高效液相色谱-串联质谱检测保健酒中非法添加物艾地那非
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摘要
目的:采用高效液相色谱-串联质谱(high performance liquid chromatography-tandem mass spectrometry,HPLC-MS/MS)法,建立保健酒中非法添加物艾地那非的检测方法。方法:使用Agilent RRDH Eclipse-plus C18色谱柱(2.1 mm×100 mm,1.8μm),以0.1%甲酸-乙腈溶液为流动相A、0.1%乙酸-20 mmol/L乙酸铵溶液为流动相B进行梯度洗脱。通过HPLC-MS/MS系统中全扫描模式对艾地那非进行定性分析,多反应监测模式对艾地那非进行定量分析。结果:该方法线性r~2大于0.99,精密度相对标准偏差小于3%,不同质量浓度样品平均回收率为97.31%~100.66%,检出限为0.6 ng/m L,定量限为1.6 ng/m L。结论:此方法测定准确、灵敏度高、分离度高,可用于保健酒中非法添加物艾地那非的筛选和检测。
Objective: To develop a detection method for aildenafil adulterated in health wine using high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods: The chromatography was performed using an Agilent RRDH Eclipse plus C18 column(2.1 mm × 100 mm, 1.8 μm), with a mobile phase consisting of acetonitrile-0.1%formic acid(phase A) and 0.1% acetic acid-20 mmol/L ammonium acetate(phase B) by gradient elution. Qualitative analysis of aildenafil was conducted under full-scan model, and quantitative analysis in the multiple reaction monitoring(MRM) model. Results: The method was linear with a correlation coefficient(r~2) > 0.99, and its precision, expressed as RSD, was < 3%. The recoveries of aildenafil at different spiked concentrations ranged from 97.31% to 100.66%. The limit of detection(LOD) was 0.6 ng/m L and the limit of quantitation(LOQ) was 1.6 ng/m L. Conclusion: This method is fast and accurate with a high sensitivity and a high degree of separation. It can be used for the screening and detection of aildenafil illegally added in health wine.
Objective: To develop a detection method for aildenafil adulterated in health wine using high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods: The chromatography was performed using an Agilent RRDH Eclipse plus C18 column(2.1 mm × 100 mm, 1.8 μm), with a mobile phase consisting of acetonitrile-0.1%formic acid(phase A) and 0.1% acetic acid-20 mmol/L ammonium acetate(phase B) by gradient elution. Qualitative analysis of aildenafil was conducted under full-scan model, and quantitative analysis in the multiple reaction monitoring(MRM) model. Results: The method was linear with a correlation coefficient(r~2) > 0.99, and its precision, expressed as RSD, was < 3%. The recoveries of aildenafil at different spiked concentrations ranged from 97.31% to 100.66%. The limit of detection(LOD) was 0.6 ng/m L and the limit of quantitation(LOQ) was 1.6 ng/m L. Conclusion: This method is fast and accurate with a high sensitivity and a high degree of separation. It can be used for the screening and detection of aildenafil illegally added in health wine.
引文
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[2]邓鲲鹏,罗卓雅,雷毅,等.补肾壮阳类健康产品中艾地那非的检测方法研究[J].中国药学杂志,2011,46(18):1441-1444.
[3]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LCMS/MS法测定[J].中国医药工业杂志,2010,41(10):755-758.DOI:10.3969/j.issn.1001-8255.2010.10.011.
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[5]王维亭,赵专友,何小云,等.爱地那非对阴茎勃起功能的影响[J].中国药理学与毒理学杂志,2005(3):220-225.DOI:10.3321/j.issn:1000-3002.2005.03.011.
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[8]国家食品药品监督管理总局.国家食品药品监督管理总局关于51家保健酒、配制酒企业69种产品违法添加行为的通告(2015年第45号)[EB/OL].(2015-07-31)[2015-11-30].http://www.sda.gov.cn/WS01/CL0087/125640.html.
[9]张园,郝刚,闵春艳,等.UPLC-DAD-Q-TOF-MS/MS测定缓解体力疲劳类保健品中非法添加的化学物质[J].中国执业药师(论著),2014,11(8):15-19.DOI:10.3969/j.issn.1672-5433.2014.08.06.
[10]高青,张喆,郭洪祝,等.中药及保健食品中PDE5抑制剂检测方法研究及未知衍生物的发现[J].中国药学杂志,2008,43(2):142-146.DOI:10.3321/j.issn:1001-2494.2008.02.019.
[11]梁丽梅.中药中违法添加枸橼酸西地那非的含量测定方法研究[J].中国药房,2006,17(24):1917-1918.DOI:10.3969/j.issn.1001-0408.2006.24.034.
[12]赵维,冉兰,魏伯平.HPLC-TOF/MS检测补肾强身胶囊中西地那非和他达那非[J].药物分析杂志,2008,28(10):1692-1697.
