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

目的：对保健酒及酒类制品中非法添加磷酸二酯酶（PDE-5）抑制剂及其衍生物进行监测，并对监测结果进行分析讨论。方法：参照“国家食品药品监督管理局药品检验补充检验方法和检验项目批准件（编号2009030）方法。LC-MS/MS法条件：采用Shim-pack XR-ODS（100 mm×2.0 mm，2.2 μm）色谱柱，以0.1%乙酸的10 mmol·L^-1乙酸铵溶液（A）-乙腈（B）为流动相，梯度洗脱（0~8 min，27% B；8~18 min，27% B→80% B，18~20 min，80% B），流速0.3 mL·min^-1；采用电喷雾离子源（ESI），正离子扫描模式，一级质谱全扫描范围为m/z 100~1 000，二级质谱全扫描范围为m/z 40~1 000。HPLC法条件：采用Inertsil ODS-SP C₁₈（4.6mm×150 mm，5 μm）色谱柱，以10 mmol·L^-1乙酸铵溶液（A）-甲醇（B）-乙腈（C）为流动相，梯度洗脱（0~15 min，10% B→25% B；15~25 min，25% B→55% B；25~35 min，55% B，保持15% C），流速1.0 mL·min^-1，柱温为室温，二极管阵列检测器，扫描范围为200~400 nm。结果：64批次样品中12批次检测到PDE-5抑制剂及其衍生物，其中检出批件中涉及的西地那非、伐地那非、氨基他达拉非和羟基豪莫西地那非4种非法添加成分。另外检出5种批件中未涉及的PDE-5抑制剂衍生物，为丙氧基苯基艾地那非、丙氧基苯基硫代艾地那非、艾地那非和羟基硫代豪莫西地那非，且有一种未见报道的新型PDE-5抑制剂衍生物（暂无命名）。结论：保健酒及酒类制品中检出非法添加PDE-5抑制剂及其衍生物，需建立快速有效的针对新型PDE-5衍生物的监测方法，并加强对相关销售渠道的监管，保障人民生命健康。

Objective: To supervise the PDE-5 inhibitors and analogues in tonic wines and wine products and then analyze the result.Methods: The supplement standard of the drugs from SFDA(No. 2009030)was taken as reference. LC-MS/MS analysis was carried out on a Shim-pack XR-ODS column(100 mm×2.0 mm, 2.2 μm)with mobile phase at a flow rate of 0.3 mL·min^-1. The mobile phase consisted of 10 mmol·L^-1 ammonium acetate containing 0.1% acetic acid(A)and acetonitrile(B), and the ratios of B were 0-8 min, 27%B; 8-18 min, 27%B→80%B, and 18-20 min, 80%B. ESI in positive electrospray ion was used with the 100-1 000 MS and 40-1 000 MS/MS scan ranges. HPLC analysis was carried out on an Inertsil ODS-SP C₁₈ column(4.6 mm×150 mm, 5 μm) with mobile phase at a flow rate of 1.0 mL·min^-1. The mobile phase consisted of 10 mmol·L^-1 ammonium acetate(A), methanol(B)and acetonitrile(C), and the ratios of B were 0-15 min, 10%B→25%B; 15-25 min, 25%B→55%B, 25-35 min, 55%B and the ratio of C was kept at 15%. The column temperature was room temperature, and the DAD scan range was from 200 to 400 nm.Results: The PDE-5 inhibitors and analogues were found in about 12 batches among a total of 64 batches of samples. Except for sildenafil, vardenafil, aminotadalafil and hydroxyhomosildenafil reported in the document, five new PDE-5 inhibitor analogues were detected, including propoxyphenyl aildenafil, propoxyphenyl thioaildenafil, aildenafil and hydroxyhomosildenafil, which are not mentioned in the document, among which there was a new compound never being reported before.Conclusion: PDE-5 inhibitors and analogues were inspected in tonic wines and wine products. There is a need to set up effective and rapid detection methods for new PDE-5 inhibitor analogues, and strengthen the supervision to protect the health of people.

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