Non-Covalent Interactions in the Design and Performance of Macromolecules for Biological Technologies
Pekkanen, Allison Marie
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Supramolecular, or non-covalent, interactions remain a hallmark of biological systems, dictating biologic activity from the structure of DNA to protein folding and cell-substrate interactions. Harnessing the power of supramolecular interactions commonly experienced in biological systems provides numerous functionalities for modifying synthetic materials. Hydrogen bonding, ionic interactions, and metal-ligand interactions highlight the supramolecular interactions examined in this work. Their broad utility in the fields of nanoparticle formulations, polymer chemistry, and additive manufacturing facilitated the generation of numerous biological materials. Metal-ligand interactions facilitated carbon nanohorn functionalization with quantum dots through the zinc-sulfur interaction. The incorporation of platinum-based chemotherapeutic cisplatin generated a theranostic nanohorn capable of real-time imaging and drug delivery concurrent with photothermal therapies. These nanoparticles remain non-toxic without chemotherapy, providing patient-specific. Furthermore, metal-ligand interactions proved vital to retaining quantum dots on nanoparticle surfaces for up to three days, both limiting their toxicity and enhancing their imaging potential. Controlled release of biologics remain highly sought-after, as they remain widely regarded as next-generation therapeutics for a number of diseases. Geometry-controlled release afforded by additive manufacturing advances next-generation drug delivery solutions. Poly(ether ester) ionomers composed of sulfonated isophthalate and poly(ethylene glycol) provided polymers well suited for low-temperature material extrusion additive manufacturing. Ionic interactions featured in the development of these ionomers and proved vital to their ultimate success to print from filament. Contrary to ionic interactions, hydrogen bonding ureas coupled poly(ethylene glycol) segments and provided superior mechanical properties compared to ionic interactions. Furthermore, the urea bond linking together poly(ethylene glycol) chains proved fully degradable over the course of one month in solution with urease. The strength of these supramolecular interactions demanded further examination in the photopolymerization of monofunctional monomers to create free-standing films. Furthermore, the incorporation of both hydrogen bonding acrylamides and ionic groups provided faster polymerization times and higher moduli films upon light irradiation. Vat photopolymerization additive manufacturing generated 3-dimensional parts from monofunctional monomers. These soluble parts created from additive manufacturing provide future scaffolds for controlled release applications. Controlled release, whether a biologic or chemotherapeutic, remains a vital portion of the biomedical sciences and supramolecular interactions provides the future of materials for these applications.
- Doctoral Dissertations