Concurrent block copolymer polymersome stabilization and bilayer permeabilization by stimuli-regulated "traceless" crosslinking.
Concurrent block copolymer polymersome stabilization and bilayer permeabilization by stimuli-regulated "traceless" crosslinking.
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DOI：
10.1002/anie.201310589
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发表时间：
2014-03
影响因子：
--
通讯作者：
Xiaorui Wang;Guhuan Liu;Jinming Hu;Guoying Zhang;Shiyong Liu
中科院分区：
文献类型：
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作者：
Xiaorui Wang;Guhuan Liu;Jinming Hu;Guoying Zhang;Shiyong Liu
表现出同步共价交联和双层透化的嵌段共聚物（BCP）囊泡（聚合物囊泡）的制造仍然是相当大的挑战，因为交联通常导致膜渗透性受损。在本文中，它演示了如何解决这一困境，采用刺激触发的交联策略与两亲性BCP含有光不稳定的氨基甲酸酯笼伯胺。在自组装成聚合物囊泡时，光触发的自分解脱笼反应释放伯胺部分，然后由于疏水环境内抑制的胺pKa而发生广泛的酰胺化反应。这导致偶然的囊泡交联，并且该过程与双层疏水性到亲水性的转变和膜透化有关。
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.