本论文中，我们利用基于葫芦脲的动态可逆的主客体相互作用，成功构筑了结构可控的葫芦脲超分子组装体，并将其可控调节的特点与抗菌材料的构筑相结合，提升了原有抗菌材料的性能。具体的研究工作如下：我们成功实现了基于ns-葫芦[10]脲的线形超分子聚合物的可控制备和可控降解。我们首先报道了ns-葫芦[10]脲、葫芦[7]脲与客体分子的自分类识别现象，通过向体系内加入刚性的葫芦[7]脲，避免了超分子聚合过程中二聚和环化对超分子聚合物结构的不利影响。因此可以得到较高分子量的基于ns-葫芦[10]脲的线形超分子聚合物，并且通过调控加入葫芦[7]脲的摩尔比来逐步调控超分子聚合物的聚合和降解。这一策略拓展了基于ns-葫芦[10]脲的超分子组装体系。我们设计并发展了一种选择性抑菌的分子自由基光热材料。实验发现，苝二酰亚胺和葫芦[7]脲形成的超分子复合物可以被兼性厌氧细菌还原生成自由基阴离子，而需氧菌则未表现出该还原现象。因此可以通过兼性厌氧菌选择性地生成自由基阴离子，在近红外光照射下经光热转化实现选择性抑菌。这种新的基于微生物原位还原能力的差异选择性光热治疗可能在调节微生物群落的平衡、药物治疗等领域有着巨大的应用前景。我们设计并发展了一种具有优异抗菌活性且可调控的抗菌超分子聚合物材料。首先合成了两边萘基、中间联苯基团的双官能度单体分子，通过利用双官能度单体分子、小分子抗菌剂和葫芦[8]脲的自分类识别性质，成功制备了侧链抗菌超分子聚合物材料。由于其具有局部富集抗菌剂的作用，因此相较小分子抗菌剂，其对大肠杆菌的抗菌效果有明显的提升，而且利用超分子聚合物可控降解的性质也可以很好地调节其抗菌性能。该抗菌材料有望在生物、医药等方面展现良好的应用前景。综上，本论文沿着“组装到功能”这一主线，开展了基于葫芦脲主客体化学的可控组装和可控功能的相关研究，期望基于葫芦脲的可控组装超分子体系在未来能够展现出更多的应用前景。
In this thesis, we fabricated cucurbiturils-based host-guest assemblies with dynamicity, reversibility and controllability, developing a novel topology of supramolecular polymers and a series of antibacterial materials. The research work can be summarized as follows:A nor-seco-cucurbit[10]uril (ns-CB[10]) based linear supramolecular polymer was firstly constructed via self-sorting. By adding CB[7] into the mixture of ns-CB[10] and monomers, the bulky of CB[7] could help to avoid two unfavorable factors of supramolecular polymerization, namely dimerization and cyclization. Therefore, high molecular weight linear supramolecular polymers could be fabricated. Besides, the polymerization and degradation of supramolecular polymers could also be controlled by regulating the molar ratio of CB[7]. This strategy has extended the supramolecular assembly based on ns-CB[10].A novel kind of supramolecular radical based photothermal material with selective bacteriostasis was designed and developed. It was found that the supramolecular complex formed by perylene diimide and CB[7] could be selectively reduced to radical anion by facultative anaerobes, while the supramolecular complex could not be reduced by aerobic bacteria. Therefore, the selective bacteriostasis could be realized by the photothermal conversion ability of radical anion under near-infrared irradiation. It is anticipated that this method may lead to a novel bacteria-responsive photothermal therapy to regulate the balance of bacterial flora, and present a great application prospect in the fields of clinical treatment in the future.An antibacterial supramolecular polymer was developed that behaved enhanced antibacterial efficacy and controlled degradability. We firstly synthesized bifunctional monomers containing two naphthyl moieties and a biphenyl moiety. The antibacterial supramolecular polymer was successfully fabricated by bifunctional monomers, antibacterial agents and CB[8] via self-sorting. Because of the local enrichment of antimicrobial agents on antibacterial supramolecular polymer, the antibacterial performance against E. coli was significantly enhanced. Moreover, the antibacterial performances could also be well regulated by controllable degradation of antibacterial supramolecular polymers. This kind of antibacterial supramolecular polymeric materials is expected to present good application prospects in medicine and clinical treatments.In summary, in this thesis, cucurbiturils-based host-guest assemblies with controllable structures and functions have been fabricated, along with a line of ‘function based on assembly’. It is anticipated that the cucurbiturils-based controllable supramolecular system may be extended to more functional applications in the future.
