College of Life Science, Zhejiang Chinese Medical University, Hangzhou, Zhejiang 310053, PR China.
Zhejiang Institute for Food and Drug Control, Hangzhou, Zhejiang 310052, PR China; Key Laboratory for Quality Evaluation of Traditional Chinese Medicine (Traditional Chinese Patent Medicine) by National Medical Products Administration (NMPA), PR China.
J Chromatogr B Analyt Technol Biomed Life Sci. 2020 May 1;1144:122077. doi: 10.1016/j.jchromb.2020.122077. Epub 2020 Mar 22.
In this paper, an ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF HRMS) method was developed and validated for screening, confirmation and quantitation of 31 anti-impotence compounds potentially illegally added to herbal-based dietary supplements. The analytes were well separated by the mobile phase consisted of 0.1% formic acid solution and acetonitrile with gradient elution at a flow rate of 0.3 mL/min. The MS analysis was operated in positive mode and the mass error of the 31 compounds were below 2.9 ppm. The method validation showed good linearity with coefficients of determination (r) higher than 0.9973 for all analytes. LODs and LLOQs ranged from 0.005 to 0.50 μg/g or μg /mL and from 0.02 to 1.24 μg /g or μg/mL, respectively. The accuracy was in the range of 86.6% to 113.7%, while the intra-and inter-day precision were in the ranges of 0.9-7.6% and 0.9-11.4%, respectively. The absolute and relative matrix effect were in the range of 65.8-115.6% and 0.6-13.3%. The mean recoveries were in the range of 80.5-116.9%. The stability ranged from 0.4% to 8.5%. Among 200 batches of herbal-based dietary supplements, sildenafil and/or tadalafil were found to be added illegally in two samples, while not very high concentration of icariin was detected in one sample. The Q-TOF mass spectrometry has been proved to be a very powerful and efficient tool for rapid screening of 31 anti-impotence compounds potentially illegally added to herbal-based dietary supplements, ensuring food safety and public health.
本文建立了一种超高效液相色谱-四极杆飞行时间串联质谱（UHPLC-Q-TOF HRMS）法，用于筛查、确证和定量分析 31 种可能非法添加到草药类膳食补充剂中的抗勃起功能障碍化合物。采用 0.1%甲酸溶液和乙腈作为流动相，梯度洗脱，流速为 0.3ml/min，可实现分析物的良好分离。MS 分析采用正离子模式，31 种化合物的质量误差均低于 2.9ppm。方法学验证结果表明，所有分析物的线性相关系数（r）均大于 0.9973。LOD 和 LOQ 范围分别为 0.005-0.50μg/g 或μg/ml 和 0.02-1.24μg/g 或μg/ml。准确度在 86.6%-113.7%范围内，日内和日间精密度分别在 0.9%-7.6%和 0.9%-11.4%范围内。绝对和相对基质效应分别在 65.8%-115.6%和 0.6%-13.3%范围内。平均回收率在 80.5%-116.9%范围内。稳定性范围在 0.4%-8.5%之间。在 200 批草药类膳食补充剂中，有两批样品中发现非法添加了西地那非和/或他达拉非，而一批样品中检测到了较高浓度的淫羊藿苷。Q-TOF 质谱法已被证明是一种快速筛查 31 种可能非法添加到草药类膳食补充剂中的抗勃起功能障碍化合物的非常强大且有效的工具，可确保食品安全和公众健康。
