Self‐assembly Promoted Crystallization of Diblock Copolypeptoids in Solution†

Abstract

Comprehensive SummaryGreat efforts have been lately devoted to fabricating well‐defined nanostructures using crystallization‐driven self‐assembly (CDSA) strategy. The influence of self‐assembly on crystallization is also of great interest. Here, a series of amphiphilic diblock copolypeptoids poly(N‐allylglycine)‐b‐poly(N‐octylglycine) modified with cysteamine hydrochloride ((PNAG‐g‐NH2)‐b‐PNOG) were synthesized by ring‐opening polymerization (ROP) and post‐polymerization functionalization. The diblock copolypeptoid is comprised of one hydrophobic crystalline PNOG block and one hydrophilic amorphous block, which can aggregate into nanostructured assemblies with soluble PNAG‐g‐NH2 as the corona layer and PNOG as the inner core in aqueous solution. With a systematic study by differential scanning calorimetry (DSC) and wide‐angle X‐ray scattering (WAXS), we demonstrated that the self‐assembly of the block copolymers strengthens the crystallization of the PNOG block.