超高效液相色谱-串联质谱法测定化妆品中乳糖酸等8种有机酸

doi:10.3969/j.issn.2097-2806.2023.08.016

摘要/Abstract

摘要：

建立超高效液相色谱-串联质谱（UPLC-MS/MS）法测定化妆品中乳糖酸、L-乳酸、柠檬酸、丁二酸、DL-扁桃酸、阿魏酸、壬二酸和硫辛酸8种有机酸含量。以甲醇-水（体积比50∶50）为提取液，用UPLC-MS/MS进行分析，乙酸铵（pH值=2.6）-水-乙腈为流动相，梯度洗脱，流速为0.35 mL/min，柱温35 ℃，采用ACQUITY UPLC^® HSS T3柱（1.8 μm, 2.1 mm×100 mm）分离，负离子多反应监测（MRM）模式进行含量测定。乳糖酸、L-乳酸、柠檬酸、丁二酸、DL-扁桃酸、阿魏酸、壬二酸和硫辛酸分别在2.52~10.10，4.54~18.16，2.82~15.30，2.30~9.22，2.41~9.63，2.27~9.08，2.33~9.33，2.16~8.65 μg/mL范围内与峰面积线性关系良好（R²≥0.99）；检出限达到0.003 μg/g。精密度、稳定性、重复性试验的RSD均小于7.79%；高、中、低不同质量浓度的加标回收率在86.52%~119.98%之间，RSD在0.55%~4.74%之间。该方法准确度高、重复性好、速度快，适用于同时检测化妆品中乳糖酸等8种有机酸成分的含量。

关键词: 超高效液相色谱-串联质谱法, 化妆品

Abstract:

The study aims to establish a method for the determination of eight organic acids in cosmetics, including lactobionic acid, L-lactic acid, citric acid, succinic acid, DL-mandelic acid, ferulic acid, azelaic acid and lipoic acid, by ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. The chromatographic column was Waters ACQUITY UPLC^® HSS T3 column （1.8 μm, 2.1 mm×100 mm） with methanol-water （volume ratio 50∶50） as the extraction solution and ammonium acetate （pH=2.6） -water-acetonitrile as the mobile phases. The flow rate is 0.35 mL/min and the column temperature is 35 ℃. The electrospray ion （ESI） source, negative ions scanning method and multiple reaction monitoring （MRM） mode are used to determine the content. There are good linear relationships （R²≥0.99） and the peak area of the eight organic acids are 2.52-10.10, 4.54-18.16, 2.82-15.30, 2.30-9.22, 2.41-9.63, 2.27-9.08, 2.33-9.33, and 2.16-8.65 μg/mL, respectively. Their minimum limits of quantitation （LOQ） are as low as 0.003 μg/g. The RSDs of precision, stability and repeatability tests are all less than 7.79%. The recoveries of high, medium and low concentrations range from 86.52% to 119.98%, with RSD ranging from 0.55% to 4.74%. The method has high accuracy, good repeatability and fast speed, and is suitable for the simultaneous determination of eight organic acids in cosmetics.

Key words: UPLC-MS/MS, cosmetics

中图分类号:

TQ658

章欣,霍永丽. 超高效液相色谱-串联质谱法测定化妆品中乳糖酸等8种有机酸[J]. 日用化学工业（中英文）, 2023, 53(8): 981-988.

Zhang Xin,Huo Yongli. Determination of eight organic acids such as lactobionic acid in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2023, 53(8): 981-988.

