Nanoengineered polypeptides from tetraphenylethylene-functionalized N-carboxyanhydride: Synthesis, self-assembly and intrinsic aggregation-induced emission

Abstract

Ring-opening polymerization of N-carboxyanhydrides (NCAs) bearing pendant groups creates functional polypeptides. In this paper, we report the design, synthesis and polymerization of tetraphenylethylene (TPE)-modified NCA, which is used to incorporate aggregation-induced emission (AIE)-active segments into polypeptides. Specifically, we attempted the synthesis of amphiphilic methoxy poly(ethyleneglycol)-block-poly(γ-benzyl-l-glutamate)-block-poly(γ-4-(1,2,2-triphenylvinyl)benzyl-l-glutamate) (PEG-PBLG-PTPELG), which had well-controlled molecular weight and narrow polydispersity. The hydrophilic PEG and hydrophobic PBLG-PTPELG assembled into micelles in aqueous solution with diameter around 70 ​nm, displaying AIE at 480 ​nm. Our work demonstrates that the TPE-modified NCA is applicable for the preparation of the AIE-active polypeptides, integrating the AIE luminogens into the polypeptides which may offer unique opportunities for tuning AIE properties by adjusting the composition and conformation of polypeptides. We preliminarily explored the use of the amphiphilic polypeptides for the formulation of doxorubicin-containing micelles that can potentially be used for real-time monitoring of the nanomedicine distribution.