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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 …

Bottom-Up Morphological Control Of Biphasic Polymer Particles Via Heterogeneous Polymerization, Heather S.C. Hamilton

Doctoral Dissertations

Heterogeneous polymerization techniques are industrially relevant, scalable methods to synthesize polymer colloids and they have emerged in recent decades as viable methods to produce biphasic and morphologically complex polymer particles. The overarching goal of this thesis is to understand how heterogeneous polymerization techniques can be modified and optimized to control particle morphology through the systematic study of process parameters. Chapter 1 introduces relevant nomenclature and provides a brief historical perspective on the development of heterogeneous polymerization. This chapter also reviews the state-of-the-art techniques used to prepare morphologically complex polymer particles, with an emphasis on the heterogeneous polymerization processes studied in …

Biomedical Applications Of Protein Films And Polymeric Nanomaterials, Sanjana Gopalakrishnan

Doctoral Dissertations

Biomaterials are widely applied for the diagnosis and treatment of numerous diseases. In addition to fulfilling specific biological functions, biomaterials must also be non-toxic, biocompatible, and sterilizable to be regarded as safe-for-use. Polymers are excellent candidates for fabricating functional biomaterials due to their wide availability and varied properties and may be natural or synthetic. Polymer precursors are fabricated into coatings, foams, scaffolds, gels, composites, and nanomaterials for several biomedical applications. This dissertation focuses on two types of polymeric biomaterials – protein-based materials and synthetic polymeric nanoparticles. Proteins are biopolymers that naturally occur with a variety of structural and functional properties. …

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 …

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 …

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 …

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 …

Modification Of 2d Materials Utilizing Functional Polymer Interfacial Layers, Ryan Selhorst

Doctoral Dissertations

This dissertation describes the modification of 2D transition metal dichalcogenides (TMDCs). These materials exhibit unique electronic properties, ranging from metallic to insulating, and can transport either electrons (n-type) or holes (p-type). Polymers containing electronically-active moieties offer a path to control the electronic properties of a 2D material without altering the inherent structure of the semiconductor. This dissertation focuses on the synthesis of polymers bearing chalcogen-rich or zwitterionic moieties to alter the electronic and solution properties of 2D materials. Chapter 2 describes polymers containing sulfur-rich tetrathiafulvalene (TTF) and their effects as electroactive coatings on the TMDC molybdenum disulfide (MoS₂). …

Conducting Polyelectrolyte Complexes: Assembly, Structure, And Transport, Michael A. Leaf

Doctoral Dissertations

Decades of progress have yielded a tremendous variety of organic electronics, with great strides in the development of photovoltaics, thermoelectrics and other flexible devices. Ubiquitous in these research areas are films of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT: PSS), a complex of oppositely-charged polyelectrolytes initially suspended in water before film formation. This material has high electronic conductivity and good water processability. Pristine film conductivity is somewhat low, but is dramatically enhanced through simple treatments like ionic liquid addition or shear. Can this enhancement be understood so that further optimization might render PEDOT: PSS commercially viable? PEDOT: PSS is a complicated material, with …

Sequence And Entropy-Based Control Of Complex Coacervates, Li-Wei Chang, Tyler K. Lytle, Mithun Radhakrishna, Joel J. Madinya, Jon Vélez, Charles E. Sing, Sarah L. Perry

Chemical Engineering Faculty Publication Series

Biomacromolecules rely on the precise placement of monomers to encode information for structure, function, and physiology. Efforts to emulate this complexity via the synthetic control of chemical sequence in polymers are finding success; however, there is little understanding of how to translate monomer sequence to physical material properties. Here we establish design rules for implementing this sequence-control in materials known as complex coacervates. These materials are formed by the associative phase separation of oppositely charged polyelectrolytes into polyelectrolyte dense (coacervate) and polyelectrolyte dilute (supernatant) phases. We demonstrate that patterns of charges can profoundly affect the charge–charge associations that drive this …

Kinetics And Dynamics Of Electrophoretic Translocation Of Polyelectrolytes Through Nanopores, Harshwardhan Katkar

Doctoral Dissertations

The idea of sequencing a DNA based on single-file translocation of the DNA through nanopores under the action of an electric field has received much attention over the past two decades due to the societal need for low cost and high-throughput sequencing. However, due to the high speed of translocation, interrogating individual bases with an acceptable signal to noise ratio as they traverse the pore has been a major problem. Experimental facts on this phenomenon are rich and the associated phenomenology is yet to be fully understood. This thesis focuses on understanding the underlying principles of polymer translocation, with an …

Engineering Polymers Through Impact Modification And Superheated Liquid Processing, Gregory Connor Evans

