RAFT聚合诱导自组装制备不同嵌段序列氧化响应性聚合物囊泡

郑晋文; 王晓; 安泽胜

doi:10.11777/j.issn1000-3304.2019.19070

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RAFT聚合诱导自组装制备不同嵌段序列氧化响应性聚合物囊泡

研究论文 | 更新时间：2021-01-26

- RAFT聚合诱导自组装制备不同嵌段序列氧化响应性聚合物囊泡
  增强出版
- Synthesis of Oxidation Responsive Vesicles with Different Block Sequences via RAFT Polymerization-induced Self-assembly
- 高分子学报 2019年50卷第11期页码：1167-1176
- 作者机构：
  
  1.上海大学环境与化学工程学院纳米化学与生物学研究所　上海 200444
  2.吉林大学化学学院超分子结构与材料国家重点实验室　长春 130012
- 作者简介：
  
  E-mail: anzesheng@jlu.edu.cn Zesheng An, E-mail: anzesheng@jlu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21674059)资助项目()
- DOI：10.11777/j.issn1000-3304.2019.19070
  中图分类号：
- 纸质出版日期：2019-11，
  
  网络出版日期：2019-7-8，
  
  收稿日期：2019-4-9，
  
  修回日期：2019-6-3，
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郑晋文, 王晓, 安泽胜. RAFT聚合诱导自组装制备不同嵌段序列氧化响应性聚合物囊泡[J]. 高分子学报, 2019,50(11):1167-1176.

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.
郑晋文, 王晓, 安泽胜. RAFT聚合诱导自组装制备不同嵌段序列氧化响应性聚合物囊泡[J]. 高分子学报, 2019,50(11):1167-1176. DOI： 10.11777/j.issn1000-3304.2019.19070.

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.

摘要

以聚

-二甲基丙烯酰胺(PDMA)为大分子链转移剂(macro-CTA)，双丙酮丙烯酰胺(DAAM)和

-丙烯酰硫吗啉(NAT)为单体，在水和二氧六环的混合溶剂中，通过聚合诱导自组装(PISA)制备了3种不同嵌段序列的聚合物纳米颗粒，分别为PDMA-PNAT-PDAAM，PDMA-PDAAM-PNAT以及PDMA-P(NAT-

-DAAM). 核磁共振氢谱(

H-NMR)表明单体转化率在5 h内接近100%. 通过凝胶渗透色谱(GPC)对聚合物相对分子量及分子量分布进行了表征. 通过透射电子显微镜(TEM)研究了嵌段共聚物纳米颗粒的形貌转化过程以及3种聚合物囊泡在双氧水溶液中的氧化响应行为. 这种具有氧化响应性的聚合物囊泡有望为药物输送和控制释放提供合适的载体.

Abstract

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-

-DAAM) (M-[N-

-D])

are prepared

via

polymerization-induced self-assembly (PISA). Soluble

-acryloyloxy thiomorpholine (NAT) and diacetone acrylamide (DAAM) are used as monomers to form insoluble core blocks in water

while PDMA

bearing a trithiocarbonate is utilized as stabilizer and macromolecular chain transfer agent (macro-CTA) to render a RAFT control. Specifically

M-[N-

-D] nano-objects are synthesized

via

direct RAFT dispersion copolymerization of NAT and DAAM at 70 °C employing PDMA

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 PDMA

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 (H

)

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

4-dioxane is used as a cosolvent to the PNAT block. So the PISA syntheses are conducted in water/1

4-dioxane (9/1

) mixture to achieve a good control over the molecular weight and narrow distribution.

H-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 H

(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.

关键词

聚合诱导自组装氧化响应聚合物囊泡嵌段序列

Keywords

Polymerization-induced self-assemblyOxidation-responsivePolymer vesiclesBlock sequence

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