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<p dir="ltr">Adhesives surround us on a daily basis without us even being aware. They are the unsung heroes of most commercial products we use. Whether it be the car you drive, the shoes you wear, or the furniture you sit on, glue is keeping everything together. Adhesives have been used since the cavemen utilizing tar for keeping stone tools together. Over time, adhesives have exploded in the scientific landscape through a multitude of chemical pathways. Current products are comprised of epoxies, cyanoacrylates, polyurethanes, and many others. The need for adhesives in the manufacturing of products is consistently increasing over the years in the goal of light weighting without compromising on performance of the final material. However, this comes at the cost of glues being both toxic and nonrecyclable. With this in mind an improvement was needed to address both augmenting the glue strength and improving the sustainability of the adhesive.</p><p dir="ltr">Hierarchical structures can be observed on the micro scale in natural materials. Tree limbs are able to withstand a tremendous amount of force applied from winds, human machinery, and animal life. Why they are so resistant lies in the fact there is an ordered structure of multiple length scales working in tandem upholding the integrity of the limb. The question to ask then relating this to adhesives is if there is a way to create a glue that can disperse the forces amongst the overall material without catastrophic failure. The use of fillers such as calcium carbonate and different adhesive strain rates can be used to mimic this interaction.</p><p dir="ltr">Addressing the sustainability factor of current glues, the need was set to create a more bio-based alternative using widely available materials that are cost effective and do not compromise on overall performance. Competing with or outperforming the current market adhesives was a goal in mind. Two generations of bio-based adhesives were generated through multiple formulations using epoxidized soybean oil as the common factor. Soybean oil is one of the most widely produced vegetable oils in the country. Utilizing the oil in a functionalized way through epoxide rings, the replacement of current epoxy technology was achieved.</p>

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<p> Dramatic advances over the past decade have occurred in the use of cryogenic electron microscopy (cryoEM) to elucidate the structures of macromolecules at atomic resolution. Unfortunately, the sample preparation process is one of the most time-consuming and empirical methods in the cryoEM workflow. Each sample must be tediously optimized to resolve issues with particle aggregation, ice quality, particle orientation, and particle density to enable high-resolution reconstruction analysis. Post-polymerization modifications of synthetic aqueous bottlebrushes offer a promising approach to streamline the workflow for cryoEM sample preparation. Our approach utilizes synthetic bottlebrush materials comprised of flexible polymer scaffolds bearing grafted side-chains, armed with high affinity ligands at the distal termini of the grafted polymers along the polymer core. Development of water-soluble one-dimensional (1D) synthetic bottlebrush polymers has led to new advancements in the biomaterials, antimicrobial, nanomedicine, and responsive materials fields. These synthetic bottlebrush materials are favorable as they confer properties that linear polymers and small molecules cannot achieve. Moreover, structural manipulations employed during post-polymerization processes can afford bottlebrush polymers with distinguishable topologies for advanced functions. These 1D constructs can be synthesized by atom transfer radical polymerization (ATRP), reversible addition- fragmentation chain-transfer polymerization (RAFT), ring-opening polymerization (ROP), cationic ring-opening polymerization (CROP), anionic ring-opening polymerization (AROP) or ring opening metathesis polymerization (ROMP). The chemical composition of the molecule, number of monomer repeats, grafting density and topology influence the morphology and function of polymer brushes. Elongated, vesicular or micellar morphologies can be specifically tuned for the desired application of the material. The morphology of the polymers can also be manipulated by concentration effects. The morphologies of amphiphilic bottlebrush materials specifically, can typically be influenced by structural topology, solvent choice, or external conditions. ROMP is a living polymerization mechanism that can suffer from catalytic backbiting, causing a loss of livingness. The synthesis of aqueous bottlebrush polymers and the comparison of morphologies via AUC, DLS, AFM and TEM will be presented in this dissertation. The synthetic amphiphilic bottlebrush polymer family presented suffered a loss of livingness and ultimately displayed distinct morphologies, relative to chemical composition, solvent, and ultimately polymerization time. Post-polymerization 11 modifications such as backbone hydrolysis and single-walled carbon nanotube complexation promoted even more unique morphologies of bottlebrushes. These synthetic materials indicate use as promising reagents for cryoEM sample preparation.  </p>