超高效液相色谱-四极杆-飞行时间高分辨质谱快速筛查确证化妆品中73种常见禁用物质

建立了超高效液相色谱-四极杆-飞行时间高分辨质谱(UPLC-Q-TOF HRMS)同时快速筛查确证化妆品中73种常见禁用物质的方法。样品经饱和氯化钠溶液分散均匀后,采用含0.2%甲酸的乙腈溶液超声提取,50 mg PSA净化,以8000 r/min高速冷冻离心除脂,采用Waters Acquity HSS T3色谱柱(100 mm×2.1 mm, 1.8 μm)分离。采用多反应监测高分辨扫描模式(MRM HR),以保留时间、一级母离子精确质量数、同位素丰度比和二级子离子精确质量数实现化妆品中73种禁用物质的快速筛查和确证,基质匹配外标法定量。实验比较了不同提取溶剂、净化吸附剂、色谱条件和质谱扫描模式对73种禁用物质测定的影响,并考察了膏霜剂和水剂的基质效应。结果表明,73种禁用物质线性关系良好,相关系数(R²)>0.99;检出限为5~150 μg/kg;定量限为15~450 μg/kg;膏霜剂及水剂两种基质在3个加标水平下的回收率为60.3%~130.3%,日内、日间RSD分别为0.8%~10.0%(n=6)和1.1%~15.0%(n=3)。日常风险监测中检出磺胺甲基异噁唑、甲基泼尼松、林可霉素、对乙酰氨基酚、甲氧苄啶、阿法骨化醇、倍他米松戊酸酯、溴莫尼定、氯霉素、氯苯那敏、氯倍他索丙酸酯、克罗米通、益康唑、酮康唑、泼尼松醋酸酯和泼尼松,检出含量范围为0.5~1136.1 mg/kg。该方法准确、快速、简便,可用于化妆品中73种常见禁用物质的检测。

Fast screening and confirmation of 73 common prohibited compounds in cosmetics by ultra performance liquid chromatography-quadrupole-time-of-flight high resolution mass spectrometry

A high throughput screening method based on ultra performance liquid chromatography-quadrupole-time-of-flight high resolution mass spectrometry (UPLC-Q-TOF HRMS) was developed for the simultaneous and rapid confirmation of 73 prohibited compounds in cosmetics. The sample was dispersed in a saturated sodium chloride solution and ultrasonically extracted using acetonitrile containing 0.2% (v/v) formic acid. The resultant solution was centrifuged and then cleaned using dispersive solid phase extraction using a primary secondary amine (PSA) sorbent. The purified solution was centrifuged, and the supernatant was filtered through a 0.22 μm membrane before determination. The optimal pretreatment method was determined by comparing the recovery rates obtained using different extraction solvents and different amounts of purifying agents. The chromatographic separation conditions and mass spectrometry scanning mode were also optimized. Chromatographic separation was performed on an Acquity UPLC HSS T3 column (100 mm×2.1 mm, 1.8 μm) with gradient elution using 0.1% (v/v) formic acid aqueous solution and methanol as mobile phases. The eluent from the column was further detected using Q-TOF HRMS with the high resolution multiple reaction monitoring (MRM HR) scanning mode. Retention time, precise mass of parent ion, isotope abundance ratio, and precise mass of fragment ions were the parameters considered for rapid untargeted screening and confirmation. The matrix effects of water- and cream-based cosmetics were investigated. The matrix effects could be addressed using the matrix matched standard curve method. The correlation coefficients for the 73 prohibited compounds were all >0.99 in the corresponding linear concentration range. The limits of detection (LODs) were in the range of 5-150 μg/kg, and the limits of quantification (LOQs) were in the range of 15-450 μg/kg. Average recoveries were in the range of 60.3%-130.3% at three spiked levels, and the intra-day and inter-day precisions were 0.8%-10.0% (n=6) and 1.1%-15.0% (n=3), respectively. A total of 692 cosmetics samples were screened; 16 positive samples were detected, namely, sulfamethoxazole, meprednisone, lincomycin, 4-acetamidophenol, trimethoprim, alfacalcidol, betamethasone 17-valerate, brimonidine, chloramphenicol, chlorpheniramine, clobetasol propionate, crotamiton, econazole, ketoconazole, prednisone 21-acetate, and prednisone, with content in the range of 0.5-1136.1 mg/kg. The optimized method is accurate, fast, and simple, and it is suitable for the routine detection and rapid screening of common prohibited compounds in cosmetics. In addition, a screening and confirmation library was established for the 650 prohibited compounds using SCIEX OS and Library View software, using information-dependent acquisition (IDA)-MS/MS mode for MS data acquisition. The database contains multiple types of information, including formulas, theoretical exact mass, retention time, precise mass of parent ion, isotope abundance ratio, and fragment ion distribution. The library can be used for the simultaneous and rapid confirmation of prohibited compounds in cosmetics.