Characterization of Fibril Hierarchical Self-Assembly of Sugar-based Poly(D-glucose carbonate) Amphiphilic Block Copolymers in Solution

Motivated by the recent drive to replace petrochemical plastics for more renewable source-based materials, our efforts focus on designing and characterizing a next generation biomolecular-based polymer for solution assembly applications. Specifically, the solution chain and assembly behavior of sugar-derived poly(D-glucose carbonate) (PGC) molecules are analyzed in the production of nanoparticles. Unlike conventional vinyl-based polymers, the PGC system is characterized by its entire backbone composed of semiflexible, hydrophobic glucose monomers where its chain rigidity and local amphiphilicity created by the backbone are expected to impact the solution chain behavior. With a PGC-containing amphiphilic BCP system, we explore kinetically controlled assembly pathways for the hierarchical fibril construction. We show that while the stiffness of the PGC backbone impacts the local BCP chain conformation within the nanostructure, the backbone hydrophobicity drives the global unidirectional hierarchical fibril growth by the formation of soft patchy precursor particles. These results suggest polymers with unconventional backbone chemistries, frequently found in natural carbohydrate-based molecules, can shed light on the effects of unique chain properties on the assembly pathway.