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Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Chemistry

Year Degree Awarded

2016

Month Degree Awarded

February

First Advisor

Vincent M. Rotello

Second Advisor

Michael J. Knapp

Third Advisor

Matthew A. Holden

Fourth Advisor

Anthony D. Dinsmore

Subject Categories

Materials Chemistry | Organic Chemistry

Abstract

The conceptual framework of supramolecular chemistry elucidates a powerful set of strategies for chemists to generate functional nanomaterials based on intermolecular forces. My research focused on tuning the molecular interactions of nanoscale components to create larger structures with enhanced properties. In one approach, I developed and optimized an additive-free, nanoimprint lithography-based methodology to generate stable thin films from a variety of proteins. The generalized process retains intrinsic properties of the protein as demonstrated by selective cellular adhesion. The heat and pressure of the nanoimprinting process induces slight structural reorganization of the peptide side chains to yield highly stable films held together by inter-protein hydrophobic forces. The selective cell adhesion shown by our initial model proteins was further harnessed using inkjet printing to control the micropatterning of biomaterial substrates in a highly modular fashion. The protein-based ‘ink’ deposition when combined with the nanoimprint lithography stabilization procedure permits the rapid creation of patterns and film compositions not achievable using other nanomanufacturing techniques. My research also demonstrates that the supramolecular interactions that occur at the surface of nanomaterials can be used to create complexes to interact with the human olfactory system. Surface functionalized gold nanoparticles serve as selective and reversible inhibitors for enzymes that upon displacement by analytes in solution generate a scent-based signal from pro-fragrance molecules. The self-assembly of nanoparticles at oil/water interfaces led to the development of an alternative method to form nanoparticle-polymer nanocomposites. The assembled composite system, generated by crosslinking and phase transferring hydrophilic nanoparticles into the hydrophobic oil core, showed remarkable stability to the phase disrupting influence of ethanol. This inside-out Pickering emulsion template later aided in the creation of a multimodal nanoparticle stabilized capsule platform for the treatment of bacterial biofilms. The amine surface functionality of the nanoparticles both improved delivery to bacterial biofilms through complementary electrostatic interactions as well as stabilized the therapeutic payload of the capsules through the formation of Schiff bases. Overall, these examples highlight the potency of using supramolecular strategies for the intelligent design of nanomaterials.

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