Polymer Science Commons^™

Development Of Soluble Bioactive Poly(Beta Amino Esters) (Pβaes) For Post-Synthesis Processing, Kelley Wiegman

Theses and Dissertations--Chemical and Materials Engineering

Polymers have proven to be a viable platform to facilitate the controlled and targeted release for a variety of therapeutic agents. Polymeric prodrugs are a growing area of drug delivery in which active pharmaceutical ingredients are covalently linked to a polymeric form in an effort to enhance stability, delivery, and pharmacology. One naturally occurring class of active ingredients, known as polyphenols, can potentially offer a vast array of beneficial therapeutic properties. However, the therapeutic efficacy of these compounds is severely limited due to poor solubility and bioavailability as well as an oxidative and thermal instability. To improve the efficacy of …

Extraction Of Micro- And Nano-Plastic Particles From Water Using Hydrophobic Natural Deep Eutectic Solvents, Jameson R. Hunter

Theses and Dissertations--Biosystems and Agricultural Engineering

The production of plastic and the amount of waste plastic that enters the environment increases every year. Synthetic polymers will gradually break down into particles on the micro- and nano-scale. The micro- and nano-plastics pose a significant ecological harm by transporting toxic chemicals and causing inflammation and cellular damage when ingested. Two common plastics are polyethylene terephthalate (PET) and Polystyrene (PS), and a newer bioplastic polylactic acid (PLA) that has become a popular alternative. Deep eutectic solvents are a recently discovered solvent composed of a hydrogen bond donor and hydrogen bond acceptor and have been proposed as a cheaper alternative …

Development Of Novel Polymeric Materials For Their Application In Monitoring And Remediation Of Environmental Pollutants, Rishabh Shah

Theses and Dissertations--Chemical and Materials Engineering

Remediation of environmental pollutants from water is one of the major challenges in the 21st century. Utilizing novel polymeric materials to accomplish this challenge has garnered a lot of interest in recent times. Flexibility in synthesizing as well as functionalizing makes them attractive for their application in pollutant remediation. This work is based on development and characterization of novel crosslinked polymeric as well as linear polymeric materials from biphenyl-based monomers, biphenyl based crosslinker and a temperature responsive monomer (Nisopropylacrylamide (NIPAAm)) for their application in remediation of toxic pollutants such as polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and iron oxide nanoparticle …

Tailoring Thermoresponsive Poly(N-Isopropylacrylamide) Toward Sensing Perfluoroalkyl Acids, Dustin Thomas Savage

Theses and Dissertations--Chemical and Materials Engineering

Widespread distribution of poly- and perfluoroalkyl substances (PFAS) in the environment combined with concerns for their potentially negative health effects has motivated regulators to establish strict standards for their surveillance. The United States Environmental Protection Agency issued a cumulative domestic threshold of 70 ppt for water supplies, and this bar is even lower in some local districts and other countries. Monitoring PFAS consequently requires sensitive analytical equipment to meet regulatory specifications, and liquid chromatography with tandem mass spectroscopy (LC/MS/MS) is the most common technique used to satisfy these requirements. Though extremely sensitive, the instrument is often burdened by pretreatment regimens, …

Polymeric Nanocomposite Membranes With Phosphorene Based Pore Fillers For Fouling Control, Joyner Eke

Theses and Dissertations--Chemical and Materials Engineering

Phosphorene is a two-dimensional material exfoliated from bulk phosphorus. Specifically, relevant to the field of membrane science, the band gap of phosphorene provides it with potential photocatalytic properties, which could be explored in making reactive membranes able to control the accumulation of compounds on the surface during filtration, or fouling. Another reason phosphorene is a promising candidate as a membrane material additive is due to its catalytic properties which can potentially destroy foulants on the membrane surface.

