Citation: Jin-wen Zheng, Xiao Wang, Ze-sheng An. Synthesis of Oxidation Responsive Vesicles with Different Block Sequences via RAFT Polymerization-induced Self-assembly[J]. Acta Polymerica Sinica, ;2019, 50(11): 1167-1176. doi: 10.11777/j.issn1000-3304.2019.19070 shu

Synthesis of Oxidation Responsive Vesicles with Different Block Sequences via RAFT Polymerization-induced Self-assembly

1.
Institute of Nanochemistry and Nanobiology, Shanghai University, Shanghai 200444
2.
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012

Corresponding author: Ze-sheng An, anzesheng@jlu.edu.cn
Received Date: 9 April 2019
Revised Date: 3 June 2019

Block copolymer (BCP) nanoparticles with three different block sequences, PDMA-PNAT-PDAAM (M-N-D), PDMA-PDAAM-PNAT (M-D-N) and PDMA-P(NAT-co-DAAM) (M-[N-co-D]), are prepared via polymerization-induced self-assembly (PISA). Soluble N-acryloyloxy thiomorpholine (NAT) and diacetone acrylamide (DAAM) are used as monomers to form insoluble core blocks in water, while PDMA₃₅ bearing a trithiocarbonate is utilized as stabilizer and macromolecular chain transfer agent (macro-CTA) to render a RAFT control. Specifically, M-[N-co-D] nano-objects are synthesized via direct RAFT dispersion copolymerization of NAT and DAAM at 70 °C employing PDMA₃₅ macro-CTA. To produce M-N-D and M-D-N triblock copolymers, PDMA-PNAT (M-N) and PDMA-PDAAM (M-D) nano-objects are prepared via RAFT dispersion PISA syntheses of NAT and DAAM respectively utilizing PDMA₃₅ macro-CTA and then used for seeded dispersion polymerization of DAAM and NAT respectively without intermediate postpolymerization purification. The thioether moiety in NAT can be oxidized by reactive oxygen species (ROS) into a hydrophilic sulfoxide. Therefore, in the precense of hydrogen peroxide (H₂O₂), oxidation-responsive morphological degradation of these nano-objects occurs due to the increasing hydrophilicity of NAT units. Given the poor control over polymerization of NAT in pure water, 1,4-dioxane is used as a cosolvent to the PNAT block. So the PISA syntheses are conducted in water/1,4-dioxane (9/1, V/V) mixture to achieve a good control over the molecular weight and narrow distribution. ¹H-NMR spectra indicate that quantitative monomer conversions (> 99%) are achieved within 5 h. Differential scanning calorimeter (DLS) and transmission electron microscopy (TEM) are used to characterize final morphologies of PISA-generated nano-objects and morphological evolution of nano-objects in the presence of H₂O₂ (10 mol/L). These aqueous sequence-controlled PISA formulations are expected to provide responsive nanoparticles with tunable kinetics due to the response-dependent morphological transitions, which may be potentially used as carriers for drug delivery and controlled release.
- Polymerization-induced self-assembly,
- Oxidation-responsive,
- Polymer vesicles,
- Block sequence
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Oxidation Responsive Vesicles with Different Block Sequences via RAFT Polymerization-induced Self-assembly

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com