Doctoral Dissertations

A new approach to toughen anionically polymerized polyamide 6 (aPA6) was applied using reaction induced phase separation (RIPS). This method solved issues with particle dispersion, mixture viscosity, and additive concentration common with conventional rubber toughening thereby making it an ideal candidate for fiber reinforced aPA6 reaction injection molding (RIM). Octamethylcyclotetrasiloxane (D₄) was used as a functional additive that undergoes RIPS during aPA6 polymerization and polymerizes to polydimethylsiloxane (PDMS). Controlled phase separation, modulus retention, and increased crystallinity were achieved at low additive concentrations. Optimal properties were achieved with 2 wt% D₄. Fracture energy was measured at high …

Protein Charge Anisotropy Mediated Self-Association And Phase Separation, Daniel P. Seeman

Doctoral Dissertations

Protein charge anisotropy results from the asymmetric distribution of charged residues on the exterior of a particular protein. Interactions between proteins and other macromolecules can be described in terms of attractive electrostatics; since electrostatic free energies, at optimal I, are on the order of kT, it is unlikely that such associations would result in desolvation, thus it is reasonable to consider such intermolecular attractions as being mediated by hydrated protein surfaces. Such interactions can be broken down in terms of a single protein interacting with a range of “binding partners”, including (1) protein-protein interactions, (2) protein-polymer interactions, and …

Aspects Of Physical Aging And Solid State Processing Of Polymeric Glasses, Angel Cugini

Doctoral Dissertations

This thesis focuses on unconventional methods to improve the mechanical properties of glassy polymers such as PMMA, Tritan™ Copolyester, and epoxy-based thermosets by influencing the intrinsic mechanical behavior through solid-state processing. The solid-state processing includes pre-stress, mechanical rejuvenation, and mechanical work hardening that cause changes in microscopic conformation structure and dynamics of glassy polymers and enhance properties such as non-linear deformation behavior and low and high velocity fracture. To utilize such unconventional techniques, one needs to understand fundamental origins of dynamics in polymeric glasses where the chain segments are not completely frozen and the segmental diffusion displays high degree of …

Ultra-Thin Polymer Films And Hierarchical Composites: Processing And Mechanical Properties, Yujie Liu

Doctoral Dissertations

Properties and fabrications of ultra-thin polymer films and hierarchical composites are of great interest in packaging, electronics, separations, and other manufacturing fields. However, due to the inherently fragile nature of ultra-thin polymer films, measuring their properties has proven difficult. Additionally, variables controlling thin polymer patterns (e.g. substrate wetting property) and composites (weight percent of particulates in matrix) formation have not been fundamentally well understood. Within this spectrum, fundamental understanding of formation mechanisms of these patterns and composites are needed. Additionally, a new characterization technique is required to be able to measure the mechanical properties of fabricated composites and thin films. …

Design, Synthesis, And Bio Relevant Applications Of Zwitterionic Amphiphilic Macromolecular Assemblies, Rajasekhar Reddy Rami Reddy

Doctoral Dissertations

Supramolecular nanoassemblies capable of reducing non-specific interactions with biological macromolecules, such as proteins, are of great importance for various biological applications especially for targeted drug delivery therapeutics. Recently, zwitterionic materials have been shown to reduce non-specific interactions with biomolecules, owing both to their charge neutrality and their ability to form strong hydration layer around zwitterions via electrostatic interactions. This dissertation focuses on design, synthesis, thorough characterization, and applications of zwitterionic amphiphilic dendrimers and polymeric materials. Firstly, A new triazole-based zwitterionic moiety was conceived and incorporated as the hydrophilic functionality in facially amphiphilic dendrons. Self-assembly characteristics and the structural and functional …

Tailoring Nanoparticles And Polymers For Cooperative Interfacial And Surface Interactions, Irem Bolukbasi

Doctoral Dissertations

This thesis describes the synthesis of chemically functionalized nanoparticles and their behavior at interfaces and in conjunction with polymers. Solid-liquid, liquid-liquid, and air-liquid interfaces are useful platforms for studying nanoparticle assembly, especially when nanoparticles are functionalized to enable their segregation to the interface. At the liquid-liquid interface, double emulsions droplets, both oil-in-water-in-oil and water-in-oil-in-water, stabilized with nanoparticles were prepared. This involved gold nanoparticles stabilizing oil-in-water droplets, and CdSe quantum dots stabilizing water-in-oil droplets. These double emulsion droplets were by simply shaking to give polydisperse droplets, or in a well-defined fashion by microcapillary flow focusing. When nanoparticle-stabilized double emulsions were sized …

Visualizing And Controlling Charge Transport In Conjugated Polymer Networks And Films, Andrew Davis

Doctoral Dissertations

VISUALIZAING AND CONTROLLING CHARGE TRANSPORT IN CONJUGATED POLYMER NETWORKS AND FILMS MAY 2014 ANDREW R. DAVIS, B.S., UNIVERSITY OF VIRGINIA M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Kenneth R. Carter The desire for more commercially feasible flexible electronic plastics has led to the development of increasingly complex conjugated polymer architectures and device geometries. Through these efforts, tremendous advances have been made in the design and performance of electronic devices fabricated with solution-processable semiconducting polymers. However, none of these materials have yet reached commercial maturity, so the opportunity for their further exploration from both a …

