化学学报 ›› 2015, Vol. 73 ›› Issue (10): 1047-1054.DOI: 10.6023/A15060405 上一篇    下一篇

研究论文

糖响应性生物基聚电解质胶囊的制备与性能研究

冉茂双, 施冬健, 董罕星, 陈明清, 赵增亮   

  1. 江南大学食品胶体与生物技术教育部重点实验室 江南大学化学与材料工程学院 无锡 214122
  • 收稿日期:2015-06-11 出版日期:2015-10-15 发布日期:2015-07-23
  • 通讯作者: 施冬健, 陈明清 E-mail:djshi@jiangnan.edu.cn, mqchen@jiangnan.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No.51173072)和中央高校科技自主项目(JUSRP51408B)资助.

Glucose Responsive Bio-based Polyelectrolyte Capsules by Layer-by-Layer Assembly: Synthesis and Properties

Ran Maoshuang, Shi Dongjian, Dong Hanxing, Chen Mingqing, Zhao Zengliang   

  1. The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122
  • Received:2015-06-11 Online:2015-10-15 Published:2015-07-23
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 51173072) and the Fundamental Research Funds for the Central Universities (JUSRP51408B).

选用功能单体3-氨基苯硼酸(APBA)和乳糖酸(LA)分别对聚谷氨酸(γ-PGA)和壳寡糖(CS)接枝改性后制备聚谷氨酸-g-氨基苯硼酸(γ-PGA-g-APBA)及糖基化壳寡糖(GC); 以二氧化硅微球为模板, 通过γ-PGA-g-APBA和GC间的静电相互作用进行层层自组装, 再经脱除模板则可获得形貌规整可控的生物基胶囊. 通过红外光谱(FTIR)和核磁共振(1H NMR)对聚合物化学结构、接枝率进行表征; 利用Zeta电位监测聚合物电解质层层自组装的进程, 并通过透射电镜(TEM)和扫描电镜(SEM)观测胶囊的形貌. 同时考察了胶囊在不同温度、盐浓度、pH值及糖浓度下的刺激响应, 研究结果表明胶囊在一定的温度、盐浓度、pH值下能稳定存在; 低浓度葡萄糖刺激时胶囊形貌完整, 而高浓度葡萄糖刺激时, 胶囊溶胀直至结构与形貌破坏, 说明功能单体LA和APBA的引入可赋予胶囊具有葡萄糖响应性. 这种具有良好稳定性和葡萄糖响应性的生物基胶囊有望应用于糖尿病的诊断和治疗.

关键词: 葡萄糖响应, 生物基胶囊, 层层自组装, 壳寡糖, 聚谷氨酸

Phenylboronic acid and derivatives that conjugate with diol units to form a reversible ester bond could be used for preparation glucose responsive materials. Glucose responsive materials, such as films, hydrogels, and nanoparticles based on phenylboronic acid have been reported to have well glucose-regulated release insulin. However, in these examples, employed polymers were not full degradability or low biocompatibility. Therefore, this study aims to prepare the bio-based capsules with multi-layers structure to response glucose through the layer-by-layer self-assembly of two natural polymers. Poly(γ-glutamic acid-g-3-aminophenylboronic acid) (γ-PGA-g-APBA) and galactosed chitosan oligosaccharide (GC) were synthesized by grafting 3-aminophenylboronic acid (APBA) and lactobionic acid (LA) to poly-γ-glutamic acid (γ-PGA) and chitosan oligosaccharide (CS), respectively, in the presence of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS) as catalysts. Chemical structures of γ-PGA-g-APBA and GC were determined by proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FT-IR) spectra. Then, polyelectrolyte microspheres (γ-PGA-g-APBA/GC)5@SiO2 were prepared with particle sizes of 240±10 nm, using functionalized silica microspheres as templates by layer-by-layer processes of γ-PGA-g-APBA and GC. Capsules ((γ-PGA-g-APBA/GC)5) with multi-layer structures were obtained by removing SiO2 templates in NH4F/HF (8 mol/L)/(2 mol/L) buffer solution. Sizes and morphologies of polyelectrolyte capsules were characterized by zeta potential, scanning electron micrographs (SEM), transmission electron microscope (TEM) and dynamic light scattering (DLS). The results showed that ((γ-PGA-g-APBA/GC)5) capsules presented unique hollow structures and had a good stability when capsules were incubated at different temperatures, salt concentrations and pH values. Moreover, ((γ-PGA-g-APBA/GC)5) capsules showed a good glucose-responsive property. The capsules were swollen and intact at low glucose concentration, while were destroyed at high glucose concentration. These ((γ-PGA-g-APBA/GC)5) capsules with good stability and glucose-response are expected to be used to the fields of the diagnosis and treatment of diabetes.

Key words: glucose-response, bio-based capsules, layer-by-layer self-assembly, chitosan oligosaccharide, poly(γ-glutamic acid)