Zhang Zi-En, Zhang Yi-Fan, Zhang Yan-Zhen, Li Hui-Ling, Sun Li-Ying, Wang Li-Juan, Han Ying-Feng
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Xi'an Key Laboratory of Functional Supramolecular Structure and Materials, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, P. R. China.
J Am Chem Soc. 2023 Apr 5;145(13):7446-7453. doi: 10.1021/jacs.3c00024. Epub 2023 Mar 22.
Herein, a series of face-capped (TrM)L (Tr = cycloheptatrienyl cationic ring; M = metal; L = organosulfur ligand) tetrahedral cages - functionalized with 12 appended crown ether moieties were designed and synthesized. The reversible binding of ammonium cations with peripheral crown ether moieties to adjust internal guest-binding was realized. Combination of a bisammonium linker and cage led to the formation of a supramolecular gel via host-guest interactions between the crown ether moieties and ammonium salts. The obtained supramolecular gel exhibited multiple-stimuli responsiveness, injectability, and excellent self-healing properties and could be further developed to a -based drug delivery system. In addition, the storage modulus of was 20 times higher than that of the model gel without Pd-Pd bonded blocks, and had better self-healing properties compared with the latter, demonstrating the importance of such cages in improving mechanical strength without losing the dynamic properties of the material. The cytotoxicity in vitro of the drug-loaded (doxorubicin or methotrexate) was significantly improved compared to that of free drugs.
在此，设计并合成了一系列用12个附加冠醚部分功能化的面封端（TrM）L（Tr = 环庚三烯基阳离子环；M = 金属；L = 有机硫配体）四面体笼。实现了铵阳离子与外围冠醚部分的可逆结合以调节内部客体结合。双铵连接体与笼的组合通过冠醚部分与铵盐之间的主客体相互作用导致形成超分子凝胶。所获得的超分子凝胶表现出多重刺激响应性、可注射性以及优异的自愈性能，并且可以进一步开发成基于a的药物递送系统。此外，a的储能模量比没有Pd-Pd键合嵌段的模型凝胶高20倍，并且与后者相比具有更好的自愈性能，这证明了此类笼在提高材料机械强度而不丧失其动态性能方面的重要性。与游离药物相比，载药（阿霉素或甲氨蝶呤）a的体外细胞毒性显著提高。
