Área de Química Orgánica, Universidad de Almería, Carretera de Sacramento, 04120, Almería, Spain.
Langmuir. 2011 Aug 16;27(16):9729-37. doi: 10.1021/la201180u. Epub 2011 Jul 12.
A convenient synthesis of β-cyclodextrin dimers in which the two cyclodextrin units are linked by rigid tethers of relatively short length through their secondary sides is reported. Compounds hexa-2,4-diynediyl- and 1,4-phenylenediethyne-briged β-cyclodextrin dimers are obtained in good yields from mono-2-O-propargyl-β-cyclodextrin through Pd-mediated oxidative homo- and heterocoupling reactions. Isothermal titration calorimetry and NMR spectroscopy (PGSE and 2D-ROESY) are used to determine the thermodynamic parameters (K, ΔH, and TΔS°) for the complexation of such β-cyclodextrin dimers with sodium cholate, deoxycholate, and chenodeoxycholate as well as to estimate the size of the supramolecular structures. The binding of bile salts is enhanced relative to that of native β-cyclodextrin. Although chenodeoxycholate salt binds in a 1:1 fashion, cholate and deoxycholate salts bind in a 1:2 sequential mode.
报道了一种通过二级羟基将两个环糊精单元以相对较短刚性连接体连接起来的β-环糊精二聚体的简便合成方法。通过 Pd 介导的氧化同偶联和杂偶联反应，从单-2-O-炔丙基-β-环糊精出发，以良好的收率得到了六亚-2,4-二炔基-和 1,4-苯二乙炔桥联β-环糊精二聚体。等温滴定量热法和 NMR 光谱（PGSE 和 2D-ROESY）用于确定此类β-环糊精二聚体与胆酸钠、脱氧胆酸钠和鹅去氧胆酸钠络合的热力学参数（K、ΔH 和 TΔS°），并估计超分子结构的大小。与天然β-环糊精相比，胆汁盐的结合增强。尽管鹅去氧胆酸盐以 1:1 的方式结合，但胆酸盐和脱氧胆酸盐以 1:2 的顺序方式结合。
