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Nanoporous Vesicular Membranes of Amphiphilic Polymers Containing Trans/Cis Isomers
CCS Chemistry ( IF 9.4 ) Pub Date : 2022-05-19 , DOI: 10.31635/ccschem.022.202201916
Hui Chen 1, 2 , Xia Yu 1 , Yujiao Fan 2 , Xiangjun Xing 3 , Sylvain Trépout 4 , Min-Hui Li 1, 2
Affiliation  

Nanoporous membranes and vesicles are interesting systems with potential in applications offering channels for material exchange. Herein, nanoporous membranes and polymersomes are developed by self-assembly of trans- and cis-stereoisomers of amphiphilic polymers. Two polymers, PEG550-TPE-Chol and PEG550-SS-TPE-SS-Chol, containing a central tetraphenylethene (TPE), a cholesterol (Chol), and a poly(ethylene glycol) (PEG550) are studied. Their difference resides in the spacers connecting the TPE to the Chol and to PEG, where PEG550-SS-TPE-SS-Chol contains disulfide bonds (–SS–) with two longer and more flexible spacers compared to PEG550-TPE-Chol. For PEG550-TPE-Chol, a progressive transformation from standard vesicles to porous vesicles, networks, and cylindrical micelles is shown as the trans/cis ratio increases. A local, hexagonal structure of nanopores is observed in the membrane of PEG550-TPE-Chol (trans/cis = 50/50), while a two-dimensional crystalline hexagonal structure of nanopores with long-range order is obtained in that of PEG550-SS-TPE-SS-Chol (trans/cis = 50/50). This self-assembly is likely driven by the microphase separation between vesicle-forming trans-isomers and micelle-forming cis-isomers, where both kinetic effects and free energy minimization play important roles. The hexagonal pore organization is facilitated by higher molecular mobility due to the softer and longer spacers or higher temperature. All nanostructures exhibit cyan aggregation-induced emission fluorescence. Moreover, PEG550-SS-TPE-SS-Chol polymersomes can be destroyed using reducing agents, which may be useful for controlled release.



中文翻译:

含有反式/顺式异构体的两亲聚合物的纳米多孔囊泡膜

纳米多孔膜和囊泡是有趣的系统,在为材料交换提供通道的应用中具有潜力。在此,纳米多孔膜和聚合物体是通过反式和顺的自组装开发的。两亲聚合物的立体异构体。研究了两种聚合物,PEG550-TPE-Chol 和 PEG550-SS-TPE-SS-Chol,它们含有一个中心四苯基乙烯 (TPE)、一个胆固醇 (Chol) 和一个聚 (乙二醇) (PEG550)。它们的区别在于将 TPE 连接到 Chol 和 PEG 的间隔物,其中 PEG550-SS-TPE-SS-Chol 含有二硫键 (-SS-),与 PEG550-TPE-Chol 相比,它们具有两个更长、更灵活的间隔物。对于 PEG550-TPE-Chol,随着反式/顺式比率的增加,显示了从标准囊泡到多孔囊泡、网络和圆柱形胶束的逐步转变。在 PEG550-TPE-Chol ( trans/cis= 50/50),而在PEG550-SS-TPE-SS-Chol(反式/顺式 = 50/50) 中获得了具有长程有序纳米孔的二维结晶六方结构。这种自组装可能是由形成囊泡的反式异构体和形成胶束的顺式异构体之间的微相分离驱动的,其中动力学效应和自由能最小化都起着重要作用。由于更柔软和更长的间隔物或更高的温度,更高的分子移动性促进了六边形孔的组织。所有纳米结构都表现出青色聚集诱导的发射荧光。此外,可以使用还原剂破坏 PEG550-SS-TPE-SS-Chol 聚合物体,这可能对控释有用。

更新日期:2022-05-20
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