Physical Sciences and Mathematics Commons^™

Nanoparticles And The Environment: Biopolymer Grafted Cellulose And Screen-Printed Carbon Nanotube Composites, Dominique Henry Porcincula

Master's Theses

A host of environmental issues will define the state of the environment in the 21^st century, with plastic pollution and water shortages among them. While solutions to these problems require large-scale, multipronged solutions, one way we can address them is through material innovation and the use of nanoparticles.

In the first project, we address the issue of plastic pollution by creating nanocomposites of biodegradable polymers (PLA and PCL) with cellulose nanofibrils. Here, PLA and PCL are grafted from the surface of cellulose nanofibrils via ring-opening polymerization of cyclic ester monomers. Polymer-grafted cellulose (PGC) is characterized with structural analysis, solubility …

Polymer-Based Nanotherapeutics To Combat Difficult-To-Treat Bacterial Infections, Jessa Marie V. Makabenta

Doctoral Dissertations

The continuous emergence and spread of antibiotic-resistant bacteria are a global health emergency, debilitating the capability to prevent and cure various infectious diseases that were once treatable. Antibiotic therapy is further rendered ineffective due to biofilm formation and the ability of bacteria to thrive and colonize inside mammalian cells. Given the diminishing efficacy of available antibiotics combined with the scarcity of new therapeutics entering the antibiotic pipeline, innovative treatment strategies are urgently in demand. Nanomaterial-based strategies offer ‘outside of the box’ approach for the treatment of antibiotic-resistant bacterial infections. Nanomaterials feature tunable physicochemical properties that can be carefully modified to …

Atom Economical Reactions Of Terpenoids And Post-Consumer Plastics With Sulfur, Charini Maladeniya

All Dissertations

The production of Ordinary Portland Cement (OPC) and its uses have a complicated environmental impact, which is influenced by infrastructure development and building operations as well as CO₂ emissions, which account for 7% of all worldwide CO₂ emissions. Due to the increasing population, production is still ongoing. The search for cement and construction materials produced with zero to low CO₂ emissions is therefore continuous. Finding recyclable, CO₂ gas-free biocomposites with high sulfur content that can rival the mechanical properties of popular building supplies like Portland cement is the primary objective of the research discussed in this …

Enhancing The Forensic Comparison Process Of Common Trace Materials Through The Development Of Practical And Systematic Methods, Meghan Nicole Prusinowski

Graduate Theses, Dissertations, and Problem Reports

An ongoing advancement in forensic trace evidence has driven the development of new and objective methods for comparing various materials. While many standard guides have been published for use in trace laboratories, different areas require a more comprehensive understanding of error rates and an urgent need for harmonizing methods of examination and interpretation. Two critical areas are the forensic examination of physical fits and the comparison of spectral data, which depend highly on the examiner’s judgment.

The long-term goal of this study is to advance and modernize the comparative process of physical fit examinations and spectral interpretation. This goal is …

Synthesis And Processing Of Polymeric Materials For Hydrogen Storage, Dominic Adrewie

Theses and Dissertations

Hydrogen is one of the most promising alternatives and clean fuel sources, but it has faced several hurdles due to storage and transportation issues. Several methods have been proposed, developed, and are being improved. Key among these is the use of polymers as safe hydrogen storage media.

This work investigated the polymerization of methyl vinyl ketone using different concentrations 2,2’-Azobis(2-methylpropionitrile) as the initiator in a free radical polymerization mechanism. There was a subsequent analysis of the effect of the initiator concentration on the conversion rate and the molecular weight of the polymers produced with the help of Gel permeation chromatography. …

Designing Polymer-Protein Complexes For Intracellular Delivery, Hazel Davis

Doctoral Dissertations

Previous work in the Tew group has demonstrated polymer cell-penetrating peptide mimics (CPPMs) as effective transporters of biological agents, including proteins and antibodies. These synthetic polymers non-covalently bind to cargo, offering a mechanism to deliver proteins in a way that does not alter protein secondary structure. However, correlations of the protein binding-delivery relationship or the role of polymer-protein complexation on intracellular activity of protein cargo are understudied. The work presented herein connects a fundamental understanding of polymer-protein complexation with intracellular internalization and cargo activity. Characterization and quantification of polymer-protein binding relationships were established using fluorescence quenching assays. In particular, the …

Comprehensive Review Of Polymer And Polymer Gel Treatments For Natural Gas-Related Conformance Control, Ali Al Brahim, Baojun Bai, Thomas P. Schuman

