a commonly used reaction used in biological systems because the reaction requires the presence of both cysteine (a common amino acid) and an aldehyde or ketone. If cysteine residues could be incorporated into a polymer then a variety of applications could be developed. Polymers containing free thiols (aka thiomers) have developed in the last decade to become great mucoadhesives. If there was a facile route to control the amount of free thiols along the polymer then more fine-tuned and potentially stronger adhesives could be made. For these reasons …

Polymers For Dna Binding, Sue Yuan Li

Seton Hall University Dissertations and Theses (ETDs)

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Analysis And Simulation Of Kinetic Model For Active Suspensions, Panon Phuworawong

Mathematics & Statistics Theses & Dissertations

In this research, we study the recently proposed kinetic model for active suspensions, where the active particles are assumed to be rigid rod and are driven in the suspension either by their own biological/chemical forces or external electric/magnetic fields. We first study the stability of the isotropic suspension in quiescent flow. Then we investigate the weak shear perturbation of the isotropic state and study some rheological properties of the suspension by explicit analytic formulas derived directly from the model. For imposed shear, we give some bifurcation diagrams of the stable states in some parametric spaces through numerical simulations. Some rheological …

Development And Extrapolation Of An Undergraduate Laboratory Experiment To An Elastomeric Spinal Muscular Atrophy Brace, Richard Sterling Brose

Master's Theses

Ever since the advent of polymer science, polyurethanes have played a huge role in the industrial world. They have been used in endless applications from furniture padding to aircraft coatings, to binders for insensitive munitions. It is therefore important that the chemistry of polyurethanes is well understood as well as the ability to draw relationships between the raw materials selected and the end-use properties of the polymer. Because of the multitude of practical applications, the development of an undergraduate polymer chemistry laboratory focused on polyurethane elastomers is developed and described herein. Polymer chemistry students are exposed to hydroxyterminated polybutadiene (HTPB) …

Synthesis Of Polymers Featuring Novel Diphosphines, Eleanor Tennyson

All Theses

This report details the synthesis of functionalized platinum-based metallopolymers featuring m-terphenyl-scaffolded and light-harvesting phosphine ligands. Substituents placed on both the phosphine and pendant alkynyl units can enhance the optical activity of the metallopolymers depending on their inherent properties. The presence of the platinum metal atom can be exploited to increase conductivity of the molecule and promises to be a unique and valuable modification for polymers to be used in light emitting diodes and photovoltaics. Light-harvesting phosphines prepared in the course of the metallopolymer development have also been used to prepare luminescent polyelectrolytes that prove valuable for well-defined composite film formation …