On The Effect Of Elasticity On Drag Reduction Due To Polymer Additives Using A Hybrid D.N.S. And Langevin Dynamics Approach, Arnout Boelens

Open Access Dissertations

In this work the effect of elasticity on turbulent drag reduction due to polymers is investigated using a hybrid Direct Numerical Simulation (D.N.S) and Langevin dynamics approach. Simulations are run at a friction Reynolds number of Re_&tau = 560 for 960.000 dumbbells with Deborah numbers of De = 0, De = 1, and De = 10. The conclusions are that it is possible to simulate a drag reduced flow using hybrid D.N.S. with Langevin dynamics, that polymers, like other occurrences of drag reduction, reduce drag through streak stabilization, and that the essential property of polymers and fibers in having a …

Wrinkling Of Floating Thin Polymer Films, Jiangshui Huang

Doctoral Dissertations 1896 - February 2014

This thesis presents an extensive study of wrinkling of thin polystyrene films, tens of nanometers in thickness, floating on the surface of water or water modified with surfactant.

First, we study the wrinkling of floating thin polystyrene films under a capillary force exerted by a drop of water placed on its surface. The wrinkling pattern is characterized by the number and length of wrinkles. A metrology for measuring the elasticity and thickness of ultrathin films is constructed by combining the scaling relations that are developed for the length of the wrinkles with those for the number of wrinkles. This metrology …

Developing Reactive Molecular Dynamics For Understanding Polymer Chemical Kinetics, Kenneth D. Smith

Open Access Dissertations

One of the challenges in understanding polymer flammability is the lack of information about microscopic events that lead to macroscopically observed species, and Reactive Molecular Dynamics is a promising approach to obtain this crucially needed information. The development of a predictive method for condensed-phase reaction kinetics can provide significant insight into polymer ammability, thus helping guide future synthesis of fire-resistant polymers. Through this dissertation, a new reactive forcefield, RMDff, and Reactive Molecular Dynamics program, RxnMD, have been developed and used to simulate such material chemistry. It is necessary to have accurate description of chemical kinetics to describe quantitative chemical kinetics. …

Synthesis And Interfacial Behavior Of Functional Amphiphilic Graft Copolymers Prepared By Ring-Opening Metathesis Polymerization, Kurt E. Breitenkamp

Open Access Dissertations

This thesis describes the synthesis and application of a new series of amphiphilic graft copolymers with a hydrophobic polyolefin backbone and pendent hydrophilic poly(ethylene glycol) (PEG) grafts. These copolymers are synthesized by ruthenium benzylidene-catalyzed ring-opening metathesis polymerization (ROMP) of PEG-functionalized cyclic olefin macromonomers to afford polycyclooctene- graft -PEG (PCOE- g -PEG) copolymers with a number of tunable features, such as PEG graft density and length, crystallinity, and amphiphilicity. Macromonomers of this type were prepared first by coupling chemistry using commercially available PEG monomethyl ether derivatives and a carboxylic acid-functionalized cycloctene. In a second approach, macromonomers possessing a variety of PEG …

Molecular Designs Toward Improving Organic Photovoltaics, Arpornrat Nantalaksakul

Doctoral Dissertations 1896 - February 2014

Organic photovoltaics (OPVs) that have been studied to date have poor power conversion efficiencies. This dissertation focuses on various molecular designs that could lead to both a fundamental understanding of photoinduced charge separation at a molecular level and also provide a solution to improve bulk properties of organic materials to overcome the poor efficiencies of OPV devices.

The effect of molecular architectures on the efficiency of electron transfer, a primary step in OPVs functioning, is evaluated in this work. We have shown that even though dendrimer provides an interesting architecture for efficient electron transfer due to the presence of multiple …

Complexation Of Polyelectrolytes., Joanna G. Pool

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Manipulating Polymers And Composites From The Nanoscopic To Microscopic Length Scales., Suresh Gupta

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Adhesion Of Patterned Polymer Interfaces., Edwin Pak-Nin Chan

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Hierarchical Nanostructures And Self-Assembly Of Polymers Containing Metal Complex In The Side Chain., Khaled A. Aamer

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Morphological Control In Nanostructured Polymers., Shujun Chen

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Solid And Melt State Processing Of Polymers And Their Composites In Supercritical Carbon Dioxide., Manuel A. Garcia-Leiner

Doctoral Dissertations 1896 - February 2014

No abstract provided.

Chemical Modification Of Solid Surfaces & Interfaces And Template-Assisted Fabrication Of Surface Nanostructures., Xinqiao Jia

Doctoral Dissertations 1896 - February 2014

No abstract provided.