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Conformance problems often exist in natural gas-related activities, resulting in excessive water production from natural gas production wells and/or excessive natural gas production from oil production wells. Several mechanical and chemical solutions were reported in the literature to mitigate the conformance problems. Among the chemical solutions, two classes of materials, namely polymer gels and water-soluble polymers, have been mostly reported. These systems have been mainly reviewed in several studies for their applications as water shutoff treatments for oil production wells. Natural gas production wells exhibit different characteristics and have different properties which could impact the performance of the chemical solutions. …

Chemical And Physical Tailoring Of Guanidine-Based Covalent Adaptable Networks, Kate A. Mcconnell, Michael B. Larsen

WWU Honors College Senior Projects

We present the synthesis of two different guanidine-based CAN materials which, unlike traditional thermoset polymer networks, can undergo an exchange reaction called thermal guanidine metathesis (TGM) and be reprocessed. Thermosets, which are polymer networks characterized by permanent covalent crosslinks between chains, have a myriad of commercial applications. However, a major drawback to thermosets is their inability to be reprocessed. To develop a more sustainable thermoset-like material, CANs exhibit breaking and reforming of crosslinks under certain conditions that enable reprocessing. To elucidate the effects of varied guanidine structure on the rheological and mechanical properties of these dissociative CANs, we synthesized two …

Sustainable Polymers: Upcycling Poly(Vinyl Chloride) And Mimicking Low Density Polyethylene, Ian Baxter

Theses and Dissertations

In this research, increasing the sustainability of polymers was investigated through two main methods. The upcycling of poly(vinyl chloride) and the creation of polymer mimics to create degradable low-density polyethylene. In the first chapter, an overview of the sustainability issues of polymers is presented and approaches are described on how their sustainability may be increased through the upcycling of polymers or the synthesis of degradable polymers that mimic the properties of petrol-based polymers.

Chapter 2 contains the progress on the upcycling of PVC using high oleic soybean oil. Soybean oil can soften PVC making it less brittle than pure PVC. …

Gene Vectors With Fluorescence Tracking Capabilities, Sophia Despina Angelopoulos

Browse all Theses and Dissertations

This project focuses on the optimization of benzothiazole-based chromophores to utilize them as fluorescent tags functionalized onto stimuli-responsive, or “smart,” polymers as non-viral gene delivery vectors for gene therapy applications. Blue-fluorescent emissive chromophores will allow tracking capabilities for the transfection pathway of the vector to be monitored as it delivers the DNA payload within intercellular space. The most appropriate chromophore must be covalently bound to a free amine within the vector, which is accomplished through NAS chemistry from fluorophenyl-benzothiazoles (F-BTZ-CBz) derivatives to amidated hyperbranched poly(ethyleneimine)(HPEI-IBAm0.61). HPEI is considered to be a synthetic polycation, which promotes tunable solubility through characteristics of …

Covalent Attachment Of Tadf Chromophores To Thermally Stable Poly(Arylene Ether)S, Samuel Farrar

Browse all Theses and Dissertations

The covalent attachment of a blue emitting, benzothiazole based TADF chromophore into poly(arylene ether) backbone polymers was explored. A benzothiazole derivative, 2-(2,4-difluorophenyl)-benzothiazole (2,4-diF-BTZ), was synthesized to form the electrophilic component of the host polymer. Two polymers were synthesized to have chromophore incorporated, using 2,4-diFBTZ and 4,4-dihydroxydiphenyl ether (DPE) or 4,4’-biphenol (BP). The chromophore was covalently incorporated at a 10% molar ratio into the polymer backbone by copolymerization with 2,4-diF-BTZ and BP, utilizing nucleophilic aromatic substitution (NAS). Structural characterization was provided via NMR spectroscopy and GC/MS analysis. The polymer syntheses provided high molecular weight materials that were able to be cast …

Teaching An Old Dog New Tricks: Synthesis And Applications Of Novel Polybenzimidazole (Pbi) Membranes, Laura Ann Murdock

Theses and Dissertations

Polybenzimidazoles (PBIs) represent a class of performance polymers that display exceptional thermal and oxidative stability. For almost thirty years, PBI membranes have been investigated as promising candidates for next-generation alternative energy devices, including high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) and vanadium redox flow batteries (VRBs). Issues with the production of PBI membranes arise from their inherent low solubility in organic solvents. Thus, conventional approaches typically yield membranes that have limited molecular weight and generate significant waste in preparation, due to the large quantity of solvent required to dissolve PBIs for membrane casting.

