School of Pharmacy, Shenyang Pharmaceutical University, Shenyang, Liaoning Province, 110016, China.
School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang, Liaoning Province, 110016, China.
Anal Bioanal Chem. 2016 Sep;408(23):6381-92. doi: 10.1007/s00216-016-9753-z. Epub 2016 Jul 23.
This report describes, for the first time, the simultaneous enantioselective determination of proton-pump inhibitors (PPIs-omeprazole, lansoprazole, pantoprazole, and rabeprazole) in environmental water matrices based on solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and chiral liquid chromatography-tandem mass spectrometry. The optimized results of SPE-DLLME were obtained with PEP-2 column using methanol-acetonitrile (1/1, v/v) as elution solvent, dichloroethane, and acetonitrile as extractant and disperser solvent, respectively. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralpak IC (250 mm × 4.6 mm, 5 μm) column, under isocratic conditions at 0.6 mL min(-1) flow rate. The analytes were detected in multiple reaction monitoring (MRM) mode by triple quadrupole mass spectrometry. Isotopically labeled internal standards were used to compensate matrix interferences. The method provided enrichment factors of around 500. Under optimal conditions, the mean recoveries for all eight enantiomers from the water samples were 89.3-107.3 % with 0.9-10.3 % intra-day RSD and 2.3-8.1 % inter-day RSD at 20 and 100 ng L(-1) levels. Correlation coefficients (r (2)) ≥ 0.999 were achieved for all enantiomers within the range of 2-500 μg L(-1). The method detection and quantification limits were at very low levels, within the range of 0.67-2.29 ng L(-1) and 2.54-8.68 ng L(-1), respectively. This method was successfully applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in wastewater and river water, making it applicable to the assessment of the enantiomeric fate of PPIs in the environment. Graphical Abstract Simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.
本报告首次描述了基于固相萃取结合分散液相微萃取（SPE-DLLME）和手性液相色谱-串联质谱法，同时测定环境水样中质子泵抑制剂（PPIs-omeprazole、lansoprazole、pantoprazole 和 rabeprazole）对映体选择性的情况。采用 PEP-2 柱，以甲醇-乙腈（1/1，v/v）为洗脱溶剂，二氯甲烷和乙腈分别为萃取和分散溶剂，对 SPE-DLLME 进行了优化。采用纤维素手性固定相，Chiralpak IC（250mm×4.6mm，5μm）柱，在 0.6mL min(-1)流速下，在反相色谱条件下进行分离和测定。采用三重四极杆质谱在多重反应监测（MRM）模式下检测分析物。使用同位素标记内标补偿基质干扰。该方法的富集因子约为 500。在最佳条件下，所有 8 种对映体从水样中的平均回收率为 89.3-107.3%，20 和 100ng L(-1)浓度下日内 RSD 为 0.9-10.3%，日间 RSD 为 2.3-8.1%。所有对映体在 2-500μg L(-1)范围内的相关系数（r (2)）均≥0.999。方法的检出限和定量限均处于很低的水平，分别为 0.67-2.29ng L(-1)和 2.54-8.68ng L(-1)。该方法成功应用于废水中和河水中目标分析物浓度和对映体分数的测定，适用于评估环境中 PPIs 的对映体命运。