The first goal of this study was to develop an innovative and robust membrane able to control and reverse fouling with minimal changes …

Bimetallic Nanoparticles Integrated Membranes For Groundwater Remediation: Synthesis, Characterization And Applications, Hongyi Wan

Theses and Dissertations--Chemical and Materials Engineering

The detoxification of chlorinated organics from groundwater, such as trichloroethylene (TCE), tetrachloroethylene (PCE), polychlorinated biphenyl (PCB) and carbon tetrachloride (CTC), is a challenging area. Reductive dechlorination has been investigated using iron and iron-based nanoparticles, such as bare Fe, sulfidized Fe (S-Fe) and palladized Fe (Pd-Fe). However, issues including particle agglomeration, difficulties in recycling and particle leaching have been reported to hinder the application and wide usage of these techniques. The integration of nanoparticles and membranes can address these issues because of the large surface area, stability, and the potential for versatile functionalities. In this study, commercial polyvinylidene difluoride (PVDF) microfiltration …

Fabrication, Characterization And Applications Of Highly Conductive Wet-Spun Pedot:Pss Fibers, Ruben Sarabia Riquelme

Theses and Dissertations--Chemical and Materials Engineering

Smart electronic textiles cross conventional uses to include functionalities such as light emission, health monitoring, climate control, sensing, storage and conversion of energy, etc. New fibers and yarns that are electrically conductive and mechanically robust are needed as fundamental building blocks for these next generation textiles.

Conjugated polymers are promising candidates in the field of electronic textiles because they are made of earth-abundant, inexpensive elements, have good mechanical properties and flexibility, and can be processed using low-cost large-scale solution processing methods. Currently, the main method to fabricate electrically conductive fibers or yarns from conjugated polymers is the deposition of the …

A Thermodynamic And Feasibility Study Of Green Solvents For The Fabrication Of Water Treatment Membranes, Xiaobo Dong

Theses and Dissertations--Chemical and Materials Engineering

Nonsolvent induced phase separation (NIPS) has been widely used to fabricate polymeric membranes. In NIPS, a polymer is dissolved in a solvent to form a dope solution, which is then cast on a substrate and immersed in a nonsolvent bath, where phase inversion occurs. Petroleum-derived organic solvents, such as N-Methyl-2-Pyrrolidone (NMP) and Dimethylacetamide (DMAc), have been traditionally used to fabricate polymeric membranes via NIPS. However, these solvents may have negative impacts on environmental and human health; therefore, using greener and less toxic solvents, preferably derived from biomass, is of great interest to make membrane fabrication sustainable. In this dissertation, two …

Synthesis, Functionalization, And Application Of Nanofiltration And Composite Membranes For Selective Separations, Andrew Steven Colburn

Theses and Dissertations--Chemical and Materials Engineering

Future nanofiltration (NF) membranes used for selective separations of ions and small organic molecules must maintain performance in environments where high concentrations of total dissolved solvents or foulants are present. These challenges can be addressed through the development of composite membranes, as well as the engineering of enhanced surface properties and operating conditions for existing commercial membranes.

In this work, ion transport through commercial thin film composite (TFC) polyamide NF membranes were studied in both lab-prepared salt solutions and industrial wastewater. The dependence of several variables on ion rejection was investigated, including ion radius, ion charge, ionic strength, and temperature. …

Towards The Rational Design And Application Of Polymers For Gene Therapy: Internalization And Intracellular Fate, Landon Alexander Mott

Theses and Dissertations--Chemical and Materials Engineering

Gene therapy is an approach for the treatment of acquired cancers, infectious disease, degenerative disease, and inherited genetic indications. Developments in the fields of immunotherapies and CRISPR/Cas9 genome editing are revitalizing the efforts to move gene therapy to the forefront of modern medicine. However, slow progress and poor clinical outcomes have plagued the field due to regulatory and safety concerns associated with the flagship delivery vector, the recombinant virus. Immunogenicity and poor transduction in certain cell types severely limits the utility of viruses as a delivery agent of nucleic acids. As a result, significant efforts are being made to develop …

Functionalization Of Iron Oxide Nanoparticles And The Impact On Surface Reactive Oxygen Species Generation For Potential Biomedical And Environmental Applications, Trang Mai