Presented herein is the development of …

Design Of Resposive Oligomeric And Polymeric Interfaces For Sensing And Controlled Release Applications, . Manisha

Doctoral Dissertations

Nature has designed magnificent responsive systems by constructing several interacting molecular level networks for the recognition and propagation of chemical and biochemical information. One of the eminent characteristics of these systems is their capability to quickly transduce molecular scale recognition events into macroscopic or visually observable responses. Inspired by these systems present in nature, we became interested in developing artificial responsive systems with similar capabilities. This dissertation will feature four such systems that employ amphiphilic oligomers and polymers which were chosen as the scaffolds because of their high thermodynamic stability, low critical aggregation concentrations, convenient handles to incorporate functional group …

Design Of Antioxidant Monomer, Augustine Osilamah Yusuf

Masters Theses & Specialist Projects

Reactive oxygen species such as hydrogen peroxide are present at the sites of inflammation in the body. Degradable polymeric nanoparticles have shown great promise in a range of biomedical applications which include preferential delivery of therapeutics to such inflamed sites. We are working towards a new class of materials expected to have tunable degradation rates in the presence of hydrogen peroxide. These new materials consist of three parts: degradable linkages, antioxidant groups, and unreactive filler monomers such as methylmethacrylate. We have synthesized a polymerization initiator with a degradable linkage, and we have shown that using this initiator to synthesize another …

Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng

Doctoral Dissertations

Electrospun fibers are high-surface-area materials widely used in applications ranging from batteries to wound dressings. Typically, an electrospinning precursor solution is prepared by dissolving a high-molecular-weight polymer in an organic solvent to form a sufficiently entangled solution. Our approach bypasses the requirement for entanglements and completely avoids toxic chemicals by focusing on using an aqueous complex coacervates solution. Coacervates are a dense, polymer-rich liquid phase resulting from the associative electrostatic complexation of oppositely charged macroions. We were the first to demonstrate that liquid complex coacervates could be successfully electrospun into polyelectrolyte complex (PEC) fibers. A canonical coacervate system was formed …

Characterization, Immobilization, And Polymer Related Applications Of Watermelon Seed Powder, A Practical Source Of Urease Enzyme, Anthony Quan Quoc Mai

LSU Doctoral Dissertations

Urease enzyme was crystallized almost a century ago, and to this day its intrinsic stability is not ideal for everyday applications. This work introduces a new process by which a naturally encapsulated material, watermelon seed powder (WMSP), is characterized for its stability and activity. WMSP enzymatic activity has been measured for over a year at various storage conditions—exposed to ambient atmosphere for a year, WMSP retained above 90% activity. In aqueous conditions, the enzyme maintained above 60% activity after two months; with the addition of a preservative that number stays at about 90%. There is a pH shift of the …

Degradation Of Natural And Synthetic Fibers In Various Aqueous Environments, Jaylin Bryant

Honors Scholars Collaborative Projects

Fabrics are one variant of polymers, macromolecules that form the foundation of our society. They consist of small subunits called monomers, which are covalently bonded together and layered over each other through intermolecular attractions. There are natural fabrics, such as cotton and silk, and synthetic fabrics like polyester and rayon. Scientists in forensic taphonomy study postmortem changes made to human remains, which can also include clothes found at the scene. In this study, the degradation rates of four white fabrics (cotton, polyester, rayon, and silk) were observed in various aqueous environments (pure, chlorinated, sea, and lake) in order to observe …

Establishing Independent Tunability Of The Mechanical And Transport Properties Of Polymer Gels, Lucas Rankin

Master’s Theses

Polymer gels can be used in the fabrication of materials for filtering liquid and gaseous media, solid-state electrolytes, and transdermal medical patches. This diverse range of applications primarily relies on the transport and mechanical properties of polymer gels. Both sets of properties have shown excellent tunability, but typically in a coupled fashion. Establishing the independent tunability of the transport and mechanical properties of polymer gels (using simple, cost-effective methods) is paramount if polymer gels are to be used to their full potential. Specifically, block copolymer gels self-assemble into organized nanoscale networks within the gel solvent, which allows for facile control …

Fabrication, Characterization And Environmental Monitoring Of Polymer-Based Materials For Biomedical And Structural Applications, Mousumi Bose

Doctoral Dissertations

"Polymers are versatile materials utilized for variety of applications. In biomedical field, luminescence quenching based optical oxygen sensors encapsulated in polymeric substances are gaining attention for early detection of surface wounds associated with tissue oxygen. A simple and low-cost fabrication technique was developed to produce sensor arrays for continuous two-dimensional oxygen tension measurement. Sensor patch along with smart phone-based readout technique is being evaluated as a smart bandage.

