TY - JOUR
T1 - Nanoporous Vesicular Membranes of Amphiphilic Polymers Containing Trans/Cis Isomers
AU - Chen, Hui
AU - Yu, Xia
AU - Fan, Yujiao
AU - Xing, Xiangjun
AU - Trépout, Sylvain
AU - Li, Min Hui
N1 - Funding Information:
This work has received financial support from the Centre National de la Recherche Scientifique (CNRS) through the Mission for Transversal and Interdisciplinary Initiatives (MITI) interdisciplinary programs, the French National Research Agency (ANR-16-CE29-0028), as well as National Natural Science Foundation of China (NSFC) (grant no. 11674217) and Shanghai Municipal Science & Technology Major Project (grant no. 2019SHZDZX01).
Funding Information:
Y.F. gratefully acknowledges the China Scholarship Council for funding her PhD scholarship. The Multimodal Imaging Centre of Institut Curie is acknowledged for providing access to the cryo-EM facility in Orsay. We also thank Vincent Semetey (Chimie ParisTech) for his help in capturing the epifluorescence microscopic images.
Publisher Copyright:
© 2022 The authors.
PY - 2022/8
Y1 - 2022/8
N2 - 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-TPEChol 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-SSTPE-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-TPESS-Chol polymersomes can be destroyed using reducing agents, which may be useful for controlled release.
AB - 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-TPEChol 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-SSTPE-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-TPESS-Chol polymersomes can be destroyed using reducing agents, which may be useful for controlled release.
KW - aggregation-induced emission
KW - amphiphilic polymers
KW - porous membrane
KW - self-assembly
KW - stereoisomers
UR - http://www.scopus.com/inward/record.url?scp=85135722651&partnerID=8YFLogxK
U2 - 10.31635/ccschem.022.202201916
DO - 10.31635/ccschem.022.202201916
M3 - Article
AN - SCOPUS:85135722651
SN - 2096-5745
VL - 4
SP - 2651
EP - 2661
JO - CCS Chemistry
JF - CCS Chemistry
IS - 8
ER -