超高效液相色谱-串联质谱法测定化妆品中同分异构体构型糖皮质激素
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摘要
目的 建立超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)测定化妆品中同分异构体构型糖皮质激素(glucocorticoids, GCs)的分析方法。方法样品经饱和氯化钠分散、乙腈提取,亚铁氰化钾-醋酸锌沉淀大分子基质后,通过分散固相萃取技术(QuEChERS)净化。以0.1%甲酸水溶液和乙腈作为流动相迚行梯度洗脱,采用多反应监测模式(multiple reaction monitoring, MRM)对美白祛斑类化妆品中同分异构体构型糖皮质激素迚行定量和定性检测。结果 本方法完成了对糖皮质激素中最难以分离的差向同分异构体倍他米松、地塞米松以及它们的衍生物倍他米松醋酸酯、地塞米松醋酸酯的分离检测。在5.0、10和20μg/kg添加水平时的回收率为78.6%～102.7%,相对标准偏差小于10.60%(n=6),方法定量限为6.0μg/kg。结论 该方法快速、稳定、灵敏度高、选择性好,适合分析检测化妆品中非法添加的GCs类化合物。
Objective To establish a method for the determination of isomer configuration glucocorticoids in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry. Methods The sample was dispersed by saturated sodium chloride, extracted by acetonitrile and precipitated macromolecular matrix by potassium ferrocyanide and zinc acetate. Matrix solid-phase dispersion extraction(QuEChERS) was used for purification. Gradient elution was performed with 0.1% formic acid(A) and acetonitrile(B) as mobile phase, and multiple reaction monitoring(MRM) was for the quantitative and qualitative of the isomer configuration glucocorticoids in whitening cosmetics and qualitative testing. Results The method accomplished the separation and detection of the isomeric isomers of betaperdone, dexamethasone and their derivatives, betamethasone acetate and dexamethasone acetate, which were the most difficult to separate in glucocorticoids. The recoveries at the addition levels of 5.0, 10 and 20 μg/kg were 78.6%-102.7%, and the relative standard deviations were less than10.60%(n=6). The limit of quantification was 6.0 μg/kg. Conclusion This method is fast, accurate, sensitive and reliable, which is suitable for the analysis and detection of illegally added GCs compounds in cosmetics.
Objective To establish a method for the determination of isomer configuration glucocorticoids in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry. Methods The sample was dispersed by saturated sodium chloride, extracted by acetonitrile and precipitated macromolecular matrix by potassium ferrocyanide and zinc acetate. Matrix solid-phase dispersion extraction(QuEChERS) was used for purification. Gradient elution was performed with 0.1% formic acid(A) and acetonitrile(B) as mobile phase, and multiple reaction monitoring(MRM) was for the quantitative and qualitative of the isomer configuration glucocorticoids in whitening cosmetics and qualitative testing. Results The method accomplished the separation and detection of the isomeric isomers of betaperdone, dexamethasone and their derivatives, betamethasone acetate and dexamethasone acetate, which were the most difficult to separate in glucocorticoids. The recoveries at the addition levels of 5.0, 10 and 20 μg/kg were 78.6%-102.7%, and the relative standard deviations were less than10.60%(n=6). The limit of quantification was 6.0 μg/kg. Conclusion This method is fast, accurate, sensitive and reliable, which is suitable for the analysis and detection of illegally added GCs compounds in cosmetics.
引文
[1]罗辉泰,黄晓兰,吴惠勤,等.QuEChERS-同位素稀释-液相色谱-高分辨飞行时间质谱法高通量筛查化妆品中86种糖皮质激素[J].分析化学,2017,(9):1381-1388.Luo HT,Huang XL,Wu HQ,et al.High throughput screening of 86 kinds of glucocorticoids in cosmetics using QuEChERS and isotope dilution-liquid chromatography coupled to high resolution time-of-flight mass spectrometry[J].J Chin J Anal Chem,2017,(9):1381-1388.
[2]闵昡艳,王鸣人,吴杨,等.UPLC-MS/MS法检测抗菌乳膏中的痕量地塞米松和倍他米松[J].药物分析杂志,2017,37(7):1248-1255.Min CY,Wang MR,Wu Y,et al.Determination of dexamethasone and betamethasone in creams of antimicrobial agent by UPLC-MS/MS[J].Chin J Pharm Anal,2017,37(7):1248-1255.
[3]张静,严小红,赖俊敏,等.液相色谱-串联质谱法同时测定化妆品中非法添加标准外的3种糖皮质激素[J].今日药学,2018,(11):733-735.Zhang J,Yan XH,Lai JM,et al.Simultaneous detection of 3 other standard glucocorticoids illegally added in cosmetics by liquid chromatography-tandem mass spectrometry[J].Pharm Today,2018,(11):733-735.
