目的:采用固相萃取-超高效液相色谱-串联质谱(SPE-UPLC-MS/MS)法建立医用冷敷贴中17个化学物质的检测方法,该法适用于常见医用冷敷贴基质。方法:重点考察了固相萃取柱类型、洗脱溶剂种类及溶剂用量。样品用甲醇超声提取后,与水以1∶9的比例混合,经Agilent Bond Elut HLB固相萃取柱净化,以甲醇-异丙醇(1∶1)进行洗脱,采用Waters ACQUITY UPLC BEH C18(100 mm×2.1 mm,1.8 μm)色谱柱,以乙腈-0.1%甲酸溶液(含0.5 mmol·L-1乙酸铵)为流动相进行分离。在电喷雾离子源(ESI)正负离子模式下电离,多反应监测(MRM)模式下测定。结果:17个化合物在相应的测定范围内呈良好的线性关系,相关系数(r)均大于0.99,该方法的检测限(LOD)为0.01~13.32 μg·g-1,定量限(LOQ)为0.02~26.64 μg·g-1。在3种加样水平下,回收率范围为77.7%~108.5%,RSD(n=6)为0.62%~4.7%。应用本方法对35批次医用冷敷贴样品进行分析检测,结果8批次检出双氯芬酸钠,每片检出量为0.09~27.55 mg。结论:该方法简便,准确度高,灵敏度好,可用于医用冷敷贴中非法添加化学药物的检测,为检测医用冷敷贴中的非法添加提供了技术支持。
Abstract
Objective: To establish a method for the determination of 17 kinds of anti-allergic compounds in medical cold compress by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry(SPE-UPLC-MS/MS). Common medical cold compress matrices were suitable for this new method. Methods: Three pretreatment methods were compared: prime pass-through column purification, SPE purification including HLB and MCX solid-phase extraction. The pretreatment was optimized by focusing on the kind of solid-phase extraction, the type and volume of elution solvents. The analytes were extracted using methanol and then mixed with water at the ratio of 1∶9 in volume, purified with an Agilent Bond Elut HLB column. Waters ACQUITY UPLC BEH C18(100 mm×2.1 mm,1.8 μm)column was used with 0.1% formic acid(with 0.5 mmol·L-1 ammonium acetate)-acetonitrile as mobile phases by gradient elution for separating 17 compounds. Detection was carried out by positive and negative electrospray ionization(ESI)mass spectrometer in multiple reaction monitor (MRM) mode. Results: All the 17 kinds of compounds showed good linearity in their reasonable ranges(r)＞0.99, the limit of detection (LOD) and quantification(LOQ)were 0.01-13.32 μg·g-1 and 0.02-26.64 μg·g-1, respectively. The average recoveries of at three spiked levels were in range of 77.7%-108.5%, with RSDs (n=6) were 0.62%-4.7%. The content range of diclofenac sodium in positive samples was 0.09-27.55 mg per tablet. Conclusion: The method is simple, sensitive and reliable, and is suitable for determination of 17 illegally add chemical drugs in medical cold compress. Moreover, the method might provide technological support for the detection of illegal additions in medical cold compress.
关键词
超高效液相色谱-串联质谱(UPLC-MS/MS) /
固相萃取(SPE) /
糖皮质激素 /
解热镇痛 /
麻醉剂 /
医用冷敷贴
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Key words
ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) /
solid phase extraction (SPE) /
glucocorticoids /
antipyretic and analgesic /
anesthetic /
medical cold compress
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脚注
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基金
* 浙江省食品药品监管系统科技计划项目(2021027)
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