Theses and Dissertations--Chemical and Materials Engineering

Iron oxide nanoparticles (IONPs) have been widely studied for a variety of applications, from biomedical applications (e.g., cell separation, drug delivery, contrast agent for magnetic resonance imaging and magnetically mediated energy delivery for cancer treatment) to environmental remediations (e.g., heavy metal removal and organic pollutants degradation). It has been demonstrated that IONPs can induce the production of reactive oxygen species (ROS) via Fenton/Haber-Weiss reactions which has been shown to be one of the key underlying mechanisms of nanoparticles toxicity. This inherent toxicity of nanoparticles has been shown to enhance the efficacy of traditional cancer therapies such as chemotherapy and radiation. …

Development Of Novel Temperature Responsive Polymeric Sorbents And Their Applications In Water Remediation, Shuo Tang

Theses and Dissertations--Chemical and Materials Engineering

Water remediation utilizing sorption has found strong interest due to its inexpensiveness, universal nature and ease of operation. In particular, thermo-responsive sorbents consisting of N-isopropylacrylamide (NIPAAm) offer significant potential as “smart” and advanced materials to remove multiple aqueous pollutants. NIPAAm exhibits excellent thermo-responsiveness, which senses the external temperature variation and changes its swelling and sorption behaviors in a sharp and rapid manner. At the beginning of this work, an extensive review of literature has been compiled to provide a summary of NIPAAm-based thermo-responsive sorbents in water/wastewater remediation applications.

Initially, we developed a novel approach to synthesize and characterize NIPAAm copolymeric …

Synthesis, Characterization And Applications Of Reduced Graphene Oxide And Composite Membranes For Selective Separations And Removal Of Organic Contaminants, Ashish Aher

Theses and Dissertations--Chemical and Materials Engineering

Among the next generation materials being investigated for membrane development, partially reduced Graphene Oxide (rGO) has received increasing attention from the membrane community. rGO-based nanofiltration membranes have shown promising results in applications such as partial desalination, organic contaminant removal, gas-phase separations, and separations from solvent media. rGO offers a unique platform compared to common polymeric membranes since it can be used for separation applications in both aqueous and organic solvent media. An rGO-based platform could also be utilized to synthesize reactive membranes, giving rGO membranes the additional capability of reactively removing organic contaminants. This research focuses on the synthesis of …

The Fabrication And Characterization Of Metal Oxide Nanoparticles Employed In Environmental Toxicity And Polymeric Nanocomposite Applications, Matthew Logan Hancock

Theses and Dissertations--Chemical and Materials Engineering

Ceria (cerium oxide) nanomaterials, or nanoceria, have commercial catalysis and energy storage applications. The cerium atoms on the surface of nanoceria can store or release oxygen, cycling between Ce³⁺ and Ce⁴⁺, and can therefore act as a therapeutic to relieve oxidative stress within living systems. Nanoceria dissolution is present in acidic environments in vivo. In order to accurately define the fate of nanoceria in vivo, nanoceria dissolution or stabilization is observed in vitro using acidic aqueous environments.

Nanoceria stabilization is a known problem even during its synthesis; in fact, a carboxylic acid, citric acid, is …

Multienzyme Immobilized Polymeric Membrane Reactor For The Transformation Of A Lignin Model Compound, Rupam Sarma, Md. Saiful Islam, Mark P. Running, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

We have developed an integrated, multienzyme functionalized membrane reactor for bioconversion of a lignin model compound involving enzymatic catalysis. The membrane bioreactors were fabricated through the layer-by-layer assembly approach to immobilize three different enzymes (glucose oxidase, peroxidase and laccase) into pH-responsive membranes. This novel membrane reactor couples the in situ generation of hydrogen peroxide (by glucose oxidase) to oxidative conversion of a lignin model compound, guaiacylglycerol-β-guaiacyl ether (GGE). Preliminary investigation of the efficacy of these functional membranes towards GGE degradation is demonstrated under convective flow mode. Over 90% of the initial feed could be degraded with the multienzyme immobilized membranes …

