I. Macromolecular and architectural effects on the polymerization of α-helices & II. Functional ROMP curing polyester thermosets

Polypeptides provide form and function to every form of life we know on earth. They have the ability to accelerate reactions that would otherwise not occur on a timescale reasonable for life, they can assemble to form extremely complex and hierarchical structures that translate nanoscale movement into macroscopic movement as exemplified in muscle tissue, and they have a unique ability to construct themselves via ribosomes. The first part of my research has concentrated on asking the question, “How can synthetic materials behave like those found in nature?”. While it is a broad question, my research has demonstrated that polymer systems can utilize cues given by their architecture to alter their behavior. In more specific terms, I have shown that polymer kinetics can be governed by not only secondary structure, but also tertiary structure. Utilizing N-carboxyanhydride monomers that polymerize to form polypeptides, the folding of the polymers into alpha-helices was shown to drastically increase the rate of propagation. Furthermore, when the alpha-helices were organized in a close, parallel array along a separate polymer scaffold, the polymerization was found to increase in rate even more substantially. The second part of my thesis focuses on a separate project altogether, sponsored by The Dow Chemical Company. This project focuses on the utilization of ring-opening metathesis polymerization (ROMP) to fabricate new useful materials. ROMP has been a widely utilized and powerful polymerization method to create extremely smart and tunable materials. While a few monomers capable of being polymerized with ROMP have found commercial success, there is substantial room for development. In the second part of my thesis I demonstrated that functional monomers capable of undergoing ROMP can be incorporated into polyesters via the alternating polymerization of epoxides and anhydrides. The utilization of these polymers as multi-functional crosslinkers for thermosets was also demonstrated, incorporating the small molecules 4-dimethylaminopyridine as an agent to limit the curing at room temperature