Fluorine-Containing Triblock Copolymer Vesicles with Microphase-Separated Structure

Abstract

Introduction of a fluorine-containing block into block copolymers is an effective method to tune block copolymer nanoassemblies with a microphase-separated structure. However, this microphase-separated structure is difficult to clearly observe due to its nanoscale size. In this work, fluorine-containing ABC triblock copolymer vesicles of poly(ethylene glycol)-block-polystyrene-block-poly(4-vinylbenzyl pentafluorophenyl ether) (PEG-b-PS-b-PVBFP) are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization under dispersed condition. Owing to the choice of a suitable degree of polymerization of the three blocks, the synthesized PEG45-b-PS197-b-PVBFP233 vesicles have a relatively large size of around 216 nm and a thin vesicular membrane with a thickness of around 28 nm. Ascribed to the relatively large size of the vesicles and the thin vesicular membrane, it is concluded that the fluorine-containing PVBFP block forms 9 nm columnar microdomains shielded by the PS phase in the vesicular membrane.

Physically and Chemically Compartmentalized Polymersomes for Programmed Delivery and Biological Applications

“…Bai et al reported dual-responsive physicalcompartmentalized polymersomes by the coassembly of βcyclodextrin-acylhydrazone-doxorubicin (β-CD-hydrazone-DOX) and azobenzene-terminated poly(2-(dimethylamino)ethyl methacrylate) (Azo-PDMA-FA) for ultraviolet light and pH triggered three-stage programmed drug release. 110 First, DOX was released from physically compartmentalized polymersomes slowly. Next, ultraviolet light promoted the dissociation of β-CD/Azo, leading to the shape transformation and quick release of DOX.…”

“…More importantly, this polymer could be integrated into the phospholipid membrane, which acted as a synthetic molecular channel and improved the permeability of the molecule. Very recently, Zhang and co-workers reported phase-separated vesicles self-assembled from a fluorine-containing triblock copolymer PEG- b -PS- b -PVBFP. As shown in Figure A,B,D, the synthesized PEG 45 - b -PS 197 - b -PVBFP 233 polymersomes were relatively large size of about 216 nm, and their membrane thickness was about 28 nm.…”

“…(C) TEM images of PEG 45 - b -PS 197 polymersomes and (D) PEG 45 - b -PS 197 - b -PVBFP 233 polymersomes. Reprinted with permission from ref . Copyright 2023 American Chemical Society.…”

“…Similarly, Zeng et al developed a thermo-responsive liposomes-in-polymersome system for the controlled release of pesticide, showing a low-temperature triggered burst release behavior due to the phase transition. Bai et al reported dual-responsive physical-compartmentalized polymersomes by the coassembly of β-cyclodextrin-acylhydrazone-doxorubicin (β-CD-hydrazone-DOX) and azobenzene-terminated poly­(2-(dimethylamino)­ethyl methacrylate) (Azo-PDMA-FA) for ultraviolet light and pH triggered three-stage programmed drug release . First, DOX was released from physically compartmentalized polymersomes slowly.…”

Preparation of diblock copolymer nano-assemblies by ultrasonics assisted ethanol-phase polymerization-induced self-assembly

“…To address these issues, the PISA method was developed. It can directly prepare diblock copolymer nanoparticles with controllable morphology [24] , [25] , [26] , [27] , [28] , [29] , [30] , [31] , [32] , [33] , [34] , [35] , [36] , [37] , [38] , [39] , [40] , [41] , [42] , [43] , [44] , [45] , and high concentration (50 wt%), offering the advantages of simplicity, efficiency, and repeatability. With the advancement of PISA, initiation is no longer limited to thermal methods, leading to the emergence of greener and more energy-efficient initiation mechanisms and supportive methods.…”