Coupling Desorption Electrospray Ionization with Solid-Phase Microextraction for Screening and Quantitative Analysis of Drugs in Urine
Coupling Desorption Electrospray Ionization with Solid-Phase Microextraction for Screening and Quantitative Analysis of Drugs in Urine
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DOI：
10.1021/ac101295g
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发表时间：
2010-09-01
影响因子：
7.4
通讯作者：
Wiseman, Justin M.
中科院分区：
文献类型：
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作者：
Kennedy, Joseph H.;Aurand, Craig;Wiseman, Justin M.
采用解吸电喷雾电离质谱仪(DESI-MS)直接分析了硅胶C-18包被的固相微萃取(SPME)纤维，用于分析尿液中的药物。该方法将一种简单、廉价、无溶剂的样品前处理技术与DESI-MS和MS/MS的专属性和快速特性结合在一起。使用专门设计的涂有硅胶-C-18固定相的SPME纤维从原始尿液中提取7种药物。每个固相微萃取装置在温和搅拌下插入未处理的尿液中，然后取出、冲洗，并直接用DESI-MS(MS/MS)进行分析。通过将该方法与飞行时间(TOF)质谱仪相结合，可在较宽的质量范围内进行快速筛选，同时使用三重四极质谱计的选择反应监测(SRM)进行定量分析。通过制备尿样中7种药物化合物的校正标准和质量控制(QC)样品来评价固相微萃取-MS/MS方法的性能，其中甲丙氨酸酯的制备范围为200~10000 ng/mL。为每个分析物构建的校准曲线的R-2>；为0.99。对于低质量控制样品，精密度(%CV)范围为1-11%，准确度范围(%偏差)为3-38%。高质量控制样品的精密度和准确度范围为0.9%至8%和-31%至-8%。用SPME-DESI-MS/MS方法对实际接触药物的尿样进行筛查，结果与常规免疫分析和GC/MS分析结果一致。固相微萃取纤维的液体解吸和LC/MS/MS方法也与固相微萃取-MS/MS方法吻合较好。
Direct analysis of silica C-18-coated solid-phase microextraction (SPME) fibers using desorption electrospray ionization mass spectrometry (DESI-MS) for the purpose of analyzing drugs from raw urine is presented. The method combines a simple, inexpensive, and solvent-less sample preparation technique with the specificity and speed of DESI-MS and MS/MS. Extraction of seven drugs from raw urine is performed using specially designed SPME fibers coated uniformly with silica-C-18 stationary phase. Each SPME device is inserted into unprocessed urine under gentle agitation and, then, removed, rinsed, and analyzed directly by DESI-MS (MS/MS). Rapid screening over a wide mass range is afforded by coupling the method with a time of flight (TOF) mass spectrometer while quantitative analysis is performed using selected reaction monitoring (SRM) using a triple quadrupole mass spectrometer. The performance of the SPME DESI-MS/MS method was evaluated by preparing calibration standards and quality control (QC) samples of the seven drug compounds from urine over a range from 20 to 1000 ng/mL, with the exception of meprobamate which was prepared from 200 to 10000 ng/mL. The calibration curves constructed for each analyte had an R-2 > 0.99. The range of precision (%CV) and accuracy values (% bias) for low QC samples was 1-11% and 3-38%, respectively. Precision and accuracy values for high QC samples range from 0.9 to 8% and -31 to -8%. Results from urine specimens of actual exposure to drugs screened using the SPME DESI-MS/MS method showed good agreement with the conventional immunoassays and GC/MS analysis. Liquid desorption of the SPME fiber followed by LC/MS/MS also showed good agreement with the SPME DESI-MS/MS method.