[4]张怀辉,候英,杨式华,等.LC-Q-TOF和LC-MS/MS测定化妆品中地索奈德及甲基泼尼松龙醋酸酯同分异构体[J].云南大学学报(自然科学版),2018,40(3):561-567.Zhang HH,Hou Y,Yang SH,et al.Rapid determination of desonide and methylprednisolone acetate in cosmetics by time of flight mass spectrometry and liquid chromatography-tandem mass spectrometry[J].JYunnan Univ(Nat Sci Ed),2018,40(3):561-567.
[5]罗辉泰,黄晓兰,吴惠勤,等.分散固相萃取-液相色谱-串联质谱法同时快速测定化妆品中81种糖皮质激素[J].色谱,2017,35(8):816-825.Luo HT,Huang XL,Wu HQ,et al.Simultaneous rapid determination of81 glucocorticoids in cosmetics by dispersive solid extraction and liquid chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2017,35(8):816-825.
[6]李杨杰,赵祥龙,岑立怡,等.高分辨质谱对化妆品中非法添加标准外糖皮质激素的快速筛查及应用[J].香料香精化妆品,2018,1(2):58-62.Li YJ,Zhao XL,Cen LY,et al.Rapid screening and detection of glucocorticoids illegally added in cosmetics by Q-TOF method[J].Flav Frag Cosmet,2018,1(2):58-62.
[7]高家敏,李红霞,项新华,等.化妆品中地塞米松检测能力验证研究[J].中国药事,2017,31(9):1017-1020.Gao JM,Li HX,Xiang XH,et al.Proficiency testing of determination of dexamethasone in cosmetics[J].Chin Pharm Aff,2017,31(9):1017-1020.
[8]阮浩澜,陈琪,罗卓雅.面膜类化妆品滥用糖皮质激素的概况与危害[J].今日药学,2018,(10):717-720.Ruan HL,Chen Q,Luo ZY.The Situation and harm of glucocorticoid abuse in cosmetic masks[J].Pharm Today,2018,(10):717-720.
[9]李兆永,王凤美,牛增元,等.超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱快速筛查化妆品中的24种激素[J].色谱,2014,32(5):477-484.Li ZY,Wang FM,Niu ZY,et al.Screening and confirmation of 24hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry[J].Chin J Chromatogr,2014,32(5):477-484.
[10]李强,张晓光,马俊美,等.超高效液相色谱-高分辨率质谱法筛查化妆品中12种糖皮质激素[J].分析测试学报,2016,35(2):179-184.Li Q,Zhang XG,Ma JM,et al.Screening of 12 glucocorticoids in cosmetics by high performance liquid chromatography-high resolution mass spectrometry[J].J Instrum Anal,2016,35(2):179-184.
[11]国家食品药品监督管理总局.化妆品安全技术规范(2015年版)[Z].China Food and Drug Administration.Safety and technical standards for cosmetics(2015 Edition)[Z].
[12]言慧洁,潘源虎.HPLC-MS/MS法同时检测抗风湿中药制剂中非法添加9种糖皮质激素的方法建立[J].中国合理用药探索,2018,15(10):68-72.Yan HJ,Pan YH.Simultaneous determination of 9 glucocorticoids illegally adulterated in anti-rheumatic Chinese medicine preparations by HPLC-MS/MS[J].Chin J Rat Drug Use,2018,15(10):68-72.
[13]GB/T 24800-2009中华人民共和国国家标准化妆品中41种糖皮质激素的测定液相色谱/串联质谱法和薄层层析法[S].GB/T 24800-2009 National Standard of the People?s Republic of China-Determination of 41 glucocorticoids in cosmetics-LC-MS/MS and TLC method[S].
[14]罗辉泰,黄晓兰,吴惠勤,等.固相萃取/液相色谱-串联质谱法同时测定面膜类化妆品中非法添加的53种糖皮质激素[J].分析测试学报,2016,35(2):119-126.Luo HT,Huang XL,Wu HQ,et al.Simultaneous determination of 53kinds of glucocorticoids illegally added in facial mask cosmetics by solid-phase extraction with liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2016,35(2):119-126.
[15]马强,王超,王星,等.超高效液相色谱-串联质谱法同时测定化妆品中的22种磺胺类药物[J].分析化学,2008,(12):1683-1689.Ma Q,Wang C,Wang X,et al.Simultaneous determination of 22sulfonamides in cosmetics by ultra performance liquid chromatography tandem mass spectrometry[J].Chin J Anal Chem,2008,(12):1683-1689.
[2]闵昡艳,王鸣人,吴杨,等.UPLC-MS/MS法检测抗菌乳膏中的痕量地塞米松和倍他米松[J].药物分析杂志,2017,37(7):1248-1255.Min CY,Wang MR,Wu Y,et al.Determination of dexamethasone and betamethasone in creams of antimicrobial agent by UPLC-MS/MS[J].Chin J Pharm Anal,2017,37(7):1248-1255.
