Preparation of Multi-chambered Vesicles by Polymerization-induced Self-assembly and the Influence of Solvophilic Fragments in the Core-forming Blocks
Received date: 2022-03-23
Online published: 2022-04-27
Supported by
National Natural Science Foundation of China(22131010); National Natural Science Foundation of China(52021002); Anhui University Scientific Research Start-up Fund(Y040418176)
The morphology of polymeric nano-objects has an important influence on its properties, among which vesicles (especially multi-chambered vesicles) have attracted much attention due to their hollow structures. Polymerization-induced self-assembly (PISA) is an efficient method for preparing polymeric nano-objects. However, there are relatively few reports on the efficient preparation of multi-chambered vesicles by PISA. In this paper, multi-chambered vesicles were successfully prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly using styrene (St) as monomer, ethanol/water (7/3, mass ratio) as the solvent and polyethylene glycol (PEG45-PETTC) as macro RAFT reagent. At the same time, RAFT copolymerization-induced self-assembly of St and oligoethylene glycol methyl ether methacrylate monomers (OEGMA) were carried out to explore the effect of introducing solvophilic moiety OEGMA into the core-forming blocks on the morphology of the resulting nano-objects. Due to the strong chain rigidity of polystyrene, the introduction of a solvophilic segment into the polystyrene segment to increase the flexibility of the core-forming blocks is a reported method to promote morphology evolution. However, in the polymerization-induced self-assembly system of St and OEGMA in ethanol/water (7/3, mass ratio), the introduction of solvophilic moieties (OEGMA) resulted in the morphology degradation of the resulting nano-objects. With the increase of solvophilic moieties in the core-forming blocks, the resulting nano-objects gradually transformed from multi-chambered vesicles to unicellular vesicles and spherical micelles. Random copolymer P(St-co-OEGMA) of the core-forming blocks in the corresponding nano-objects were formed by RAFT copolymerization of St and OEGMA. The solvated degree of the core-forming blocks increased due to the introduction of solvophilic OEGMA moieties. Moreover, the large side groups may also increase the free volume of core-forming blocks. The increasing of the free volume and solvated degree of the core-forming blocks synergistically weakened the packing strength of the core-forming blocks, leading to adversely effects on morphology transition of the nano-objects. We believe that the results of this study is a good complement to the current polymerization-induced self-assembly system.
Jamshid Kadirkhanov , Feng Zhong , Wenjian Zhang , Chunyan Hong . Preparation of Multi-chambered Vesicles by Polymerization-induced Self-assembly and the Influence of Solvophilic Fragments in the Core-forming Blocks[J]. Acta Chimica Sinica, 2022 , 80(7) : 913 -920 . DOI: 10.6023/A22030128
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