UPLC-MS/MS法测定补肾抗疲劳中成药及保健食品中非法添加的9种PDE-5抑制剂及其衍生物
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摘要
目的建立补肾抗疲劳类中成药及保健食品中非法添加9种5型磷酸二酯酶(PDE-5)抑制剂及其衍生物的超高效液相色谱-串联三重四级杆质谱(UPLC-MS/MS)快速检测方法。方法采用Agilent Zorbax SB C18(100 mm×2.1 mm,1.8μm)色谱柱分离,以乙腈-10 mmol·L~(-1)乙酸铵(含体积分数0.1%甲酸)为流动相,梯度洗脱,在电喷雾离子化正离子模式下,以动态多反应监测模式(DMRM)检测。结果 9种PDE-5抑制剂及其衍生物在相应浓度范围内与峰面积均呈良好线性关系,r均大于0.998,检测限(S/N=3)为0.03~0.22 ng·mL~(-1),3个浓度水平回收率均在92.4%~109.8%,RSD均在0.70%~4.0%(n=6)。收集的86批样品中有58批呈非法添加阳性。结论本方法快速,准确,灵敏度高和专属性强,可用于补肾抗疲劳类中成药及保健食品中9种PDE-5抑制剂及其衍生物的定性筛查和定量检测。
Objective To develop a method for the simultaneous determination of 9 phosphodiesterase-5 inhibitors which were illegally added to invigorant herbal medicines and dietary supplements by UPLC-MS/MS. Methods Samples was separated on an Agilent Zorbax SB C18(100 mm×2.1 mm, 1.8 μm) column with gradient elution. The mobile phase consisted of acetonitrile-10 mmol·L~(-1) ammonium acetate water solution containing 0.1% formic acid. Electrospray ionization source in positive ion mode was used to analyze 9 phosphodiesterase-5 inhibitors in the dynamic multiple reaction monitoring mode. Results A good resolution of 9 phosphodiesterase-5 inhibitors was obtained. The correlation coefficients within the linearity were above 0.998. The limits of detection(S/N = 3) ranged 0.03-0.22 ng·mL~(-1). The average recoveries were at 92.4%-109.8% with relative standard deviations at 0.70%-4.0%(n = 6) at 3 spiked levels. Illegal addition of chemical drugs was found in 58 of the 86 tested samples. Conclusion The method is rapid, accurate, sensitive and suitable for the confirmation of 9 illegally added phosphodiesterase-5 inhibitors in invigorant herbal medicines and dietary supplements.
Objective To develop a method for the simultaneous determination of 9 phosphodiesterase-5 inhibitors which were illegally added to invigorant herbal medicines and dietary supplements by UPLC-MS/MS. Methods Samples was separated on an Agilent Zorbax SB C18(100 mm×2.1 mm, 1.8 μm) column with gradient elution. The mobile phase consisted of acetonitrile-10 mmol·L~(-1) ammonium acetate water solution containing 0.1% formic acid. Electrospray ionization source in positive ion mode was used to analyze 9 phosphodiesterase-5 inhibitors in the dynamic multiple reaction monitoring mode. Results A good resolution of 9 phosphodiesterase-5 inhibitors was obtained. The correlation coefficients within the linearity were above 0.998. The limits of detection(S/N = 3) ranged 0.03-0.22 ng·mL~(-1). The average recoveries were at 92.4%-109.8% with relative standard deviations at 0.70%-4.0%(n = 6) at 3 spiked levels. Illegal addition of chemical drugs was found in 58 of the 86 tested samples. Conclusion The method is rapid, accurate, sensitive and suitable for the confirmation of 9 illegally added phosphodiesterase-5 inhibitors in invigorant herbal medicines and dietary supplements.
引文
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[15]胡婷婷,曲晓宇,康明芹,等.高效液相色谱-高分辨质谱快速筛查和确证保健品中非法添加的壮阳药物[J].色谱,2015,33(8):897-901.
[16]Kee CL,Ge X,Gilard V,et al.A review of synthetic phosphodiesterase type 5 inhibitors(PDE-5i)found as adulterants in dietary supplements[J].J Pharm Biomed Anal,2018,147(SI):163-170.
[2]张小龙,王昆,吴先富,等.中药及保健食品中非法添加状况分析[J].中国药师,2014,17(10):1749-1753.
[3]段琼,马春艳,封淑华.保健酒及酒类制品中非法添加PDE-5抑制剂及其衍生物的监测及结果分析[J].药物分析杂志,2017,37(2):277-282.
[4]张鲁南,张梦琪,陈莉,等.性保健品中可能违禁添加7种药物的LC-MS/MS法测定[J].中国医药工业杂志,2014,41(10):755-758.
[5]Erica LB,Anna TK,Jeffrey PW,et al.A case report of fatal desmethyl carbodenafil toxicity[J].J Anal Toxicol,2017,41(3):250-255.
[6]石岩,魏锋,朱晓鹏,等.中药及保健食品中PDE5抑制剂检测的再研究[J].药物分析杂志,2014,34(1):121-125.
[7]周嵩煜,周天祥.NIR法对补肾壮阳类中成药浓缩丸中非法添加西地那非的定性分析[J].中国药事,2010,24(12):1210-1215.
[8]彭耀文,申兰慧,杨敏智,等.建立应急检验模型快速筛查及确证片剂中添加的枸橼酸西地那非[J].中国药事,2015,29(3):303-307.
[9]王玉,曹玲,罗疆南.显微共聚焦拉曼光谱法检测非法添加的化学壮阳药[J].中国药学杂志,2011,46(10):789-795.
[10]欧爱芬,张挺,彭述辉.胶体金免疫层析试纸条法和HPLC-QTOF-MS法检测保健品中那非类化学药物的比较[J].仲恺农业工程学院学报,2017,30(3):32-36.
[11]邢俊波,曹红,张炯,等.高效液相色谱法同时测定补肾壮阳类中成药及保健食品中非法添加7种化药成分[J].时珍国医国药,2014,25(2):451-453.
[12]雷毅,黄艳婷,陈林,等.高效液相色谱法同时快速测定壮阳类保健品中的18种非法添加物[J].理化检验(化学分册),2016,52(3):249-254.
[13]曲晓宇,董雷,张四喜,等.HPLC-MS/MS法同时检测抗疲劳药物及保健品中非法添加的7种壮阳类化学药物[J].中国药房,2013,24(33):3129-3131.
[14]马云云,谭金峰,徐玉文,等.液相色谱-高分辨质谱法测定壮阳类保健品中非法添加物[J].理化检验(化学分册),2015,51(3):325-330.
[15]胡婷婷,曲晓宇,康明芹,等.高效液相色谱-高分辨质谱快速筛查和确证保健品中非法添加的壮阳药物[J].色谱,2015,33(8):897-901.
[16]Kee CL,Ge X,Gilard V,et al.A review of synthetic phosphodiesterase type 5 inhibitors(PDE-5i)found as adulterants in dietary supplements[J].J Pharm Biomed Anal,2018,147(SI):163-170.