对市售白芍饮片芍药苷含量低于中国药典标准的深入探讨

目的: 探讨硫磺熏蒸对白芍化学成分的影响,阐明导致市售白芍饮片芍药苷含量普遍低于中国药典标准的原因。 方法: 依照2010年版中国药典(一部)方法对市售白芍饮片和产地白芍药材中的芍药苷含量进行测定;采用HPLC、HPLC-MS方法从化学成分质和量的方面分别对市售白芍饮片和白芍药材进行对比和分析,同时在实验室环境中模拟硫磺熏蒸过程,自制硫磺熏蒸白芍饮片,并对其进行分析测定做为验证。HPLC方法采用Lichrospher C₁₈(150 mm×4.6 mm,5 μm)色谱柱,其他色谱条件与2010年版中国药典相应项下相同。HPLC-MS方法采用Pursuit XRs C₁₈(250 mm×4.6 mm,5 μm)色谱柱,流动相为0.1%甲酸(A)-乙腈(B),梯度洗脱(0~10 min,97%A;10~20 min,97%A→95%A;20~20.1 min,95%A→91%A;20.1~85 min,91%A→80%A;85~95 min,80%A→15%A;95~100 min,15%A),流速0.8 mL·min^-1,检测波长270 nm,柱温35 ℃,质谱采用电喷雾电离源(ESI),负离子模式检测,扫描质量范围m/z 100~1000。 结果: 硫磺熏蒸可使包括芍药苷在内的6种单萜苷类有效成分发生化学转化,并导致市售白芍饮片中芍药苷的含量显著降低。 结论: 硫磺熏蒸使白芍有效成分发生质和量的改变,应控制该方法在白芍加工中的使用。

Objective: To investigate the impact of sulfur-fumigation process to chemical constituents in Radix Paeoniae Alba,and elucidate the reason for paeoniflorin contents of commercial Radix Paeoniae Alba prepared Chinese crude drug lower than the standard of Chinese Pharmacopeia. Methods: The concentration determination method for paeoniflorin contents in Radix Paeoniae Alba from markets and habitats was according to the method in Chinese Pharmacopeia(Edition 2010,VolⅠ);HPLC and HPLC-MS techniques were adopted to analyze and compare the differences of chemical constituents in terms of both quality and quantity between Radix Paeoniae Alba prepared Chinese crude drug and medical material.The chromatographic column was Lichrospher C₁₈(150 mm×4.6 mm,5 μm) for HPLC,and the other chromatographic conditions were in accordance with that of Chinese Pharmacopeia.The chromatographic column was Pursuit XRs C₁₈(250 mm×4.6 mm,5 μm) for HPLC-MS,the mobile phase was composed of 0.1% formic acid(A) and acetonitrile(B) with gradient elution(0-10 min,97%A;10-20 min,97%A→95%A;20-20.1 min,95%A→91%A;20.1-85 min,91%A→80%A;85-95 min,80%A→15%A;95-100 min,15%A),the flow rate was 0.8 mL·min^-1,the detection wavelength was set at 270 nm,and the column temperature was 35 ℃.The detections equipped with an electrospray ionization (ESI) source,and the analyses were performed using full scan with the mass range set at m/z 100~1000 in negative ion mode. Results: The effective constituents of six monoterpene glycosides including paeoniflorin were chemically changed,and paeoniflorin contents of commercial Radix Paeoniae Alba prepared Chinese crude drug were also decreased remarkably after sulfur-fumigation process. Conclusion: Sulfur-fumigation process can influence the effective constituents of Radix Paeoniae Alba in terms of both quality and quantity,thus this method should be restricted during the processing of Radix Paeoniae Alba.