超高效液相色谱-串联质谱法测定化妆品中13种 α-羟基酸

茹歌; 许勇; 韩晶; 张凯; 彭兴盛; 郑荣

doi:10.19428/j.cnki.sjpm.2024.23583

摘要:

目的建立化妆品中葡糖醛酸、酒石酸、羟基乙酸、苹果酸、乳酸、柠檬酸、2⁃羟基丁酸钠、扁桃酸、二苯乙醇酸、羟基辛酸、乳糖酸、葡糖酸、N⁃乙酰神经氨酸等13种α⁃羟基酸类化合物的超高效液相色谱⁃串联质谱（UHPLC⁃MS/MS）测定法。

方法水剂、膏霜、乳液类化妆品经超声提取、澄清剂净化、10 000.0 r·min^-1高速离心处理，上层溶液经0.22 μm微孔滤膜过滤后进样。采用Poroshell 120 EC⁃C₁₈反相色谱柱（2.7 μm，4.6 mm×100 mm）分离，以0.1%甲酸水溶液⁃乙腈梯度洗脱，采用电喷雾负离子源（ESI^-），多反应监测（MRM）扫描方式监测，外标法定量测定。

结果葡糖醛酸、酒石酸、苹果酸、2⁃羟基丁酸钠、二苯乙醇酸、羟基辛酸、N⁃乙酰神经氨酸等7种化合物在50.0~2 000.0 μg·L^-1的浓度范围内呈线性关系（r>0.995）；羟基乙酸、乳酸、柠檬酸、扁桃酸等4种化合物在100.0~5 000.0 μg·L^-1的浓度范围内呈线性关系（r>0.995）；乳糖酸、葡糖酸等2种化合物在50.0~5 000.0 μg·L^-1的浓度范围内呈线性关系（r>0.995）。考察了水剂、膏霜、乳液类化妆品的加标回收率。回收率结果在92.3%~114.1%，相对标准偏差（RSD）在0.9%~6.0%。葡糖醛酸、酒石酸、苹果酸、柠檬酸、2⁃羟基丁酸、二苯乙醇酸、羟基辛酸、乳糖酸、葡糖酸、N⁃乙酰神经氨酸的方法检出限均为0.003%；羟基乙酸、乳酸、扁桃酸的方法检出限均为0.006%。10批市售化妆品中8批为阳性。

结论 UHPLC⁃MS/MS法高效、灵敏、准确，适用于化妆品中葡糖醛酸、酒石酸、羟基乙酸、苹果酸、乳酸、柠檬酸、2⁃羟基丁酸、扁桃酸、二苯乙醇酸、羟基辛酸、乳糖酸、葡糖酸、N⁃乙酰神经氨酸等13种α⁃羟基酸的检测。

Abstract:

Objective To establish a UHPLC-MS/MS quantitative method for the determination of glucuronic acid， tartaric acid， glycolic acid， malic acid， lactic acid， citric acid， DL-2-hydroxybutyric acid sodium， mandelic acid， benzilic acid， hydroxycaprylic acid， lactobionic acid， gluconic acid and N-acetylneuraminic acid in cosmetics.

Methods Samples were prepared by ultrasonic extraction， cleansed by precipitating reagent and followed by high-speed centrifugation of the extraction solution. The supernatant was filtered by 0.22 μm Millipore filter. The continued filtrate was taken for analysis. A reversed phase column， Poroshell 120 EC-C₁₈ （2.7 μm， 4.6 mm×1 000 mm） was used with 0.1% formic acid buffer and acetonitrile as the mobile phase under the condition of gradient elution. The analytes were detected with electrospray ionization source in negative ion mode （ESI^-） and multiple reactions monitoring （MRM）， and quantified by external standard curve.

Results The method showed a good linearity of glucuronic acid， tartaric acid， malic acid， DL-2-hydroxybutyric acid sodium， benzilic acid， hydroxycaprylic acid and N-acetylneuraminic acid within the concentration range of 50.0‒2 000.0 μg·L^-1 （r>0.995）. The method showed a good linearity of glycolic acid， lactic acid， citric acid and mandelic acid within the concentration range of 100.0‒5 000.0 μg·L^-1 （r>0.995）. The method showed a good linearity of lactobionic acid and gluconic acid within the concentration range of 50.0‒5 000.0 μg·L^-1 （r>0.995）. The recoveries were in the range of 92.3%‒114.1%； the relative standard deviations （RSD） were in the range of 0.9%‒6.0% （n=3）. The detection limits of glucuronic acid， tartaric acid， malic acid， citric acid， DL-2-hydroxybutyric acid sodium， mandelic acid， benzilic acid， hydroxycaprylic acid， lactobionic acid， gluconic acid and N-acetylneuraminic acid were 0.003% while the detection limits of glycolic acid， lactic acid and mandelic acid were 0.006%. In 10 batches of commercially available cosmetics， eight batches showed positive result.

Conclusion The UHPLC-MS/MS method is efficient， sensitive and accurate and is applicable to the determination of 13 α-hydroxy acidic components in cosmetics.

超高效液相色谱-串联质谱法测定化妆品中13种 α-羟基酸

Determination of α-hydroxy acids in cosmetics by UHPLC-MS/MS