[13]高咏莉,邬晓鸥,肖丽和,等.HPLC-MS/MS法测定补肾壮阳类药品或保健品中非法添加羟基豪莫西地那非的研究[J].中成药,2009,31(7):1058-1061.DOI:10.3969/j.issn.1001-1528.2009.07.022.
[14]ZOU P,SHARON S Y,HOU P L,et al.Simultaneous determination of synthetic phosphodiesterase-5 inhibitors found in a dietary supplement and pre-mixed bulk powders for dietary supplements using high-performance liquid chromatography with diode array detection and liquid chromatography-electrospray ionization tandem mass spectrometry[J].Journal of Chromatography A,2006,1104(1/2):113-122.DOI:10.1016/j.chroma.2005.11.103.
[15]陈安珍,王尊文,杨钊,等.UPLC-MS/MS检测补肾壮阳类中成药及保健品中添加的化学药[J].中成药,2009,31(11):1712-1714.
[16]张翠英,李振国,徐金玲,等.超高效液相色谱-串联质谱法测定中成药中非法添加枸橼酸西地那非的研究[J].中成药,2007,29(9):1315-1318.DOI:10.3969/j.issn.1001-1528.2007.09.022.
[17]GE X W,LOW M Y,ZOU P,et al.Structural elucidation of a PDE-5 inhibitor detected as an adulterant in a health supplement[J].Journal of Pharmaceutical and Biomedical Analysis,2008,48(4):1070-1075.DOI:10.1016/j.jpba.2008.08.019.
[18]申国华,董培智,裴社强,等.HPLC-MS-MS法测定降糖类中成药中非法添加物格列波脲[J].中成药,2014,36(6):1213-1217.DOI:10.3969/j.issn.1001-1528.2014.06.022.
[19]林芳,李涛,耿庆光,等.超高效液相色谱-二极管阵列检测器法快速测定保健食品中违法添加的14种性功能药物[J].食品科学,2014,35(4):163-169.DOI:10.7506/spkx1002-6630-201404034.
[20]朱峰,阮丽萍,马永健,等.超高效液相色谱-串联质谱联用法同时检测降糖类和减肥类保健品中20种非法添加的化学降糖药物[J].色谱,2014,32(1):13-20.DOI:10.3724/SP.J.1123.2013.08035.
[21]沈国芳,朱建,裘一婧.UPLC-MS/MS检测减肥类保健食品中的西布曲明及其去甲基衍生物[J].中国药学杂志,2011,46(20):1609-1611.
[22]吴杨,张圆,闵春艳,等.辅助降血糖类保健食品非法添加化学物质检测方法研究[J].中国执业药师,2014,11(10):11-14.DOI:10.3969/j.issn.1672-5433.2014.10.003.
[23]BLOK-TIP L,ZOMER B,BAKKER F,et al.Structure elucidation of sildenafil analogues in herbal products[J].Food Additives and Contaminants,2004,21(8):737-748.DOI:10.1080/02652030412331272467.
[24]赵侠,孙培红,周颖,等.枸橼酸爱地那非片Ⅰ期临床耐受性研究[J].中国新药杂志,2008,17(17):1535-1538.DOI:10.3321/j.issn:1003-3734.2008.17.020.
[25]王维亭,赵专友,何小云,等.爱地那非对阴茎勃起功能的影响[J].中国药理学与毒理学杂志,2005,19(3):220-225.DOI:10.3321/j.issn:1000-3002.2005.03.011.
[26]李文成,刘军,刘宝顺,等.枸橼酸爱地那非治疗勃起功能障碍的疗效和安全性观察[J].山东医药,2009,49(22):6-7.DOI:10.3969/j.issn.1002-266X.2009.22.003.
[2]邓鲲鹏,罗卓雅,雷毅,等.补肾壮阳类健康产品中艾地那非的检测方法研究[J].中国药学杂志,2011,46(18):1441-1444.
[3]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LCMS/MS法测定[J].中国医药工业杂志,2010,41(10):755-758.DOI:10.3969/j.issn.1001-8255.2010.10.011.
[4]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):3129-3130.DOI:10.6039/j.issn.1001-0408.2013.33.20.
[5]王维亭,赵专友,何小云,等.爱地那非对阴茎勃起功能的影响[J].中国药理学与毒理学杂志,2005(3):220-225.DOI:10.3321/j.issn:1000-3002.2005.03.011.
[6]PATEL D N,LI L,KEE C L,et al.Screening of synthetic PDE-5inhibitors and their analogues as adulterants:analytical techniques and challenges[J].Journal of Pharmaceutical and Biomedical Analysis,2014,87:176-190.DOI:10.1016/j.jpba.2013.04.037.
[7]SHI F,GUO C,GONG L,et al.Application of a high resolution benchtop quadrupole-orbitrap mass spectrometry for the rapid screening,confirmation and quantification of illegal adulterated phosphodiesterase-5 inhibitors in herbal medicines and dietary supplements[J].Journal of Chromatography A,2014,1344:91-98.DOI:10.1016/j.chroma.2013.12.030.