Comparison Of Eosin And Fluorescein Conjugates For The Photoinitiation Of Cell-Compatible Polymer Coatings, Jacob L. Lilly, Anuhya Gottipati, Calvin F. Cahall, Mohamed Agoub, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

Targeted photopolymerization is the basis for multiple diagnostic and cell encapsulation technologies. While eosin is used in conjunction with tertiary amines as a water-soluble photoinitiation system, eosin is not widely sold as a conjugate with antibodies and other targeting biomolecules. Here we evaluate the utility of fluorescein-labeled bioconjugates to photopolymerize targeted coatings on live cells. We show that although fluorescein conjugates absorb approximately 50% less light energy than eosin in matched photopolymerization experiments using a 530 nm LED lamp, appreciable polymer thicknesses can still be formed in cell compatible environments with fluorescein photosensitization. At low photoinitiator density, eosin allows more …

Surface Engineering And Monomer Design For Light-Mediated Ring Opening Metathesis Polymerization, Ishan A. Fursule

Theses and Dissertations--Chemical and Materials Engineering

Stimuli-responsive materials are changing the landscape of actuated materials, optoelectronics, molecular machines, solar cells, temporary memory storage, and biomedical materials. Specifically, photo-responsive polymers have gained acceleration in research and application since the last two decades in the form of a surface coating and micro-patterns. Light as a stimulus can be coherent, mono or polychromatic, tunable for power (intensity) and energy (wavelength), and has precise spatiotemporal control. Conventional surface coating techniques such as spin coating are unable to impart properties to the coatings in terms of sturdiness, homogeneity, uniformity over the complex surface, post deposition modification, and process efficiency. Also, in …

Surface Functionalization Via Photoinitiated Radical Polymerization For Rare Cell Isolation And Mechanical Protection, Calvin Frank Cahall

Theses and Dissertations--Chemical and Materials Engineering

Surface functionalization of living cells for cell therapeutics has gained substantial momentum in the last two decades. From encapsulating islets of Langerhans, to cell laden gels for tissue scaffolds, to individual cell encapsulation in thin hydrogels, to surface adhesives and inert surface camouflage, modification of living cell surfaces has a wide array of important applications. Here we use hydrogel encapsulation of individual cells as a mode of protection from mechanical forces for high throughput cell printing, and chemical stimuli for the isolation of rare cells in blood.

In the first study, we review methods of surface functionalization and establish a …

Design And Analysis Of Curcumin Conjugated Poly(Beta-Amino Ester) Networks For Controlled Release In Oxidative Stress Environments, Carolyn T. Jordan

Theses and Dissertations--Chemical and Materials Engineering

Oxidative stress, the imbalance of free radical generation with antioxidant defenses, leads to cellular inflammation, apoptosis and cell death. This compromised environment results in debilitating diseases, such as oral mucositis (OM), atherosclerosis, and ischemia/reperfusion injury. Antioxidant therapeutics has been a proposed strategy to ameliorate these imbalances and maintain homeostatic environments. However, the success of these approaches, specifically curcumin, has been limited due to characteristics such as hydrophobicity and high reactivity when released as bolus doses to contest to oxidative stress induced diseases. The development of a controlled release system to aid in protection of the antioxidant capacity of curcumin, as …

Synthesis And Characterization Of Poly(Simvastatin) - Incorporated Copolymers And Blends For Bone Regeneration, Theodora Asafo-Adjei

Theses and Dissertations--Biomedical Engineering

Common biodegradable polyesters such as poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) and poly(ε-caprolactone) (PCL) are used as drug delivery vehicles for tissue regenerative applications. However, they are typically bioinert, with drug loading limitations. Polymerizing the active agent or precursor into its respective biodegradable polymer would control drug loading via molar ratios of drug to initiator used for synthesis. Simvastatin was chosen due to its favorable anti-inflammatory, angiogenic, and osteogenic properties. In addition, its lactone ring lends itself to ring-opening polymerization and, consequently, the synthesis of poly(simvastatin) with controlled simvastatin release.

