Date of Award
12-2025
Degree Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
School
Polymer Science and Engineering
Committee Chair
Sarah Morgan
Committee Chair School
Polymer Science and Engineering
Committee Member 2
Derek Patton
Committee Member 2 School
Polymer Science and Engineering
Committee Member 3
James Rawlins
Committee Member 3 School
Polymer Science and Engineering
Committee Member 4
Olivia McNair
Committee Member 4 School
Polymer Science and Engineering
Committee Member 5
Jeffery Wiggins
Committee Member 5 School
Polymer Science and Engineering
Abstract
The focus of this dissertation is the development of polyelectrolyte-based materials with controlled compositions for therapeutic delivery applications. Understanding how glycopolymer loading, saccharide stereochemistry, and cationic density influence material properties provides a platform for the design of polyelectrolyte delivery systems for diverse biomedical applications.
The first chapter provides an overview of biomedical applications addressed in this dissertation, along with polymeric materials and design principles relevant to the development of therapeutic delivery coatings and hydrogels. In the second chapter, the synthesis of novel cationic glycopolymer hydrogels is presented, and the effects of glycopolymer type and cationic loading on viscoelastic properties, release kinetics, and stimulus responsiveness are evaluated. We report that glycopolymer type and loading were found to influence polymer structure, gel strength, self-healing properties, and cargo release kinetics, while pH-responsiveness was primarily governed by cationic content. As a proof-of-concept, it was demonstrated that the cationic terpolymer hydrogels successfully crossed the peritrophic membrane and entered the tick midgut, supporting their potential as RNAi delivery vehicles. In the third chapter, cationic emulsion coatings were developed for therapeutic biomolecule delivery in wound healing applications. We report that processing conditions and saccharide stereochemistry of the biomolecule affect emulsion quality, while coating thickness dictates coating degradation behavior. Proof-of-concept studies demonstrated that silk sutures coated with therapeutic biomolecule-containing emulsions significantly enhanced wound healing compared to uncoated sutures and sutures coated with non-therapeutic formulations. Finally, the fourth chapter summarizes the major conclusions of this work and outlines future directions to further advance the design and applications of polyelectrolyte-based therapeutic delivery systems.
Copyright
Zoe Lequeux 2025
Recommended Citation
Lequeux, Zoe, "Structure-Property Relationships of Cationic Materials for Biomedical Applications" (2025). Dissertations. 2407.
https://aquila.usm.edu/dissertations/2407