The environmental concerns and limited petroleum supply demand for replacing petroleum-based polymers with renewable bio-based sources while maintaining comparable properties. A sustainable and green approach was adopted to synthesize soy polyol-derived rigid …

Advances In Polymer Based Friedlander Quinoline Synthesis, Rajendra Patil, Jagdish Chavan, Shivnath Patel, Anil Beldar

Turkish Journal of Chemistry

Nitrogen containing heterocyclic compounds has acquired their remarkable and distinct place in the wide area of organic synthesis due to the broad range of applications. Among them, quinoline motifs have attracted researchers in the synthetic chemistry because of its presence in the large number of pharmacologically active compounds. Different methods for synthesis of quinoline derivatives are reported, among them the Friedlander synthesis have provided comparatively more efficient approach. Many of the reported conventional Friedlander methodologies have some problems such as difficult product isolation procedures, poor yields and use of expensive catalysts, etc. Recently, polymer or solid supported synthetic approaches have …

Photothermal And Photochemical Strategies For Lightinduced Shape-Morphing Of Soft Materials, Alexa Simone Kuenstler

Doctoral Dissertations

Engineering materials with the capability to transform energy from photons into mechanical work is an outstanding technical challenge with implications across myriad disciplines. Despite decades of work in this area, comprehensive understanding of how to prescribe shape change and work output in photoactive systems remains limited. To this end, this dissertation explores strategies to assemble photothermal and photochemical moieties in soft material systems to fabricate photoaddressable devices capable of specific shape changes upon illumination. Chapters 2 and 3 describe a methodology for spatially patterning plasmonic nanoparticles in liquid crystal elastomer fibers and sheets to specify local photothermally-induced strain profiles. Using …

Functionalized Materials From Atom Transfer Radical Processes, Sean Fischer

Electronic Theses and Dissertations

This work is focused on the synthesis, characterization, and application of functionalized materials prepared from atom transfer radical processes. Atom transfer radical processes encompass both atom transfer radical addition (ATRA) and polymerization (ATRP) reactions, both of which are catalyzed by ppm amounts of copper complexes. The synthetic efforts of ATRA include increasing adduct selectivity through optimization of reaction conditions to generate small molecules in high to moderate yields. ATRA provides retention of the halogen moiety, which is an attractive functional group that can be further modified with other transformations. Specifically, the copper-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) allows for the realization …

Control Of Corrosion On Ss316l Using Surface Initiated Polymers, Alexander Rupprecht

Electronic Theses and Dissertations

Pitting corrosion is arguably one of the most destructive and dangerous forms of corrosion, resulting in damage to structures, the environment, and public health. In addition, damage caused to structures such as bridges, pipelines, and boats, corrosion also has a profound effect on the biomedical community. Implanted metallic devices (i.e., vascular stents and artificial joints) are prone to pitting corrosion caused by aggressive ions present in extracellular fluid. To provide a corrosion-resistant surface on SS316L, films of poly(styrene), poly(methyl acrylate), and poly(methyl methacrylate) were formed using surface-initiated atom transfer radical polymerization (SI-ATRP). The resulting hydrophobic polymer films had a fractional …

Transesterification Of Poly(Ethyl Glyoxylate): A Route To Structurally Diverse Polyglyoxylates, Rebecca E. Yardley, Amir Rabiee Kenaree, Xiaoli Liang, Elizabeth R. Gillies

Chemistry Publications

Polyglyoxylates are a class of self-immolative polymers that depolymerize in solution and the solid state. The glyoxylic acid degradation product is a metabolite in the glyoxylate cycle and can also be processed in the liver in humans, making polyglyoxylates attractive for applications in the environment and in medicine. Although expanding the scope of available polyglyoxylates would enable new properties and applications, highly pure glyoxylate monomers are required for polymerization, and this level of purity is difficult to achieve for many potential monomers. To address this challenge, we report here the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed post-polymerization transesterification of poly(ethyl glyoxylate) (PEtG) as a …

Thermoresponsive Self-Immolative Polyglyoxylamides., Amir Rabiee Kenaree, Quinton E. A. Sirianni, Kyle Classen, Elizabeth R. Gillies

