中文摘要
通过超分子相互作用,共聚物(尤其是嵌段共聚物)在溶液中可以自组装形成丰富多样的胶束形态,为构筑功能性纳米材料提供了广阔的应用前景。接枝共聚物主链骨架上可以提供数量可观的功能团,更容易实现自组装结构的功能化,但复杂的枝化结构限制了其自组装形态多样性的研究。在此,本项目以可生物降解的低聚糖为主链骨架,通过三甲基硅部分保护/己内酯开环共聚/脱保护三步法,得到了结构可控的两类两亲性生物降解接枝共聚物,低聚壳聚糖-g-聚己内酯和麦芽七糖-g-聚己内酯。通过调控接枝共聚物中主链和支链的长度比,特别强调合成具有主链短-支链长的长缨状(tassel-shaped)接枝共聚物,而且由于主链骨架由糖环组成,具有一定的刚性,因此形成的接枝共聚物为rod-coil型共聚物。这两类rod-coil型长缨状接枝共聚物可以在水溶液中形成囊泡、内嵌式囊泡、囊泡串等多种自组装形态,同时支链聚己内酯链段的结晶诱导形成了复合的分级有序结构。由于所得接枝共聚物具有良好的生物降解性和生物相容性,作为功能性纳米材料在生物医药领域将具有非常重要的实用价值。
英文摘要
Copolymers (especially block copolymers) in selective solvents can self-organize into abundant micellar morphologies by supramolecular interaction, which provide abundant applications in building the functional nano materials. Compared with linear block copolymers, graft counterparts may provide integration of considerable functionalities onto polymer backbone that can be addressed chemically after the self-assembly process. However, in most cases, the complicated branched structure of a graft copolymer precludes studies on morphological diversity. Here, two kinds of biodegradable graft copolymers, COS-g-PCL and MH-g-PCL, were controlled synthesized using protection/deprotection technique of COS via trimethylsilyl groups and ring-opening polymerization of ε-caprolactone, based on chitooligosaccharide(COS) and maltoheptose(MH) as the hydrophilic short rigid backbone and poly(ε-caprolactone) (PCL) as the hydrophobic long side chain. The obtained graft copolymers are rod-coil and tassel-shaped and can form multiple self-assembled morphologies such as vesicles, interconnected vesicles, cluster of vesicles and so on. At the same time, more hierarchical structures can be formed due to the crystalline of PCL graft chains. The formation of biodegradable and biocompatible aggregates makes them interesting systems as potential attractive functional nano-hybrid materials with potential applications in biotechnology.
结题摘要
通过超分子相互作用,共聚物(尤其是嵌段共聚物)在溶液中可以自组装形成丰富多样的胶束形态,为构筑功能性纳米材料提供了广阔的应用前景。接枝共聚物主链骨架上可以提供数量可观的功能团,更容易实现自组装结构的功能化,但复杂的枝化结构限制了其自组装形态多样性的研究。在此,本项目以可生物降解的低聚糖为主链骨架,通过三甲基硅部分保护/己内酯开环共聚/脱保护三步法,得到了结构可控的两类两亲性生物降解接枝共聚物,低聚壳聚糖-g-聚己内酯和麦芽七糖-g-聚己内酯。通过调控接枝共聚物中主链和支链的长度比,特别强调合成具有主链短-支链长的长缨状(tassel-shaped)接枝共聚物,而且由于主链骨架由糖环组成,具有一定的刚性,因此形成的接枝共聚物为rod-coil型共聚物。这两类rod-coil型长缨状接枝共聚物可以在水溶液中形成囊泡、内嵌式囊泡、囊泡串等多种自组装形态,同时支链聚己内酯链段的结晶诱导形成了复合的分级有序结构。由于所得接枝共聚物具有良好的生物降解性和生物相容性,作为功能性纳米材料在生物医药领域将具有非常重要的实用价值。
