Date of Award
Spring 2026
Document Type
Open Access Dissertation
Department
Chemistry and Biochemistry
First Advisor
Morgan Stefik
Abstract
Mixing additives with polymer micelles through physical attraction is of vital importance for drug delivery, nanoreactors, solution stabilizers, and template- based synthesis, often where size and morphology dictate overall performance for these applications. Kinetic control of polymer micelles, such that they do not change size, morphology, or aggregation number allows for the consistent and systematic study of mixing polymers with select additives e.g. metal nanoparticles. However, achieving this kinetic control is often challenging due to the narrow window of solution processing available, as well as lack of understanding how polymer chain architecture impacts mixing. To deepen the understanding of micelle-additive mixing, molecular design handles were tuned and studied across a couple of applications: expanded block polymer synthesis and solution processing to produce solvent inert micelles, and direct observations of how molecular architecture of the corona influences equilibrium additive mixing.
The first challenge is resolved with a new class of micelle immobilization (crosslinked core). Here, kinetic control is achieved through photo-crosslinkable monomer units, such that UV irradiation will covalently transform an aggregate of polymer chains into a single molecule. This new modality of kinetic control is important for the expanded synthesis of nanomaterials that was once limited to a select range of solvents. The second challenge is addressed by familiar route of kinetic control via vitrification (glass core segment) with the objective of isolating only the micelle corona behavior. Herein, three micelle samples of varying corona architecture (linear vs bottlebrush) underwent material loading experiments at various nanoparticle fractions to investigate how these different architectures influence mixing equilibrium. SAXS and advanced SEM image analysis were employed to display that linear coronas exhibit uniform mixing at every mass loading, while the stiffer, shorter backbones of the bottlebrush polymers were the limiting factor in particle mixing, leading to disordered composites. Collectively, these advancements in micelle research expand the scope of nanomaterial formulation by expanding synthetic windows and deepening understanding of architecture’s role in additive mixing.
Rights
© 2026, Coby Santos Collins
Recommended Citation
Collins, C. S.(2026). Role of Molecular Design on Polymer Micelle Control. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/8752