Nishi Yuki, Yamane Naoe, Tanimoto Toshiko
School of Pharmaceutical Sciences, Mukogawa Women's University, 11-68 Koshien, Nishinomiya 663-8179, Japan.
Carbohydr Res. 2007 Nov 5;342(15):2173-81. doi: 10.1016/j.carres.2007.06.016. Epub 2007 Jun 23.
Three positional isomers of 6(I),6(n)-di-O-(beta-L-fucopyranosyl)-cyclomaltoheptaose [6(I),6(n)-di-O-(beta-L-Fuc)-beta-cyclodextrin, -betaCD, n=II-IV] were chemically synthesized using the corresponding authentic compounds, 6(I),6(n)-di-O-(tert-butyldimethylsilyl)-betaCD (n=II-IV), as the fucosyl acceptors, and 2,3,4-tri-O-acetyl-L-fucopyranosyl trichloroacetimidate as the fucosyl donor. Their structures were analyzed by HPLC, MS, and NMR spectroscopy. The hemolytic activities of L-Fuc-betaCDs were lower than that of betaCD, while the solubilities of these branched CDs in water were much higher than that of betaCD. The molecular interaction between these compounds and the fucose-binding lectin Aleuria aurantia lectin (AAL) was investigated using an optical biosensor based on a surface plasmon resonance (SPR) technique. The order of binding affinity, as a function of the fucose-binding position, was 6(I),6(IV)->6(I),6(III)->6(I),6(II)-di-O-(beta-L-Fuc)-betaCD>6-O-(beta-L-Fuc)-betaCD.
以相应的纯品化合物6(I),6(n)-二-O-(叔丁基二甲基甲硅烷基)-β-环糊精（n = II-IV）作为岩藻糖基受体，2,3,4-三-O-乙酰基-L-岩藻糖基三氯乙酰亚胺酯作为岩藻糖基供体，化学合成了6(I),6(n)-二-O-(β-L-岩藻糖基吡喃糖基)-环麦芽七糖[6(I),6(n)-二-O-(β-L-岩藻糖基)-β-环糊精，-βCD，n = II-IV]的三种位置异构体。通过高效液相色谱法、质谱法和核磁共振光谱法对其结构进行了分析。L-Fuc-βCDs的溶血活性低于βCD，而这些支链环糊精在水中的溶解度远高于βCD。使用基于表面等离子体共振（SPR）技术的光学生物传感器研究了这些化合物与岩藻糖结合凝集素橙黄网柄牛肝菌凝集素（AAL）之间的分子相互作用。作为岩藻糖结合位置的函数，结合亲和力顺序为6(I),6(IV)->6(I),6(III)->6(I),6(II)-二-O-(β-L-岩藻糖基)-βCD>6-O-(β-L-岩藻糖基)-βCD。