Chemistry Publications

Thermoresponsive polymers with lower critical solution temperatures (LCSTs) are of significant interest for a wide range of applications from sensors to drug delivery vehicles. However, the most widely investigated LCST polymers have nondegradable backbones, limiting their applications

Phosphonium Versus Ammonium Compact Polyelectrolyte Complex Networks With Alginate-Comparing Their Properties And Cargo Encapsulation., Tristan D. Harrison, Alexandre J. Salmon, John R. De Bruyn, Paul J. Ragogna, Elizabeth R. Gillies

Chemistry Publications

Phosphonium and ammonium polymers can be combined with polyanions to form polyelectrolyte complex (PEC) networks, with potential application in self-healing materials and drug delivery vehicles. While various structures and compositions have been explored, to the best of our knowledge, analogous ammonium and phosphonium networks have not been directly compared to evaluate the effects of phosphorus versus nitrogen cations on the network properties. In this study, we prepared PECs from sodium alginate and poly[triethyl(4-vinylbenzyl)phosphonium chloride], poly[triethyl(4-vinylbenzyl)ammonium chloride], poly[tri(

Uniform Dispersion Of Nanoparticles In Pmma Waveguides For Luminescent Solar Concentrators, Daniel Korus

Scholars Week

With the rise of emissions-related climate change, novel renewable energy sources must be realized. At the same time, evolution of the electric distribution grid away from traditionally large, centralized producers toward smaller, decentralized sources drives the need for next generation technologies that can be more readily integrated into the built environment. Nanocrystal (NC)-doped luminescent solar concentrators (LSCs) are waveguides that absorb diffuse and direct broadband sunlight across their surface and direct narrow-bandwidth, high-brightness light to their edges, for conversion into electricity by coupled, bandgap-matched, photovoltaic (PV) cells. LSCs are insensitive to incident light orientation, partial shading, and can be integrated …

Discriminating Azo Dyes: Conjugated Polymers, The Inner Filter Effect, And Array Sensors, Erin Crater

Honors Theses

Azo dyes are abundant pollutants that contaminate water supplies and threaten humans, biota, and ecosystem health. Their detection and discrimination are an incredible challenge due to the structural, chemical, and optical similarities between dyes, the complexity of the wastewater environment in which they are found, and their low environmental concentrations. In this work, the inner filter effect (IFE), combined with conjugated polymer array-based sensing, is utilized for the quantitative profiling of these pollutants. The array was constructed using three fluorescent, anionic conjugated polyelectrolytes whose varying spectroscopic properties led to distinct IFE patterns in the presence of the dyes. The unique …

Polymers For Extrusion‐Based 3d Printing Of Pharmaceuticals: A Holistic Materials–Process Perspective, Mohammad A. Azad, Deborah Olawuni, Georgia Kimbell, Abu Zayed Badruddoza, Md. Shahadat Hossain, Tasnim Sultana

Publications and Research

Three dimensional (3D) printing as an advanced manufacturing technology is progressing to be established in the pharmaceutical industry to overcome the traditional manufacturing regime of ʹone size fits for allʹ. Using 3D printing, it is possible to design and develop complex dosage forms that can be suitable for tuning drug release. Polymers are the key materials that are necessary for 3D printing. Among all 3D printing processes, extrusion‐based (both fused deposition modeling (FDM) and pressure‐assisted microsyringe (PAM)) 3D printing is well researched for pharmaceutical manufacturing. It is important to understand which polymers are suitable for extrusion‐based 3D printing of pharmaceuticals …

Polyacrylamide In Glycerol Solutions From An Atomistic Perspective Of The Energetics, Structure, And Dynamics, Scott D. Hopkins, Gideon K. Gogovi, Eric Weisel, Robert A. Handler, Estela Blaisten-Barojas

VMASC Publications

All-atom molecular dynamics is used to investigate the structural, energetic, and dynamical properties of polyacrylamide (PAM) oligomers of different lengths solvated in pure glycerol, a 90:10 glycerol–water mixture, and pure water. We predict that the oligomers’ globular structure is obtained only when the modeling strategy considers the solvent as a continuous background. Meanwhile, for all-atom modeled solvents, the glycerol solutions display a strong tendency of trapping the oligomers in instantaneous elongated random coiled structures that remain locked-in over tens of nanoseconds. In pure water, the oligomers acquire considerably shorter random coiled structures of increased flexibility. The all-atom force field, generalized …