Tabani Hadi, Mahyari Mojtaba, Sahragard Ali, Fakhari Ali Reza, Shaabani Ahmad
Department of Pure Chemistry, Faculty of Chemistry, Shahid Beheshti University, Evin, Tehran, I.R. Iran.
Electrophoresis. 2015 Jan;36(2):305-11. doi: 10.1002/elps.201400370. Epub 2014 Nov 14.
Introducing a new class of chiral selectors is an interesting work and this issue is still one of the hot topics in separation science and chirality. In this study, for the first time, sulfated maltodextrin (MD) was synthesized as a new anionic chiral selector and then it was successfully applied for the enantioseparation of five basic drugs (amlodipine, hydroxyzine, fluoxetine, tolterodine, and tramadol) as model chiral compounds using CE. This chiral selector has two recognition sites: a helical structure and a sulfated group which contribute to three corresponding driving forces; inclusion complexation, electrostatic interaction, and hydrogen binding. Under the optimized condition (buffer solution: 50 mM phosphate (pH 3.0) and 2% w/v sulfated MD; applied voltage: 18 kV; temperature: 20°C), baseline enantioseparation was observed for all mentioned chiral drugs. When instead of sulfated MD neutral MD was used under the same condition, no enantioseparation was observed which means the resolution power of sulfated MD is higher than neutral MD due to the electrostatic interaction between sulfated groups and protonated chiral drugs. Also, the countercurrent mobility of negatively charged MD (sulfated MD) allows more interactions between the chiral selector and chiral drugs and this in turn results in a successful resolution for the enantiomers. Furthermore, a higher concentration of neutral MD (approximately five times) is necessary to achieve the equivalent resolution compared with the negatively charged MD.
引入一类新型手性选择剂是一项有趣的工作,并且这个问题仍然是分离科学和手性领域的热门话题之一。在本研究中,首次合成了硫酸化麦芽糊精(MD)作为一种新型阴离子手性选择剂,然后使用毛细管电泳(CE)成功地将其应用于对五种碱性药物(氨氯地平、羟嗪、氟西汀、托特罗定和曲马多)作为模型手性化合物进行对映体分离。这种手性选择剂有两个识别位点:一个螺旋结构和一个硫酸化基团,它们分别产生三种相应的驱动力;包合络合、静电相互作用和氢键作用。在优化条件下(缓冲溶液:50 mM磷酸盐(pH 3.0)和2% w/v硫酸化MD;施加电压:18 kV;温度:20°C),所有上述手性药物均实现了基线对映体分离。当在相同条件下使用中性MD而非硫酸化MD时,未观察到对映体分离,这意味着由于硫酸化基团与质子化手性药物之间的静电相互作用,硫酸化MD的拆分能力高于中性MD。此外,带负电荷的MD(硫酸化MD)的逆流迁移率使得手性选择剂与手性药物之间有更多的相互作用,这反过来又导致对映体的成功拆分。此外,与带负电荷的MD相比,需要更高浓度(约五倍)的中性MD才能实现等效的拆分。