SPE-UPLC-Q-TOF MS测定育发化妆品中人参和甘草类功效成分

Determination of Active Constituents of Ginseng and Glycyrrhizae in Hair Growth Cosmetics by SPE-UPLC-Q-TOF MS

  • 摘要: 建立了甲醇超声提取,阴离子交换固相萃取(SPE)净化,超高效液相色谱-四极杆飞行时间质谱法(UPLC-Q-TOF MS)测定育发化妆品中3种人参皂甙(Rg1、Rb1、Re)和2种甘草类功效成分(甘草次酸和光甘草定)。样品采用甲醇超声提取,MAX(500 g/6 L)固相萃取小柱净化,以甲醇0.002%甲酸水溶液为流动相,梯度洗脱,在色谱柱HSS T3(2.1 m×100 mm×1.8 μm)上分离,于UPLC-Q-TOF MS负离子模式下检测。同时,对固相萃取条件和色谱质谱条件进行了优化,并对方法学进行了验证。结果表明:5种目标化合物在5~200 μg/L浓度范围内均呈良好的线性关系,线性相关系数大于0.999;方法检出限为0.03~0.1 mg/kg(S/N=3);在膏霜和洗发水基质中的加标回收率为71.9%~94.2%,相对标准偏差小于15.4%(n=6);分子质量偏差小于5×10-6。该方法适用于育发化妆品(特别是表面活性剂及油脂含量高的样品)中人参皂甙和甘草类功效成分的定性定量检测。

     

    Abstract: A method for the determination of three active constituents of ginseng (ginsenoside Rg1, ginsenoside Rb1 and ginsenoside Re) and two active constituents of glycyrrhizae (glycyrrhetic acid and glabridin) in hair growth cosmetics was developed by strong anion exchange-solid phase extraction (SPE) combined with ultra-performance liquid chromatography quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF MS). The sample was extracted by methanol through ultrasonic wave, and purified by SPE (MAX, 500 g/6 L) cartridge. Chromatographic separation was conducted on an UPLC HSS T3 (2.1 m×100 mm×1.8 μm) column with gradient elution using methanol and 0.002% fomic acid solution as mobile phases. MS analysis was set in electrospray ionization operated in negative mode. The experiment conditions of SPE (adsorbing materials and washing solvents) and UPLC-Q-TOF MS (mobile phases, ionization mode and mass spectrometric parameters) were optimized. The results demonstrate that the method shows good linearity in the concentration range of 5200 μg/L, with correlation coefficients no less than 0.999 for the five investigated analytes. The limits of detection are in the range of 0.03-0.1 mg/kg (S/N=3). The average recoveries in sample matrix of cream and paste shampoo are from 71.9% to 94.2% with relative standard deviations (RSDs) less than 15.4% (n=6). High resolution Q-TOF MS gives accurate mass measurement for identification of the target analytes from complicated matrices, with mass errors below 5×10-6. The method is suitable for the determination of ginsenoside Rg1, ginsenoside Rb1, ginsenoside Re, glycyrrhetic acid and glabridin in hair growth cosmetics, particularly for those containing high content of surfactants and greases.

     

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