Hierarchical self-assembly of biocompatible comb-dendrtic block copolymers

POLY 461

Lu Tian, lutian@mit.edu and Paula T. Hammond, hammond@mit.edu. Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139
A series of biocompatible comb-dendritic block copolymers rationally designed as “tree-shaped” self-assembly building blocks were developed based on a hydrophilically modified polyester dendritic block and poly (g-n-dodecyl-L-glutamate) as a hydrophobic comb block. With a highly persistent shape due to the rigid rod nature of the polypeptide block and the hydration and repulsive charge of the dendritic block, designed copolymers present controllable self assembly behaviors that enable direct application of theory relating molecular geometric shape to final aggregation form. The comb block is a rigid, helical polypeptide with flexible alkyl side groups, resulting in the formation of extremely stable hydrophobic packing. The resulted self-assembled structures (polymer micelles and vesicles) obtain high stability that allows us to image these structures as spherical nanoparticles on surfaces using atomic force microscopy and transmission electron microscopy without any further stabilization. The self-assembled structures also present dendritic structures as the exterior, providing a highly functional surface that can be used to cluster biocompatible ligands for efficient targeting and sensing capabilities.