Theranostics Based On Linear Dendritic Block Copolymers

When combining imaging and therapeutic motifs, known as theranostics, amphiphilic diblock copolymers have a strong precedent of success. These polymers can self-assemble into a variety of morphologies that are known to concentrate in areas of inflammation such as tumors. However, prediction of size and morphology from polymer structure still remains an open challenge. Another system with promise of therapeutic efficacy are tree-like struc- tures known as dendrimers, such as poly(amidoamine) (PAMAM) and bis-(hydroxymethyl) propionic acid (bMPA), which can uptake drugs and dyes into their branches. It is desireable to combine these two motifs, using linear-dendritic block copolymers (LDBCs). These represent significant synthetic difficulty. Herein is presented novel synthetic routes and char- acterization for two systems of LDBCs. The first is a biocompatible PAMAM-polylactide (PLA) hybrid, synthesized with different PLA chain lengths and monomer stereochemistries with the aim of predicting size and morphology. This work developed an efficient synthetic route to these polymers, which were found to self-assemble into monodisperse spheres. The second system involves in-situ self-assembly, known as polymerization-induced self-assembly (PISA). LDBCs derived from bMPA dendrons linear portions, consisting of benzyl and tri-fluoroethyl methacrylate, were synthesized for the first time. This allomore precise examination of structure-property relationships at industrially relevant concentrations, and revealed a difference in mechanism for the self-assembly of each polymer. This represents the first time LDBCs have been studied by PISA, allowing the variety of applications of PISA formulations to have unprecedented access to the unique advantages of dendrimers