氧化还原响应性长链超分子超支化聚合物的构筑及药物控释研究

刘婷婷; 王景霞; 宋彦丽; 原红星; 田威

doi:10.11777/j.issn1000-3304.2017.17132

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氧化还原响应性长链超分子超支化聚合物的构筑及药物控释研究

研究论文 | 更新时间：2021-01-26

- 氧化还原响应性长链超分子超支化聚合物的构筑及药物控释研究
- Redox-responsive Long Chain Supramolecular Hyperbranched Polymer for Controlled Drug Release
- 高分子学报 2018年第4期页码：482-489
- 作者机构：
  
  陕西省高分子科学与技术重点实验室西北工业大学理学院西安 710072
- 作者简介：
  
  王景霞, E-mail: wjx@nwpu.edu.cn Jing-xia Wang, E-mail: wjx@nwpu.edu.cn
  田威, E-mail:happytw_3000@nwpu.edu.cn Wei Tian, E-mail: happytw_3000@nwpu.edu.cn
- 基金信息：
  
  国家自然科学基金(21674086);国家自然科学基金(21374088)
- DOI：10.11777/j.issn1000-3304.2017.17132
  中图分类号：
- 纸质出版日期：2018-4-20，
  
  收稿日期：2017-5-14，
  
  修回日期：2017-6-10，
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刘婷婷, 王景霞, 宋彦丽, 原红星, 田威. 氧化还原响应性长链超分子超支化聚合物的构筑及药物控释研究[J]. 高分子学报, 2018,(4):482-489.

Ting-ting Liu, Jing-xia Wang, Yan-li Song, Hong-xing Yuan, Wei Tian. Redox-responsive Long Chain Supramolecular Hyperbranched Polymer for Controlled Drug Release[J]. Acta Polymerica Sinica, 2018,(4):482-489.
刘婷婷, 王景霞, 宋彦丽, 原红星, 田威. 氧化还原响应性长链超分子超支化聚合物的构筑及药物控释研究[J]. 高分子学报, 2018,(4):482-489. DOI： 10.11777/j.issn1000-3304.2017.17132.

Ting-ting Liu, Jing-xia Wang, Yan-li Song, Hong-xing Yuan, Wei Tian. Redox-responsive Long Chain Supramolecular Hyperbranched Polymer for Controlled Drug Release[J]. Acta Polymerica Sinica, 2018,(4):482-489. DOI： 10.11777/j.issn1000-3304.2017.17132.

摘要

首先合成了一种同时含有端巯基、端炔基且具有

-环糊精（

-CD）/二茂铁（Fc）超分子主客体作用的AB

型长链大分子单体（MM），再利用其巯基和炔基的点击反应可以合成出氧化还原响应性长链超分子超支化聚合物（SHP）.利用一维和二维核磁共振谱对MM和SHP的聚合物结构和超分子作用进行了表征和确认.动态光散射和透射电子显微镜测试结果表明：在水溶液中，SHP可自发地形成支化自组装形貌；而当加入H

后，由于

-CD/Fc主客体作用的解离，支化自组装体结构被破坏、且进一步二次组装球形胶束.对比于线型超分子聚合物自组装体，SHP具有更高的载药效率.利用紫外分光光度计测试载药SHP自组装体对抗癌药物阿霉素（DOX）的累积释放曲线发现H

可有效调控SHP自组装体中DOX的释放速率，即：当加入H

后，DOX的释放速率明显加快.

Abstract

Stimuli-responsiveness in biological body and high drug loading efficiency are two of the prerequisites to conduct controlled drug release of supramolecular hyperbranched polymers (SHPs). Herein

the redox-responsive long chain SHP was constructed by click reaction of AB

type macromonomer (MM)

which contains thiol and alkynyl groups as well as

-cyclodextrin (

-CD)/Fcrrocene (Fc). A linear cationic polymer with thiol group at one end and

-cyclodextrin at the other end was first synthesized by the combination of reversible addition-fragmentation chain transfer polymerization (RAFT)

ring-opening reaction and end group modification. And then

the AB

-type macromonomer was prepared by the inclusion complexation between

-CD and Fc in aqueous solution. The final SHP was achieved by click reaction of thiol group with alkynyl group under UV irradiation. The polymer structure and supramolecular interaction of MM and SHP were confirmed by

H nuclear magnetic resonance and 2D NOSEY spectra. The self-assembly of SHP in aqueous solution was further investigated through transmission electron microscopy (TEM) and dynamic light scattering (DLS). Both TEM and DLS results indicated that SHP self-assembled into branched aggregates without external stimuli

and then dissociated and secondly self-assembled into irregular spherical self-assemblies due to the dissociation of

-CD and Fc complexes induced by reducing agent H

. The SHP self-assemblies possess a high doxorubicin (DOX) loading capacity compared with linear supramolecular polymer self-assemblies. Furthermore

by utilizing the above H

-tuned self-assembly morphology transition feature

a smart drug delivery behavior was observed through the cumulative release curves of DOX-loaded SHP self-assemblies. The controlled drug release behavior of SHP self-assemblies embedded DOX under pH=7.4 and 5.0 was deeply studied. The results indicated that H

broke the host-guest interaction between

-CD and Fc

leading to a fast release of DOX. Meantime

the dissociation of SHP self-assemblies further self-assembled into small solid micelles. Therefore

the release behavior of DOX-loaded SHP self-assemblies presented the redox-responsive characteristics.

关键词

超分子超支化聚合物主客体作用氧化还原响应性药物控释

Keywords

Supramolecular hyperbranched polymerRedox-responsivenessHost-guest interactionControlled drug release

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