Library of Derivatizable Multiblock Copolymers by Nucleophilic Substitution Polymerization and Targeting Specific Properties.

Multiblock copolymers (MBCs) are fascinating in the field of biology-polymer chemistry interfaces. Synthesizing libraries of MBCs with tailor-made functionality is challenging as it involves multiple steps. Herein, a simple synthesis, analogous to polyurethane/Michael addition reactions, has been introduced to obtain a library of derivatizable MBCs. Nucleophilic substitution polymerization (SNP) of poly(ε-caprolactone) and poly(ethylene glycol) blocks containing activated halide termini by primary mono/di/coamines or clickable amines provides functional MBCs. The structure of amines directs the properties of the MBCs. The self-assembly of small molecular weight primary diamine-based MBCs shows controlled release of hydrophobic model guest molecules and therapeutics. The primary diamine (no dangling chain) helps to form MBC micelles having a relatively tight core with a low diffusion property. Antimicrobial property in the MBCs has been introduced by separating the cationic centers from the lipophilic groups using a coamine as a nucleophilic agent and a small molecular weight dihalide as a chain extender. Clickable MBCs were synthesized by changing the structure of the nucleophile to obtain degradable amphiphilic conetworks and hydrogels. Varieties of macromolecular entities could be obtained by switching the nucleophilic agent and introducing a small molecular weight chain extender. This synthesis approach provides an opportunity to tune the chemical functionality, topological structure, and biological properties of macromolecular entities.