摘要
以(邻、间、对)苯二胺为连接臂将葡萄糖酸与胆固醇相连接,设计合成了3种含苯环结构的糖类小分子胶凝剂.通过核磁、质谱、红外光谱、元素分析对所得化合物进行了结构表征,系统考察了3种胶凝剂分子在常见30种溶剂中的胶凝行为.实验结果表明,间位连接的胶凝剂C2G的胶凝能力明显优于邻位和对位连接的胶凝剂C1G和胶凝剂C3G,且C2G在DMSO中最低胶凝浓度可达0.06%(w/v).胶凝剂的分子结构及浓度,以及溶剂极性对胶凝剂在溶剂中的胶凝行为、自组装聚集体的形貌和流变学性能均有显著影响.流变学结果表明C2G/DMSO凝胶体系具有较好的机械稳定性和剪切触变性.红外光谱和变温、变浓度核磁表明胶凝剂分子中葡萄糖酸残基之间的氢键及胆固醇和苯环之间的π-π堆积作用是该类超分子凝胶形成的两大驱动力.XRD结果表明胶凝剂C2G在DMSO中以层状模型堆积.
Three glucose derivatives containing benzene rings were designed and prepared by using(o-,m-,p-) phenylenediamine as linkers to connect gluconic acid with cholesterol.The structures and compositions of all these compounds are characterized by ~1H NMR,MS(ESI),FTIR spectroscopy,and elemental analysis.Their gelation abilities were evaluated in 30 commonly used solvents.It can be seen that the gelation abilities of the compounds are dependent strongly on the spacer structures of them,compound C2G with a critical gelation concentration(CGC) of 0.06%(w/v) in DMSO.The spacer structure,the concentration of the gelator and the nature of the solvent play a crucial role in the morphologies and rheological properties of their xerogels.It is worth mentioning that C2G/DMSO gel possesses smart and reversible thixotropic property.As revealed by FT-IR and ~1H NMR,hydrogen-bonding between glucono units and π-π stacking between cholesteryl and benzene groups are important in the formation of the gels.XRD study revealed that C2G assembled into a layered structure in its DMSO gel.
引文
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