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Full-Text Articles in Chemistry

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian Oct 2022

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …


Intracellular Delivery Of Therapeutic Biomolecules Through Versatile Polymer Nanotechnology, David C. Luther Oct 2022

Intracellular Delivery Of Therapeutic Biomolecules Through Versatile Polymer Nanotechnology, David C. Luther

Doctoral Dissertations

Advancing pharmaceutical technology has made it possible to treat diseases once considered ‘undruggable.’ Access to these new pharmaceutical targets is possible thanks to the advent of protein and nucleic acid therapeutics. Responses to the COVID-19 pandemic, as well as cutting-edge treatments for cancer and multiple sclerosis have centered on these biologic therapies, promising even greater value in the future. However, their utility is limited at a cellular level by inability to cross the plasma membrane. Nanocarrier technologies encapsulate therapeutics and facilitate uptake into the cell but are often trapped and degraded in endosomes. Arginine-functionalized gold nanoparticles (Arg-NPs) provide efficient, direct …


Expanding The Polymer Zwitterion Library – Novel Phosphonium-Based Polymer Zwitterions And Analogous Structures, Marcel U. Brown Oct 2022

Expanding The Polymer Zwitterion Library – Novel Phosphonium-Based Polymer Zwitterions And Analogous Structures, Marcel U. Brown

Doctoral Dissertations

This dissertation encompasses the synthesis, characterization and application of novel polymer zwitterions that significantly expand the library of available zwitterionic polymers. Their facile synthesis is facilitated by the preparation of a novel functional sultone precursor molecule, which can be ring-opened by commercially available phosphine, amine and sulfide nucleophiles, affording phosphonium, ammonium or sulfonium sulfonate monomers, respectively. Most notably, this work describes the invention of phosphonium-based polymer zwitterions, establishing a new class of zwitterionic polymer structures with unique solution and interfacial properties. Furthermore, the incorporation of these phosphonium sulfonates into block copolymer architectures with conventional polymer zwitterions, and the resulting switchable …


Enabling Nanoimprint Lithography Techniques Across Multiple Manufacturing Processes, Vincent Einck Sep 2022

Enabling Nanoimprint Lithography Techniques Across Multiple Manufacturing Processes, Vincent Einck

Doctoral Dissertations

Advanced nanooptics in the areas of flat lenses, diffractive elements, and tunable emissivity require a route to high throughput manufacturing. Nanooptics are often demanding of high refractive index materials, nanometer precision and ease of fabrication. Nanoimprint lithography (NIL) is a low-cost, high throughput manufacturing technique beginning to be realized in commercial industry.1,2 The NIL process is an ideal manufacturing candidate due to its ability to have a fast process time, efficient use of materials, repeatability and high precision while also having wide diversity of potential structures and material choices. Appling NIL techniques to other facets of manufacturing enable the …


Designing Polymer-Protein Complexes For Intracellular Delivery, Hazel Davis Jun 2022

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 …


Developing Injectable And Implantable Polymer Zwitterion Platforms For Glioblastoma Treatment, Sarah Ward Mar 2022

Developing Injectable And Implantable Polymer Zwitterion Platforms For Glioblastoma Treatment, Sarah Ward

Doctoral Dissertations

This dissertation describes the synthesis, characterization, and application of novel polymer zwitterion-drug conjugates intended for treating glioblastoma, with a particular focus on phosphorylcholine (PC) and temozolomide (TMZ). Using versatile TMZ-containing monomers, injectable polymer prodrugs and implantable polymeric hydrogels were prepared over a broad range of drug incorporations with tunable properties, making them ideally suited for further in vivo and clinical evaluations. The work presented here greatly expands the knowledge base of TMZ formulations and gives rise to several routes which circumvent the challenges associated with its use. Chapter 2 describes the incorporation of a novel TMZ-methacrylate monomer into random and …


Synthesis, Fabrication, And Assembly Of Mesoscale Polymer Filaments, Dylan M. Barber Mar 2022

Synthesis, Fabrication, And Assembly Of Mesoscale Polymer Filaments, Dylan M. Barber

Doctoral Dissertations

Mesoscale materials, with feature sizes in the range of one hundred nanometers to tens of micrometers, are ubiquitous in Nature. In organisms, mesoscale building blocks connect the properties of underlying molecular and nanoscructures to those of macroscale, organism-scale materials through hierarchical assemblies of recurring structural motifs. The collective action of large numbers of mesoscale features can afford stunning features like the structural color of the morpho butterfly wing, calcium ion-mediated movement in muscle, and wood structures like xylem that can support enormous external compressive loads and negative internal pressure to transport nutrients throughout an organism. In synthetic systems, the design, …


Designing Nonflammable Polymers And Blends Containing Deoxybenzoin Derivatives, Elizabeth Stubbs Feb 2022

Designing Nonflammable Polymers And Blends Containing Deoxybenzoin Derivatives, Elizabeth Stubbs

Doctoral Dissertations

The importance of synthetic polymers in everyday life continues to grow, owing to their societal importance for improving our standard-of-living and enabling advances spanning medicine, electronics, construction materials, transportation. While niche applications occupy a small fraction of the overall volume of polymers produced, large scale applications tend to employ lower cost materials, such as polyethylene, polypropylene, and polystyrene. In addition to environmental considerations connected to these polymerized hydrocarbons, produced in excess of 380 million tons per year worldwide, their inherent flammability creates additional requirements associated with their manufacturing and use. Societal benefits of such polymers are extensive, and thus, there …