结合大分子拥挤环境下的糖基化反应与自组装两步法,制备了安全而新型的具有核壳结构的纳米凝胶.首先,通过水相体系中的Maillard反应使亲水性大豆多糖(SSPS)共价连接到大豆分离蛋白(SPI)上形成两亲性嵌段共聚物;然后,在疏水聚集及静电吸引作用力的驱动下诱导接枝共聚物自组装形成SPI-SSPS纳米凝胶.原子力显微镜与透射电子显微镜分析表明,SPI-SSPS纳米凝胶为分布均匀、具有核壳结构的球形粒子,以亲水性的SPI为壳,以交联的SSPS为核;利用圆二色光谱法与荧光光谱法表征了SPI-SSPS纳米凝胶的结构,结果表明,SPI-SSPS纳米凝胶中蛋白的三级结构发生改变,疏水基团暴露于蛋白表面使纳米凝胶内部形成疏水微区,有利于荷载疏水性药物;稳定性实验结果表明,所制备的SPI-SSPS纳米凝胶具有环境稳定性,在一定的pH值与生理离子强度范围内粒子基本不变,于4℃能稳定储藏120 d以上.因此,SPI-SSPS纳米凝胶在生物医药领域具有广阔的应用前景.
A "two-step"method,which involved Maillard reaction in macromolecular crowding environment and self-assembly approach,has been adopted to fabricate the novel and safe core-shell nanogels. First,amphiphilic graft copolymers were synthesized by soluble soy polysaccharide( SSPS) covalently attaching to soy protein isolate( SPI) via Maillard wet-heating reaction. Second,the resultant conjugates( SSC) were induced by both hydrophobic and electrostatic interaction to self-assemble soy protein isolate-soluble soy polysaccharide( SPI-SSPS) nanogels. Microscopic technology indicated that the SPI-SSPS nanogels were well-separated and spherical in shape with obvious core-shell structures: the hydrophilic soy polysaccharide constituted the shell and the cross-linked soy protein constituted the core. Spectroscopy investigation revealed that the tertiary structure of protein in nanogels was changed and the non-polar groups were exposed to the surface of soy protein to develop the hydrophobic compartments in the core of SPI-SSPS nanogels,which might offer a promising potential for drugs encapsulating via hydrophobic attraction. The SPI-SSPS nanogels exhibited remarkable stability against pH and NaCl concentration change,and they were pretty stable against 120 d storage at 4 ℃. All of these valuable properties provide a great potential for practical application in the field of biomedicine.