Simvastatin was first polymerized with a 5kDa methyl-terminated poly(ethylene glycol) …

Functionalization Of Silver Nanoparticles On Membranes And Its Influence On Biofouling, Conor G. Sprick

Theses and Dissertations--Chemical and Materials Engineering

Ultrafiltration (UF) processes are often used as pretreatment before more retentive/costly processes, such as nanofiltration and reverse osmosis. This study shows the results of low-biofouling nanocomposite membranes, loaded with casein-coated silver nanoparticles (casein-Ag-NPs). Membranes were cast and imbedded with Ag-NPs using two approaches, physical blending of Ag-NPs in the dope solution (^PAg-NP/CA membranes) and chemical attachment of Ag-NPs to cast membranes (^CAg-NP/CA membranes), to determine their biofouling control properties. The functionalization of Ag-NPs onto the CA membranes was achieved via attachment with functionalized thiol groups with the use of glycidyl methacrylate (GMA) and cysteamine chemistries. The …

Formulation And Characterization Of Poly(Β-Amino Ester) Networks For Controlled Delivery Of Antioxidants In Pharmaceutical Applications, Vinod Shivaji Patil

Theses and Dissertations--Chemical and Materials Engineering

Oxidative stress, which reflects an imbalance between oxidants and endogenous antioxidants, is known to be a cause as well as an effect of health conditions such as cancer, diabetes, Alzheimer’s disease, Parkinson’s disease and ischemia-reperfusion injury. Antioxidants have shown promising results in vitro in controlling oxidative stress. However, years of in vitro studies have failed to translate into effective clinical interventions for controlling oxidative stress in the disease conditions. This has been due to low bioavailability and lower stability of antioxidants. Poly(antioxidant β-amino esters) (PABAE) are a recently-developed class of biodegradable polymeric hydrogels that have shown promise in their ability …

Tunable Nanocomposite Membranes For Water Remediation And Separations, Sebastián Hernández Sierra

Theses and Dissertations--Chemical and Materials Engineering

Nano-structured material fabrication using functionalized membranes with polyelectrolytes is a promising research field for water pollution, catalytic and mining applications. These responsive polymers react to external stimuli like temperature, pH, radiation, ionic strength or chemical composition. Such nanomaterials provide novel hybrid properties and can also be self-supported in addition to the membranes.

Polyelectrolytes (as hydrogels) have pH responsiveness. The hydrogel moieties gain or lose protons based on the pH, displaying swelling properties. These responsive materials can be exploited to synthesize metal nanoparticles in situ using their functional groups, or to immobilize other polyelectrolytes and biomolecules. Due to their properties, these …

Development Of Pvdf Membrane Nanocomposites Via Various Functionalization Approaches For Environmental Applications, Douglas M. Davenport, Minghui Gui, Lindell E. Ormsbee, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Membranes are finding wide applications in various fields spanning biological, water, and energy areas. Synthesis of membranes to provide tunable flux, metal sorption, and catalysis has been done through pore functionalization of microfiltration (MF) type membranes with responsive behavior. This methodology provides an opportunity to improve synthetic membrane performance via polymer fabrication and surface modification. By optimizing the polymer coagulation conditions in phase inversion fabrication, spongy polyvinylidene fluoride (PVDF) membranes with high porosity and large internal pore volume were created in lab and full scale. This robust membrane shows a promising mechanical strength as well as high capacity for loading …

Surface-Initiated Polymerizations For The Rapid Sorting Of Rare Cancer Cells, Jacob L. Lilly

Theses and Dissertations--Chemical and Materials Engineering

Cancer metastasis directly accounts for an estimated 90% of all cancer related deaths and is correlated with the presence of malignant cells in systemic circulation. This observed relationship has prompted efforts to develop a fluid biopsy, with the goal of detecting these rare cells in patient peripheral blood as surrogate markers for metastatic disease as a partial replacement or supplement to tissue biopsies. Numerous platforms have been designed, yet these have generally failed to support a reliable fluid biopsy due to poor performance parameters such as low throughput, low purity of enriched antigen positive cells, and insufficiently low detection thresholds …

