一种通过两个二硫键连接的γ-环糊精双链体：合成、结构与包合物
A γ-cyclodextrin duplex connected with two disulfide bonds: synthesis, structure and inclusion complexes.
作者信息
Volkov Sergey, Kumprecht Lukáš, Buděšínský Miloš, Lepšík Martin, Dušek Michal, Kraus Tomáš
机构信息
Institute of Organic Chemistry and Biochemistry AS CR, v.v.i., Flemingovo nám. 2, 166 10 Prague 6, Czech Republic.
出版信息
Org Biomol Chem. 2015 Mar 14;13(10):2980-5. doi: 10.1039/c4ob02464h.
Per(2,3,6-tri-O-benzyl)-γ-cyclodextrin was debenzylated by DIBAL-H to produce a mixture of C6(I),C6(IV) and C6(I),C6(V) isomeric diols, which were separated and isolated. The C2-symmetrical C6(I),C6(V) diol was transformed into dithiol and dimerized to produce a γ-cyclodextrin duplex structure. A crystal structure revealed tubular cavity whose peripheries are slightly elliptically distorted. The solvent accessible volume of the cavity of the γ-CD duplex is about 740 Å(3). Due to this large inner space the duplex forms very stable inclusion complexes with steroids; bile acids examined in this study show binding affinities to the γ-cyclodextrin duplex in the range of 5.3 × 10(7) M(-1)-1.9 × 10(8) M(-1).
通过二异丁基氢化铝（DIBAL-H）对全（2,3,6-三-O-苄基）-γ-环糊精进行脱苄基反应，生成C6（I）、C6（IV）和C6（I）、C6（V）异构二醇的混合物，对其进行分离和提纯。将具有C2对称性的C6（I）、C6（V）二醇转化为二硫醇并二聚化，以生成γ-环糊精双链体结构。晶体结构显示出其管状空腔的周边略有椭圆畸变。γ-环糊精双链体空腔的溶剂可及体积约为740 ų。由于这种较大的内部空间，双链体与甾体形成非常稳定的包合物；本研究中检测的胆汁酸对γ-环糊精双链体的结合亲和力在5.3×10⁷ M⁻¹至1.9×10⁸ M⁻¹范围内。
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