甘油掺杂提高4-正十六烷氧基苯甲腙干凝胶降低冰片挥发性作用研究

Study on glycerol doping to enhance the volatility-reducing effect of 4-n-hexadecyloxybenzaldehyde hydrazone xerogel on borneol

摘要

目的: 制备“冰片-小分子胶凝剂”干凝胶,评价其对冰片挥发性的影响。方法: 以对羟基苯甲醛为起始化合物,经过Williamson醚化反应、缩合反应得到目标小分子胶凝剂;将冰片与小分子胶凝剂溶于无水乙醇,制备“冰片-小分子胶凝剂”凝胶,真空冷冻干燥后得到“冰片-小分子胶凝剂”干凝胶;利用扫描电子显微镜(scanning electron microscope,SEM)观察干凝胶微观形态,差示扫描量热仪(differential scanning calorimetry,DSC)测定干凝胶相变温度,傅里叶变换红外光谱(Fourier transform infrared spectroscopy,FT-IR)分析凝胶形成的驱动力;通过加速挥发实验对比冰片、“冰片-小分子胶凝剂”干凝胶、“冰片-小分子胶凝剂-甘油”干凝胶在10 h内冰片的挥发损失率。结果: “冰片-小分子胶凝剂”质量比2∶1、3∶1、4∶1时在无水乙醇中均形成凝胶;小分子胶凝剂SEM图为多层片状结构,“冰片-小分子胶凝剂”干凝胶质量比2∶1、3∶1、4∶1时的微观结构分别为块状、片状、网状结构,证明形成组装体;甘油加入“冰片-小分子胶凝剂”体系后形成干凝胶,其微观结构未发生显著改变。DSC中不同质量比“冰片-小分子胶凝剂”干凝胶吸热峰有相应变化;FT-IR中“冰片-小分子胶凝剂”干凝胶与“冰片-小分子胶凝剂-甘油”干凝胶中羟基伸缩振动峰向低波数移动,证实氢键参与凝胶形成。在50 ℃加速挥发实验中,冰片在5 h内损失率为39.34%,“冰片-小分子胶凝剂”干凝胶质量比 4∶1 时在5 h内冰片损失率为17.40%,添加甘油后,冰片损失率降低至9.98%。结论: “冰片-小分子胶凝剂”干凝胶可以降低冰片挥发性,且甘油的加入可进一步降低冰片挥发。

Abstract

Objective: To prepare a borneol-low molecular organic gelator xerogel and evaluate its effect on borneol volatility. Methods: 4-Hydroxybenzaldehyde was used as the starting material, and the target low molecular organic gelator was synthesized through Williamson etherification reaction and condensation reaction. The gel was prepared by dissolving borneol and low molecular organic gelator in anhydrous ethanol and subsequently undergoing vacuum freeze-drying to remove the solvent, resulting in the borneol-low molecular organic gelator xerogel. The microscopic morphology of the xerogel was observed by scanning electron microscope (SEM). The phase transition temperature was determined by differential scanning calorimeter (DSC). The driving force for the gel formation was analyzed by Fourier transform infrared spectroscopy (FT-IR). The loss of borneol from borneol sample, borneol-low molecular organic gelator xerogel, and the borneol-low molecular organic gelator-glycerol xerogel were compared by accelerated evaporation experiment over 10 h. Results: Mixtures of borneol and low molecular organic gelator with mass ratios of 2∶1, 3∶1 and 4∶1 formed a gel in anhydrous ethanol. SEM imaging revealed that the low molecular organic gelator showed a multilayered sheet-like structure. In contrast, the microstructures of the borneol-low molecular organic gelator xerogel with mass ratios of 2∶1, 3∶1 and 4∶1 showed a bulk, sheet-like and reticulate structure, respectively, which proved that the assemblies were formed. Furthermore, the addition of glycerol to the borneol-low molecular organic gelator system did not significantly alter the microstructure of the resulting xerogel. DSC analysis showed that the heat absorption peaks of the borneol-low molecular organic gelator xerogel varied with the mass ratios. FT-IR analysis revealed a shift in the hydroxyl group stretching vibration to lower wavenumbers for both borneol-low molecular organic gelator xerogel and borneol-low molecular organic gelator-glycerol xerogel, confirming that hydrogen bonding was involved in the formation of gel. After the 5 h accelerated volatilization test at 50 ℃, the borneol loss rate was 39.34% from borneol sample, while it was 17.40% from the 4∶1 borneol-low molecular organic gelator xerogel, and 9.98% after glycerol was added. Conclusion: The borneol-low molecular organic gelator xerogel reduces the volatility of borneol, with a further reduction observed upon the addition of glycerol.

关键词

小分子胶凝剂 / 冰片 / 自组装 / 挥发性 / 甘油掺杂

Key words

low molecular organic gelators / borneol / self-assembly / volatility / glycerol doping

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基金资助

国家中医药管理局高水平中医药重点学科建设项目(304-174010324025);陕西中医药大学校级项目(604200002/303)