Concurrent Block Copolymer Polymersome Stabilization and Bilayer Permeabilization by Stimuli‐Regulated “Traceless” Crosslinking

作者：Xiaorui Wang, Guhuan Liu, Jinming Hu, Guoying Zhang, Shiyong Liu · 发表于：Angewandte Chemie International Edition · 年份：2014 · DOI：10.1002/anie.201310589 · 被引用次数：225 · 研究领域：Advanced Polymer Synthesis and Characterization、Supramolecular Self-Assembly in Materials、Covalent Organic Framework Applications

The fabrication of block copolymer (BCP) vesicles (polymersomes) exhibiting synchronized covalent crosslinking and bilayer permeabilization remains a considerable challenge as crosslinking typically leads to compromised membrane permeability. Herein it is demonstrated how to solve this dilemma by employing a stimuli-triggered crosslinking strategy with amphiphilic BCPs containing photolabile carbamate-caged primary amines. Upon self-assembling into polymersomes, light-triggered self-immolative decaging reactions release primary amine moieties and extensive amidation reactions then occur due to suppressed amine pKa within hydrophobic milieu. This leads to serendipitous vesicle crosslinking and the process is associated with bilayer hydrophobicity-to-hydrophilicity transition and membrane permeabilization.