2-呋喃甲硫醇修饰环糊精形成互锁式螺旋柱状超分子的自组装行为

doi:10.6023/A12121070

摘要/Abstract

利用单-(6-氧-对甲基苯磺酰基)-β-环糊精和2-呋喃甲硫醇反应得到单修饰环糊精, 单[6-硫-6-(2-甲基呋喃)]-β-环糊精. 通过X-ray衍射分析及核磁光谱等方法研究了其在溶液和固态中形成线状超分子的分子自组装行为. 结果表明, 化合物在固态中通过呋喃基团从第二面羟基连续插入到另一个环糊精的空腔, 形成了互锁式螺旋柱状超分子, 而且在溶液中也显示了相似的自组装行为, 其键合常数K及聚合度n分别为450 mol^-1·L和1.9.

关键词: 修饰环糊精, 2-呋喃甲硫醇, 自组装, 晶体结构, 超分子

The mono-modified β-cyclodextrin, mono-[6-S-6-(2-methylfuran)]-β-cyclodextrin, was synthesized by the substituting 2-furanmethanethiol for toluenesulfonyl group at the primary rim of β-cyclodextrin. Its self-assembly behavior was measured in both solution and the solid state by X-ray crystallography and ¹H NMR spectroscopy. In the crystal structure, the complex, C₄₇H₁₀₆O₅₁S, crystallizes in the orthorhombic space group P212121. The furan group is located above the primary rim of β-cyclodextrin and stretches slantwise along the side wall of β-cyclodextrin with the dihedral angle of 104.4° between furan ring and the plane of glycosidic oxygen atoms O(4) of β-cyclodextrin. The furan group is inserted deeply into the hydrophobic cavity of the adjacent β-cyclodextrin from the second hydroxyl rim and makes an angle of 67.6° with the O(4) atoms plane of the adjacent β-cyclodextrin. The dihedral angle of the O(4) atoms plane between the adjacent β-cyclodextrin is 38.4°. The consequence is the formation of an interlocked helical columnar superstructure formed by the self-assembly of the complex molecules in which the modified cyclodextrins are stacked along a two-fold screw axis parallel to the a crystal axis. Thus each molecule behaves both a host and a guest molecule. And the position and orientation of the furan ring within the cyclodextrin cavity is determined by host guest interactions which include the van der Waals contacts and hydrogen bonds between the furan ring and cyclodextrin. The interlocked helical column is stabilized by the hydrogen bonds formed between the primary and secondary hydroxyl groups of the adjacent cyclodextrin or through intervening water molecules. Furthermore, ROESY data indicate that the furan ring is included in the cyclodextrin cavity, which is in accordance with the conformation of the solid state structure. ¹H NMR concentration dependent studies show that the complex molecule forms a dimer at concentrations of >10^-4 mol·L^-1. And the effective binding constant K and the aggregation number n were calculated to be 450 mol^-1·L and 1.9, respectively.

Key words: modified cyclodextrin, 2-furanmethanethiol, self-assembly, crystal structure, supramolecule

引用此文

韩聪, 徐喆, 刁春华, 陈鑫, 刘靖, 郭敏杰, 樊志. 2-呋喃甲硫醇修饰环糊精形成互锁式螺旋柱状超分子的自组装行为[J]. 化学学报, 2013, 71(03): 439-442.

Han Cong, Xu Zhe, Diao Chunhua, Chen Xin, Liu Jing, Guo Minjie, Fan Zhi. Self-assembly Behavior of Interlocked Helical Supramolecule of Cyclodextrin Modified by 2-Furanmethanethiol[J]. Acta Chimica Sinica, 2013, 71(03): 439-442.

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