Date of Completion


Embargo Period



supramolecular, self-assembly, macromolecule, nanoparticle, polypeptide, supramolecular polymerization, thermodynamic analysis, bio-inspired, electrostatic interaction, charged subunit

Major Advisor

Yao Lin

Associate Advisor

Jing Zhao

Associate Advisor

Mu-Ping Nieh

Field of Study



Doctor of Philosophy

Open Access

Campus Access


The objective of this research is to develop regulated supramolecular polymerization from synthetic subunits by coupling the assembly processes with the chemical reactions of the monomers in aqueous solution. Many of the current self-assembly processes from synthetic macromolecules or nanoparticles rely on a nucleation mechanism, which may require a very specific solution condition and can be quite slow. In nature, protein polymerization is often accelerated by specific regulating molecules that interact with proteins and increase their association strengths. Herein, I describe how the controlled interactions of charged polypeptides can be utilized to guide the self-assembly of nanoparticles and how the integrated attractive and repulsive interactions may influence the shape and size of the resulting supramolecular structures. Using the principle, I further develop a system using synthetic macromolecular and small organic molecular subunits to demonstrate how the in-situ modulation of interactions between the charged molecules would affect the supramolecular structures and the kinetic of their formation. Thermodynamic analysis indicates the delicate role of the electrostatic interactions between the charged subunits in the assembly process. This approach may also be applicable for assembling a variety of ionic soft matter that is amenable to chemical reactions in-situ. This bio-inspired mechanism may be instructive to develop new pathways for regulating the supramolecular polymerization and de-polymerization of synthetic subunits in aqueous solution.