pH和氧化双响应性聚β硫酯化合物的制备及其聚集性质的研究

doi:10.6023/A15120787

化学学报 ›› 2016, Vol. 74 ›› Issue (3): 234-240.DOI: 10.6023/A15120787 上一篇下一篇

研究论文

pH和氧化双响应性聚β硫酯化合物的制备及其聚集性质的研究

赵文静^a, 乔增莹^b, 段中余^a, 王浩^b

a. 河北工业大学化工学院天津 300130;
b. 国家纳米科学中心纳米科学卓越创新中心纳米生物效应与安全性重点实验室北京 100190

投稿日期:2015-12-19 发布日期:2016-02-23
通讯作者: 段中余, 王浩 E-mail:zyduan@hebut.edu.cn;wanghao@nanoctr.cn
基金资助:
项目受国家自然科学基金(Nos. 21374026, 51373046, 51473045)和河北省自然科学基金(B2014202209)资助.

Synthesis and Self-assembly of pH and ROS Dual Responsive Poly(β-thioester)s

Zhao Wenjing^a, Qiao Zengying^b, Duan Zhongyu^a, Wang Hao^b

a School of Chemical Engineering, Hebei University of Technology, Tianjin 300130;
b CAS Center for Excellence in Nanoscience, CAS Key Laboratory for Biological Effects of Nanomaterials and Nanosafety, National Center for Nanoscience and Technology (NCNST), Beijing 100190

Received:2015-12-19 Published:2016-02-23
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21374026, 51373046, 51473045) and Hebei Provincial Natural Science Foundation of China (B2014202209).

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1. pH和氧化双响应性聚β硫酯化合物的制备及其聚集性质的研究.PDF(356KB)

摘要/Abstract

以二丙烯酸二乙二醇酯(DEDA), 二硫苏糖醇(DTT), 丙烯酰氯(AC), 巯基聚乙二醇(PEG-SH, M_n=2000 Da)为原料, 通过迈克尔加成反应合成了pH和活性氧(ROS)双响应型的两亲性聚β硫酯化合物(D-D-P), 利用核磁共振(NMR)对聚合物结构进行了表征, 利用凝胶渗透色谱(GPC)表征了聚合物D-D-P分子量(M_n=50400). 利用透析法使D-D-P自组装成纳米粒子, 用纳米粒度分析仪(DLS)表征了粒径约280 nm, 用透射电子显微镜(TEM)表征了其形貌. 通过粒径变化测试和尼罗红(NR)荧光测试对纳米粒子在酸性(pH≈5)和氧化条件下(H₂O₂)的解散行为进行了研究, 验证了D-D-P的pH和ROS双响应性能. 通过紫外吸收测试对包裹抗癌药物阿霉素(DOX)的纳米粒子在酸性和氧化条件下的释放进行了研究, 并且在MCF-7细胞中对DOX的释放进行了进一步的验证.

关键词: 聚β硫酯, 纳米粒子, pH响应, ROS响应, 自组装

The Michael addition reaction, which is a mild reaction between activated olefins and nucleophiles, has been widely used in synthesis of tailored macromolecular architectures. We designed a copolymer nanoparticle to obtain the ROS and pH dual responsive capability. We synthesized the amphiphilic poly(β-thioester)s copolymers (D-D-P) composed of di(ethylene glycol) diacrylate (DEDA), DL-dithiothreitol (DTT), acryloyl chloride (AC) and hydrophilic PEG-SH with average M_n=2000 g·mol^-1 via Michael addition reaction. The reactions are facile and controllable, and the structures of acquired copolymers are well characterized. The structures of the polymers were confirmed by ¹H NMR, and the number molecular weight and distribution of the copolymer D-D-P was measured by GPC (M_n=50400). D-D-P could self-assemble into nanoparticles with core-shell structures by dialysis method due to the composition of hydrophilic side chains and hydrophobic polymer backbones. After the preparation of ROS and pH dual responsive D-D-P nanoparticles in phosphate buffer solution, the morphology and size of D-D-P nanoparticles were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) showed that the number size distribution of nanoparticles was around 280 nm. Nile Red (NR) is a unique neutral hydrophobic molecule, which shows very weak fluorescence in aqueous solution and can emit strong fluorescence in the hydrophobic environment. NR absorption and emission spectra are strongly dependent on environment polarity, which make it as a probe molecule that is widely used in the evaluation of microenvironment polarity. The disassembly behaviors of D-D-P nanoparticles were investigated by the change of the nanoparticle size and NR fluorescence spectra. The diameter of nanoparticle decreased under pH 5 and ROS environment conditions, and the NR fluorescence also became weak under pH 5 and ROS environment conditions, which could be attributed to the gradual dissociation of nanoparticles, proving the ROS and pH dual responsive properties of the poly(β-thioester)s. The release behaviors of the DOX encapsulated D-D-P nanoparticles in acidic and oxidative condition were studied by the UV absorption and were further proved in MCF-7 cells.

Key words: poly(β-thioester)s, nanoparticles, pH-responsive, ROS-responsive, self-assembly

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赵文静, 乔增莹, 段中余, 王浩. pH和氧化双响应性聚β硫酯化合物的制备及其聚集性质的研究[J]. 化学学报, 2016, 74(3): 234-240.

Zhao Wenjing, Qiao Zengying, Duan Zhongyu, Wang Hao. Synthesis and Self-assembly of pH and ROS Dual Responsive Poly(β-thioester)s[J]. Acta Chim. Sinica, 2016, 74(3): 234-240.

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pH和氧化双响应性聚β硫酯化合物的制备及其聚集性质的研究

Synthesis and Self-assembly of pH and ROS Dual Responsive Poly(β-thioester)s

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