Preparation of Multi-chambered Vesicles by Polymerization-induced Self-assembly and the Influence of Solvophilic Fragments in the Core-forming Blocks

doi:10.6023/A22030128

Abstract

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.

Key words: polymerization-induced self-assembly, multi-chambered vesicles, morphology evolution

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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.

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Fig. & Tab. 8

Scheme 1. (A) Multi-chambered vesicles are prepared by polymerization-induced self-assembly (PISA) using PEG45-PETTC-mediated RAFT polymerization of styrene (St) in ethanol/water (7/3, mass ratio). (B) Morphology degradation in the PISA system of RAFT copolymerization of St and oligoethylene glycol methyl ether methacrylate (OEGMA)

Figure 1. (A) 1H NMR spectra of the macro RAFT agent PEG45-PETTC in CDCl3. (B) GPC trace of the macro RAFT agent PEG45-PETTC

Figure 2. (A) The curve of monomer conversion vs. polymerization time and (B) the curve of ln([M]0/[M]t) vs. polymerization time in the RAFT polymerization-induced self-assembly system with the feed molar ratio (600/1) of St/PEG45-PETTC and mass ratio (7/3) of ethanol/water as the solvent

Figure 3. TEM images of the PEG45-b-PSt nano-objects obtained by RAFT polymerization of St in ethanol/water (7/3, mass ratio) with feed molar ratio (600/1) of St/PEG45-PETTC at different polymerization time, (A) 12 h, (B) 15 h, (C) 18 h and (D) 24 h. In the image, the subscript number of St is the monomer conversion at this time. (E) The magnified image of (D)

Figure 4. TEM images of the PEG45-b-P(St-co-OEGMA) nano-objects obtained by RAFT copolymerization of St and OEGMA in ethanol/water (7/3, mass ratio) with feed molar ratio (600/10/1) of St/OEGMA/ PEG45-PETTC at different polymerization time, (A) 12 h and (B) 24 h. St represents styrene, the subscript number of St is the conversion of styrene at this time, O represents OEGMA, and the subscript number of O is the conversion of OEGMA at this time

Figure 5. TEM images of the PEG45-b-P(St-co-OEGMA) nano-objects obtained by RAFT copolymerization of St and OEGMA in ethanol/water (7/3, mass ratio) with different feed molar ratio of St/OEGMA/PEG45-PETTC, (A1) 10/300/1, (B1) 10/400/1, (C1) 10/500/1, (D1) 10/600/1, (A2) 30/300/1, (B2) 30/400/1, (C2) 30/500/1 and (D2) 30/600/1. St represents styrene, the subscript number of St is the conversion of styrene, O represents OEGMA, and the subscript number of O is the conversion of OEGMA

Figure 6. (A) The typical 1H NMR spectrum of PEG45-b-P(St-co-OEGMA) obtained by RAFT copolymerization of St and OEGMA at St/OEGMA/PEG45-PETTC (300/10/1, molar ratio). (B) GPC results of the PEG45-b-P(St-co-OEGMA) obtained by RAFT copolymerization of St and OEGMA at different feed molar ratio of St/OEGMA/PEG45-PETTC, black line: 300/10/1, red line: 400/10/1, green line: 500/10/1 and blue line: 600/10/1. (C) GPC results of the PEG45-b-P(St-co-OEGMA) obtained by RAFT copolymerization of St and OEGMA at different feed molar ratio of St/OEGMA/PEG45-PETTC, black line: 300/30/1, red line: 400/30/1, green line: 500/30/1 and blue line: 600/30/1

Sample^a	C_St^b	N_St^b	C_OEGMA^b	N_OEGMA^b	M_n^c	M_w/M_n^c	Morphology^d
OEGMA/St/PEG₄₅-PETTC (0/600/1)	87.8%	527	—	—	56100	1.21	mcv
OEGMA/St/PEG₄₅-PETTC (10/300/1)	96.1%	288	44.2%	4.4	31900	1.20	v
OEGMA/St/PEG₄₅-PETTC (10/400/1)	94.5%	378	25.9%	2.6	40600	1.21	v
OEGMA/St/PEG₄₅-PETTC (10/500/1)	95.2%	476	29.1%	2.9	50400	1.22	v
OEGMA/St/PEG₄₅-PETTC (10/600/1)	89.9%	539	38.9%	3.9	52000	1.24	v
OEGMA/St/PEG₄₅-PETTC (30/300/1)	83.2%	250	30.4%	9.1	29200	1.17	ir
OEGMA/St/PEG₄₅-PETTC (30/400/1)	89.6%	358	27.7%	8.3	41600	1.17	s
OEGMA/St/PEG₄₅-PETTC (30/500/1)	88.6%	443	24.5%	7.4	46500	1.18	s+v
OEGMA/St/PEG₄₅-PETTC (30/600/1)	86.6%	520	20.7%	6.2	53700	1.19	v
OEGMA/St/PEG₄₅-PETTC (50/600/1)	84.9%	509	19.0%	9.5	54100	1.26	s

Table 1. The monomer conversion, number of St and OEGMA units in the solvophobic blocks, Mn and Mw/Mn of the resultant polymer PEG45-b-P(St-co-OEGMA), and morphology of the nano-objects obtained by PISA with different feed molar ratio of OEGMA/St/PEG45-PETTC

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