物理化学学报 >> 2013, Vol. 29 >> Issue (09): 2005-2012.doi: 10.3866/PKU.WHXB201306142

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基于胆固醇的新型小分子胶凝剂的合成与胶凝行为

薛敏1,2, 苗青2, 房喻2   

  1. 1 西安文理学院化学与化学工程学院, 西安 710065;
    2 陕西师范大学化学化工学院, 应用表面与胶体化学教育部重点实验室, 西安 710062
  • 收稿日期:2013-03-27 修回日期:2013-06-13 发布日期:2013-08-28
  • 通讯作者: 房喻 E-mail:yfang@snnu.edu.cn
  • 基金资助:

    国家自然科学基金(21273141)资助项目

Synthesis and Gelation Properties of Cholesterol-Based New Low-Molecular-Mass Gelators

XUE Min1,2, MIAO Qing2, FANG Yu2   

  1. 1 School of Chemistry and Chemical Engineering, Xi'an University of Arts and Science, Xi'an 710065, P. R. China;
    2 Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China
  • Received:2013-03-27 Revised:2013-06-13 Published:2013-08-28
  • Contact: FANG Yu E-mail:yfang@snnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21273141).

摘要:

设计合成了3种以丙二胺为连接臂(L)、苯环为A单元的A(LS)2型双胆固醇(S)类小分子胶凝剂: 化合物1(邻位), 化合物2(间位)和化合物3(对位), 考察了其在30种溶剂中的胶凝行为. 结果表明, 苯环取代位置的不同对化合物的胶凝性质有决定性影响. 就胶凝溶剂的数量来讲, 对位取代的化合物3的胶凝能力明显高于邻位和间位取代的化合物12. 此外, 化合物23可以形成5个室温胶凝体系, 且化合物3/二甲苯凝胶透明、柔韧,以至于可以形成超分子薄膜. 傅里叶变换红外(FTIR)光谱和核磁共振氢谱(1H NMR)研究表明, 胶凝剂分子之间的氢键和π-π堆积作用在凝胶形成过程中发挥了一定的作用. X射线衍射(XRD)研究表明在化合物1/苯凝胶中, 胶凝剂分子聚集为六方堆积结构, 进而形成贯穿整个凝胶体系的网络结构.

关键词: 小分子胶凝剂, 胆固醇, 自组装, 室温胶凝, 凝胶薄膜

Abstract:

Three novel dimeric cholesteryl-based low-molecular-mass gelators (LMMGs), which have the structure A(LS)2, were designed and synthesized. In the structures, 1,3-diaminopropane is a linker (L), A is a benzene ring, and S is cholesteryl. According to the positions of the substituents on the benzene ring, the as-prepared compounds are denoted by 1 (o-position), 2 (m-position), and 3 (p-position), respectively. Their gelation properties were evaluated in 30 solvents. It was revealed that the relative positions of the two cholesteryl moieties on the benzene ring play a crucial role in the gelation behaviors of the compounds. In terms of the number of solvents gelled by the tested compounds, compound 3 is a more versatile gelator than compounds 1 and 2; compounds 2 and 3 can form five gels at room temperature. Furthermore, the compound 2/xylene gel is transparent and flexible, and forms a supramolecular filmin the wet state. Fouriertransform infrared (FTIR) spectroscopy and 1H nuclear magnetic resonance (1H NMR) spectroscopy studies demonstrated that intermolecular hydrogen bonding and π-π stacking among the molecules of the gelators play important roles in the gelation process. X-ray diffraction (XRD) analysis showed that the aggregate of compound 1 from its benzene gel adopts a hexagonal packing mode as the elementary structure of the gel networks.

Key words: Low-molecular-mass gelator, Cholesterol, Self-assembly, Roomtemperature gelation, Gel film

MSC2000: 

  • O641.3