[8]国家食品药品监督管理总局.国家食品药品监督管理总局关于51家保健酒、配制酒企业69种产品违法添加行为的通告(2015年第45号)[EB/OL].(2015-07-31)[2015-11-30].http://www.sda.gov.cn/WS01/CL0087/125640.html.
[9]张园,郝刚,闵春艳,等.UPLC-DAD-Q-TOF-MS/MS测定缓解体力疲劳类保健品中非法添加的化学物质[J].中国执业药师(论著),2014,11(8):15-19.DOI:10.3969/j.issn.1672-5433.2014.08.06.
[10]高青,张喆,郭洪祝,等.中药及保健食品中PDE5抑制剂检测方法研究及未知衍生物的发现[J].中国药学杂志,2008,43(2):142-146.DOI:10.3321/j.issn:1001-2494.2008.02.019.
[11]梁丽梅.中药中违法添加枸橼酸西地那非的含量测定方法研究[J].中国药房,2006,17(24):1917-1918.DOI:10.3969/j.issn.1001-0408.2006.24.034.
[12]赵维,冉兰,魏伯平.HPLC-TOF/MS检测补肾强身胶囊中西地那非和他达那非[J].药物分析杂志,2008,28(10):1692-1697.
[13]高咏莉,邬晓鸥,肖丽和,等.HPLC-MS/MS法测定补肾壮阳类药品或保健品中非法添加羟基豪莫西地那非的研究[J].中成药,2009,31(7):1058-1061.DOI:10.3969/j.issn.1001-1528.2009.07.022.
[14]ZOU P,SHARON S Y,HOU P L,et al.Simultaneous determination of synthetic phosphodiesterase-5 inhibitors found in a dietary supplement and pre-mixed bulk powders for dietary supplements using high-performance liquid chromatography with diode array detection and liquid chromatography-electrospray ionization tandem mass spectrometry[J].Journal of Chromatography A,2006,1104(1/2):113-122.DOI:10.1016/j.chroma.2005.11.103.
[15]陈安珍,王尊文,杨钊,等.UPLC-MS/MS检测补肾壮阳类中成药及保健品中添加的化学药[J].中成药,2009,31(11):1712-1714.
[16]张翠英,李振国,徐金玲,等.超高效液相色谱-串联质谱法测定中成药中非法添加枸橼酸西地那非的研究[J].中成药,2007,29(9):1315-1318.DOI:10.3969/j.issn.1001-1528.2007.09.022.
[17]GE X W,LOW M Y,ZOU P,et al.Structural elucidation of a PDE-5 inhibitor detected as an adulterant in a health supplement[J].Journal of Pharmaceutical and Biomedical Analysis,2008,48(4):1070-1075.DOI:10.1016/j.jpba.2008.08.019.
[18]申国华,董培智,裴社强,等.HPLC-MS-MS法测定降糖类中成药中非法添加物格列波脲[J].中成药,2014,36(6):1213-1217.DOI:10.3969/j.issn.1001-1528.2014.06.022.
[19]林芳,李涛,耿庆光,等.超高效液相色谱-二极管阵列检测器法快速测定保健食品中违法添加的14种性功能药物[J].食品科学,2014,35(4):163-169.DOI:10.7506/spkx1002-6630-201404034.
[20]朱峰,阮丽萍,马永健,等.超高效液相色谱-串联质谱联用法同时检测降糖类和减肥类保健品中20种非法添加的化学降糖药物[J].色谱,2014,32(1):13-20.DOI:10.3724/SP.J.1123.2013.08035.
[21]沈国芳,朱建,裘一婧.UPLC-MS/MS检测减肥类保健食品中的西布曲明及其去甲基衍生物[J].中国药学杂志,2011,46(20):1609-1611.
[22]吴杨,张圆,闵春艳,等.辅助降血糖类保健食品非法添加化学物质检测方法研究[J].中国执业药师,2014,11(10):11-14.DOI:10.3969/j.issn.1672-5433.2014.10.003.
[23]BLOK-TIP L,ZOMER B,BAKKER F,et al.Structure elucidation of sildenafil analogues in herbal products[J].Food Additives and Contaminants,2004,21(8):737-748.DOI:10.1080/02652030412331272467.
[24]赵侠,孙培红,周颖,等.枸橼酸爱地那非片Ⅰ期临床耐受性研究[J].中国新药杂志,2008,17(17):1535-1538.DOI:10.3321/j.issn:1003-3734.2008.17.020.
[25]王维亭,赵专友,何小云,等.爱地那非对阴茎勃起功能的影响[J].中国药理学与毒理学杂志,2005,19(3):220-225.DOI:10.3321/j.issn:1000-3002.2005.03.011.
[26]李文成,刘军,刘宝顺,等.枸橼酸爱地那非治疗勃起功能障碍的疗效和安全性观察[J].山东医药,2009,49(22):6-7.DOI:10.3969/j.issn.1002-266X.2009.22.003.