摘要
分别合成了苯硼酸修饰的嵌段聚合物聚乙二醇-b-聚(天冬氨酸-co-天冬酰氨基苯硼酸)[PEG-b-P(Aspco-AspPBA)]和含有二硫键及多元二醇的小分子3,3'-二硫代二[1,2(S)-丙二醇](DTBPD).以DTBPD为小分子交联剂,通过二醇单元与苯硼酸之间的共价酯化作用,诱导PEG-b-P(Asp-co-AspPBA)自组装形成以苯硼酸环酯为核、PEG为壳的交联胶束.利用核磁共振氢谱和激光光散射对胶束的结构进行了表征,并分别测定了该胶束在葡萄糖和氧化-还原试剂二硫苏糖醇(DTT)刺激下的响应行为.结果表明,DTBPD可与聚合物链上的苯硼酸形成苯硼酸环酯,通过交联作用诱导聚合物形成胶束.交联度不同时,胶束对于外界刺激(葡萄糖和DTT的响应行为也不同:随着DTT和葡萄糖浓度的增加,交联度高的胶束只发生响应性溶胀,交联度低的胶束则先溶胀,之后溶胀程度较大的部分胶束则发生解体,导致胶束的平均粒径减小.
Phenylboronic acid modified polymer poly (ethylene glycol)-b-poly (aspartic acid-co-aspartamidophenylboronic acid) [ PEG-b-P (Asp-co-AspPBA) ] as well as a cross-linker 3,3 '-dithiobis [ 1,2 ( S ) -propanediol] (DTBPD) which contained disulfide bond and dual-diol groups was successfully synthesized. PEG-b- P(Asp-co-AspPBA) could be mildly cross-linked by DTBPD based on the reaction of PBA and the dual-diol groups, leading to the formation of a novel dual-responsive micelle with boronic ester core and PEG shell. The structure, morphology, and the glucose/redox dual-responsive behavior of the micel]es were systematically investigated by nuclear magnetic resonance(NMR) spectrum and dynamic laser light scattering(DLS). It was demonstrated that the ratio of diol to PBA ( D : B) had influence on the dual-responsive behavior of the micelles. At higher ratio of D : B, only responsive swelling of micelles was observed. While for the micelles with lower ratio of D : B, larger degree of swelling happened and the micelles gradually dissociated under higher concentrations of glucose ordithiothreitol(DTT). This kind of dual-responsive micelles may find application in drug delivery in the future.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2014年第7期1570-1578,共9页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:21274001,91127045,51390483)
国家“九七三”计划项目(批准号:2011CB932503)
教育部长江学者和创新团队发展计划项目(批准号:IRT1257)资助~~
关键词
苯硼酸
二硫键
交联胶束
葡萄糖响应
氧化还原响应
双响应性胶束
Boronic acid
Disulfidebond
Cross-linked micelle
Glucose-response
Redox-response
Dual-responsive mieelle