[3]张静,严小红,赖俊敏,等.液相色谱-串联质谱法同时测定化妆品中非法添加标准外的3种糖皮质激素[J].今日药学,2018,(11):733-735.Zhang J,Yan XH,Lai JM,et al.Simultaneous detection of 3 other standard glucocorticoids illegally added in cosmetics by liquid chromatography-tandem mass spectrometry[J].Pharm Today,2018,(11):733-735.
[4]张怀辉,候英,杨式华,等.LC-Q-TOF和LC-MS/MS测定化妆品中地索奈德及甲基泼尼松龙醋酸酯同分异构体[J].云南大学学报(自然科学版),2018,40(3):561-567.Zhang HH,Hou Y,Yang SH,et al.Rapid determination of desonide and methylprednisolone acetate in cosmetics by time of flight mass spectrometry and liquid chromatography-tandem mass spectrometry[J].JYunnan Univ(Nat Sci Ed),2018,40(3):561-567.
[5]罗辉泰,黄晓兰,吴惠勤,等.分散固相萃取-液相色谱-串联质谱法同时快速测定化妆品中81种糖皮质激素[J].色谱,2017,35(8):816-825.Luo HT,Huang XL,Wu HQ,et al.Simultaneous rapid determination of81 glucocorticoids in cosmetics by dispersive solid extraction and liquid chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2017,35(8):816-825.
[6]李杨杰,赵祥龙,岑立怡,等.高分辨质谱对化妆品中非法添加标准外糖皮质激素的快速筛查及应用[J].香料香精化妆品,2018,1(2):58-62.Li YJ,Zhao XL,Cen LY,et al.Rapid screening and detection of glucocorticoids illegally added in cosmetics by Q-TOF method[J].Flav Frag Cosmet,2018,1(2):58-62.
[7]高家敏,李红霞,项新华,等.化妆品中地塞米松检测能力验证研究[J].中国药事,2017,31(9):1017-1020.Gao JM,Li HX,Xiang XH,et al.Proficiency testing of determination of dexamethasone in cosmetics[J].Chin Pharm Aff,2017,31(9):1017-1020.
[8]阮浩澜,陈琪,罗卓雅.面膜类化妆品滥用糖皮质激素的概况与危害[J].今日药学,2018,(10):717-720.Ruan HL,Chen Q,Luo ZY.The Situation and harm of glucocorticoid abuse in cosmetic masks[J].Pharm Today,2018,(10):717-720.
[9]李兆永,王凤美,牛增元,等.超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱快速筛查化妆品中的24种激素[J].色谱,2014,32(5):477-484.Li ZY,Wang FM,Niu ZY,et al.Screening and confirmation of 24hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry[J].Chin J Chromatogr,2014,32(5):477-484.
[10]李强,张晓光,马俊美,等.超高效液相色谱-高分辨率质谱法筛查化妆品中12种糖皮质激素[J].分析测试学报,2016,35(2):179-184.Li Q,Zhang XG,Ma JM,et al.Screening of 12 glucocorticoids in cosmetics by high performance liquid chromatography-high resolution mass spectrometry[J].J Instrum Anal,2016,35(2):179-184.
[11]国家食品药品监督管理总局.化妆品安全技术规范(2015年版)[Z].China Food and Drug Administration.Safety and technical standards for cosmetics(2015 Edition)[Z].
[12]言慧洁,潘源虎.HPLC-MS/MS法同时检测抗风湿中药制剂中非法添加9种糖皮质激素的方法建立[J].中国合理用药探索,2018,15(10):68-72.Yan HJ,Pan YH.Simultaneous determination of 9 glucocorticoids illegally adulterated in anti-rheumatic Chinese medicine preparations by HPLC-MS/MS[J].Chin J Rat Drug Use,2018,15(10):68-72.
[13]GB/T 24800-2009中华人民共和国国家标准化妆品中41种糖皮质激素的测定液相色谱/串联质谱法和薄层层析法[S].GB/T 24800-2009 National Standard of the People?s Republic of China-Determination of 41 glucocorticoids in cosmetics-LC-MS/MS and TLC method[S].
[14]罗辉泰,黄晓兰,吴惠勤,等.固相萃取/液相色谱-串联质谱法同时测定面膜类化妆品中非法添加的53种糖皮质激素[J].分析测试学报,2016,35(2):119-126.Luo HT,Huang XL,Wu HQ,et al.Simultaneous determination of 53kinds of glucocorticoids illegally added in facial mask cosmetics by solid-phase extraction with liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2016,35(2):119-126.
[15]马强,王超,王星,等.超高效液相色谱-串联质谱法同时测定化妆品中的22种磺胺类药物[J].分析化学,2008,(12):1683-1689.Ma Q,Wang C,Wang X,et al.Simultaneous determination of 22sulfonamides in cosmetics by ultra performance liquid chromatography tandem mass spectrometry[J].Chin J Anal Chem,2008,(12):1683-1689.