Although micellar electrokinetic chromatography-mass spectrometry (MEKC-MS) using bare silica capillary filled with molecular micelles is an advantageous hyphenated technique for chiral analysis, it is still in the developmental stage. This is mainly because of the lower repeatability of retention time and peak area associated with the difficulty in controlling electroosmotic flow on bare silica capillaries. Besides the lower robustness and electrospray erosion of the fused-silica capillary tip, the lifetime is limited for 10-15 runs per capillary column. We have tested a new MEKC-MS method to eradicate this problem using a covalently bonded 2-acrylamido-2-methyl-1-propane-sulfonic acid (AMPS) column filled with free floating molecular micelles, polysodium N-undecenoxy carbonyl-L-leucinate (poly-L-SUCL). Simultaneous enantiomeric separations and MS/MS detection of three β-blockers [atenolol (ATEN), metoprolol (METO) and, pindolol (PINDO)] was achieved within 25 min with improved column lifetime of at least 45-50 runs. Excellent repeatability of retention time was observed for β-blockers, as evidenced by the relative standard deviation of less than 2% and 3% for intra-capillary and inter-capillary column, respectively. The linear calibration range of both β-blockers was simultaneously established using enantiomers of PINDO as an internal standard. The limit of detection and the lower limit of quantitation were 0.2 μg/mL and 0.5 μg/mL, respectively, for both ATEN and METO. Acceptable recovery of the enantiomeric content of the commercial METO tablet (98-99.5%) and ATEN tablet (89-92.5%) were obtained with adequate system suitability for the precision of peak area (≤10% RSD) under optimum conditions. The developed MEKC-MS approach was extended, which provided broader repeatibility of chiral separation to a panel of primary, secondary and tertiary amines as well as one anionic chiral compound.

中文翻译：

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在胶束电动色谱质谱法中建立手性分离的可重复性和耐用性：结合使用共价键合的毛细管柱和分子胶束。

尽管使用填充有分子胶束的裸露二氧化硅毛细管的胶束电动色谱-质谱法（MEKC-MS）是一种有利的手性分析联用技术，但它仍处于开发阶段。这主要是由于保留时间和峰面积的重现性较低，与在裸露的二氧化硅毛细管上难以控制电渗流有关。除了较低的耐用性和熔融石英毛细管尖端的电喷雾腐蚀外，每个毛细管色谱柱的使用寿命还受到10-15次运行的限制。我们已经测试了一种新的MEKC-MS方法，该方法可以使用共价键合的2-丙烯酰胺基-2-甲基-1-丙烷-磺酸（AMPS）色谱柱来消除此问题，该色谱柱填充有自由浮动的分子胶团，聚N-十一碳烯基羰基-L-钠亮氨酸（poly-L-SUCL）。在25分钟内完成了三种β受体阻滞剂[atenolol（ATEN），metoprolol（METO）和pindolol（PINDO）]的同时对映体分离和MS / MS检测，色谱柱寿命延长了至少45-50次。β-阻滞剂的保留时间具有极好的重复性，毛细管内和毛细管间色谱柱的相对标准偏差分别小于2％和3％，这证明了这一点。使用PINDO的对映异构体作为内标同时建立了两个β受体阻滞剂的线性校准范围。ATEN和METO的检出限和定量下限分别为0.2μg/ mL和0.5μg/ mL。商用METO片剂（98-99.5％）和ATEN片剂（89-92）的对映体含量的可接受回收率。获得了5％（％）的样品，并且具有足够的系统适用性，可在最佳条件下获得峰面积的精密度（RSD≤10％）。扩展了已开发的MEKC-MS方法，为一组伯，仲和叔胺以及一种阴离子手性化合物提供了更广泛的手性分离重复性。