Synthesis And Characterization Of Curcumin Polymer For Application In Radiation Induced Lung Damage, Mark C. Bailey

Theses and Dissertations--Chemical and Materials Engineering

Radiotherapy is used as a primary treatment for many cancers, including lung cancer. Although radiotherapy has proven to be an effective cancer treatment, its use is heavily limited due to the peripheral toxicity to healthy tissue. In this work, the antioxidant, curcumin, was tested as a radioprotectant to reduce radiation damage to healthy cells. Curcumin has been limited in use due to its poor bioavailability. In order to avoid problems associated with free curcumin delivery, curcumin poly(beta-amino ester) (CPBAE) was synthesized.

The first study investigated the in vitro radioprotection effect of curcumin in HUVEC dosed with gamma radiation. Cells treated …

Bioactive Poly(Beta-Amino Ester) Biomaterials For Treatment Of Infection And Oxidative Stress, Andrew L. Lakes

Theses and Dissertations--Chemical and Materials Engineering

Polymers have deep roots as drug delivery tools, and are widely used in clinical to private settings. Currently, however, numerous traditional therapies exist which may be improved through use of polymeric biomaterials. Through our work with infectious and oxidative stress disease prevention and treatment, we aimed to develop application driven, enhanced therapies utilizing new classes of polymers synthesized in-house. Applying biodegradable poly(β-amino ester) (PBAE) polymers, covalent-addition of bioactive substrates to these PBAEs avoided certain pitfalls of free-loaded and non-degradable drug delivery systems. Further, through variation of polymer ingredients and conditions, we were able to tune degradation rates, release profiles, cellular …

Synthesis And Characterization Of Antioxidant Conjugated Poly(Βeta-Amino Ester) Micro/Nanogels For The Suppression Of Oxidative Stress, Prachi Gupta

Theses and Dissertations--Chemical and Materials Engineering

Oxidative stress is a pathophysiological condition defined by an increased production of reactive oxygen species (ROS), which can result in the growth arrest of cells followed by cell disintegration or necrosis. A number of small molecule antioxidants (e.g. curcumin, quercetin and resveratrol) are capable of directly scavenging ROS, thereby short-circuiting the self-propagating oxidative stress state. However, poor solubility and rapid 1^st pass metabolism results in overall low bioavailability and acts as a barrier for its use as a drug to suppress oxidative stress efficiently.

To overcome this limitation, these small molecule antioxidants were covalently conjugated into poly(β-amino ester) (PβAE) …

Inhalable Nanocomposites And Anticancer Agents For Cancer Therapy, Nathanael A. Stocke

Theses and Dissertations--Chemical and Materials Engineering

Cancer is designated as the leading cause of mortality worldwide and lung cancer is responsible for nearly 30% of all cancer related deaths. Over the last few decades mortality rates have only marginally increased and rates of recurrence remain high. These factors, among others, suggest the need for more innovative treatment modalities in lung cancer therapy. Targeted pulmonary delivery is well established for treating pulmonary diseases such as asthma and provides a promising platform for lung cancer therapy. Increasing local deposition of anticancer agents (ACAs) and reducing systemic exposure of these toxic moieties could lead to better therapeutic outcomes and …

Biomimetic Oral Mucin From Polymer Micelle Networks, Sundar Prasanth Authimoolam

Theses and Dissertations--Chemical and Materials Engineering

Mucin networks are formed by the complexation of bottlebrush-like mucin glycoprotein with other small molecule glycoproteins. These glycoproteins create nanoscale strands that then arrange into a nanoporous mesh. These networks play an important role in ensuring surface hydration, lubricity and barrier protection. In order to understand the functional behavior in mucin networks, it is important to decouple their chemical and physical effects responsible for generating the fundamental property-function relationship. To achieve this goal, we propose to develop a synthetic biomimetic mucin using a layer-by-layer (LBL) deposition approach. In this work, a hierarchical 3-dimensional structures resembling natural mucin networks was generated …