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参考文献 20

[1]	Ditre C M, Griffin T D, Murphy G F, et al. Effects of alpha-hydroxy acids on photoaged skin: a pilot clinical, histologic, and ultrastructural study[J]. J. Am. Acad. Dermatol., 1996, 34 (2) : 187-195. doi: 10.1016/S0190-9622(96)80110-1
[2]	Sharad J. Glycolic acid peel therapy-a current review[J]. Clinical, Cosmetic and Investigational Dermatology, 2013, 6(default): 281-288.
[3]	Puizina-Ivić N. Skin aging[J]. Acta Dermatovenerol. Alp. Pannonica. Adriat., 2008, 17 (2) : 47-54. pmid: 18709289
[4]	Saeedi M, Eslamifar M, Khezri K. Kojic acid applications in cosmetic and pharmaceutical preparations[J]. Biomed. Pharmacother., 2019, 110: 582-593. doi: S0753-3322(18)36747-7 pmid: 30537675
[5]	Cosmetic Ingredient Review Expert Panel. Cosmetic ingredient review[S]. America: Cosmetic Ingredient Review Expert Panel, 2020.
[6]	National Medical Products Administration. Scientific understanding of “brush acid” beauty[EB]. National Medical Products Administration, 2021.
[7]	Kapuścińska A, Nowak I. Use of organic acids in acne and skin discolorations therapy[J]. Postepy Hig. Med. Dosw. (Online), 2015, 69: 374-383. pmid: 25811473
[8]	Tang S C, Yang J H. Dual effects of alpha-hydroxy acids on the skin[J]. Molecules, 2018, 23 (4) : 863. doi: 10.3390/molecules23040863
[9]	The State Food and Drug Administration.Safety and technical standards for cosmetics (2015 Edition)[S]. Beijing: The State Food and Drug Administration, 2016.
[10]	Shi Kexin, Zhang Weiwei, Ma Yuexin, et al. Determination of four flavor frganic acids in oligopeptide powders from different sources by HPLC[J]. Journal of Tianjin University of Science & Technology, 2022, 37 (3) : 21-27.
[11]	Yuan Xiaoli, Xia Lunchao, Kai Feng, et al. Determination of maleic acid, succinic acid and fumaric acid by high performance liquid chromatography[J]. Technology & Development of Chemical, 2021, 50 (5) : 64-66.
[12]	Wang Yuan. Determined the contents of 10 α-hydroxy acids in several cosmetics on the market bu HPLC[J]. Shandong Chemical Industry, 2021, 50 (11) : 90-92.
[13]	Zhang Yanyan, Sun Xiaokang, Zhang Xiaoyuan, et al. Fast and effective determination of ten kind of organic acids by HPLC[J]. Food and Drug, 2022, 24 (1) : 44-47.
[14]	National Pharmacopoeia Commission. The Chinese pharmacopoeia-part IV[M]. The State Food and Drug Administration, 2022: 63.
[15]	Mu Yingqi, Wu Yixuan, Wang Xiao, et al. Determination of 10 organic acids in alcoholic products by ion chromatography-tandem mass spectrometry[J/OL]. Chinese Journal of Chromatography, 2022[2022-08-17]. https://sso.gzlib.org.cn/interlibSSO/goto./75/+jmr9bmjh9mds/kcms/detail/21.1185.O6.20220517.0922.002.html.
[16]	Dong Meng, Xin Ran, Zhang Yuying, et al. Simultaneous monitoring of 22 organic acids in foods by ultra-high performance liquid chromatography coupled to tandem mass spectro metry[C]// The 18^th Annual Meeting of Cifst, 2022: 532-533.
[17]	Wang Siwei, Liu Yanping, Wang Xiaonan, et al. Determination of ten organic acids content in fresh litchi based on high performance liquid chromatography with triple quadrupole mass spectrometry technique[J]. Chinese Journal of Pesticide Science, 2019, 21 (3) : 359-365.
[18]	Yu Sheng, Zhang Li, Shan Mingqiu, et al. Simultaneous determination of eight organic acids in chaenomelis fructus by UFLC-MS[J]. Chinese Traditional and Herbal Drugs, 2016, 47 (14) : 2465-2469.
[19]	Yang Jiangtao, Zeng Weihong, Tian Guoli, et al. Consensus of experts on detection of various organic acids in urine by gas chromatography-mass spectrometry[J]. Journal of Rare and Uncommon Diseases, 2022, 29 (8) : 1-5.
[20]	Liu Yuling, Lin Liangliang, Pan Xiaohong, et al. Detection of nine components including retinol in cosmetics by high performance liquid chromatography[J]. China Surfactant Detergent & Cosmetics, 2021, 51 (10) : 1032-1038.

序号	中文名称	CAS NO.	化学式	分子量
1	乳糖酸	96-82-2	C₁₂H₂₂O₁₂	358.11
2	L-乳酸	79-33-4	C₃H₆O₃	90.03
3	柠檬酸	77-92-9	C₆H₈O₇	192.12
4	琥珀酸	110-15-6	C₄H₆O₄	118.09
5	DL-扁桃酸	90-64-2	C₈H₈O₃	152.15
6	阿魏酸	1135-24-6	C₁₀H₁₀O₄	194.18
7	壬二酸	123-99-9	C₉H₁₆O₄	188.22
8	硫辛酸	62-46-4	C₈H₁₄O₂S₂	206.32

物质名称	保留时间/min	母离子/（m/z）	定量子离子/（m/z）	锥孔电压/V	碰撞电压/V
乳糖酸	0.74	357.14	74.86	-60	-24
L-乳酸	1.13	89.02	42.85	-10	-8
柠檬酸	1.14	191.02	110.80	-5	-10
琥珀酸	1.58	117.02	72.90	-10	-10
DL-扁桃酸	3.18	151.04	106.85	-10	-7
阿魏酸	3.68	193.06	133.95	-20	-13
壬二酸	3.81	187.10	125.00	-10	-13
硫辛酸	4.31	205.04	171.02	-10	-7

序号	物质名称	回归方程	相关系数R²	线性范围/ （μg/mL）	检出限/（μg/g）		定量限/（μg/g）
序号	物质名称	回归方程	相关系数R²	线性范围/ （μg/mL）	标样	基质	标样	基质
1	乳糖酸	y=5 384.8x-4.858 4	0.998 9	2.52~10.10	0.058 5	0.059 8	0.195 1	0.199 4
2	L-乳酸	y=3 118.1x+3 366.5	0.994 4	4.54~18.16	0.110 8	0.115 6	0.369 2	0.385 3
3	柠檬酸	y=45 699x-91 179	0.993 5	2.82~15.30	0.821 3	0.752 3	2.737 7	2.507 7
4	琥珀酸	y=30 536x+1 899.5	0.996 9	2.30~9.22	0.617 6	0.431 7	2.058 7	1.439 1
5	DL-扁桃酸	y=24 484x-9 502.8	0.996 4	2.41~9.63	0.039 8	0.038 3	0.132 6	0.127 8
6	阿魏酸	y=39 069x+4 515.4	0.997 6	2.27~9.08	0.003 0	0.003 0	0.009 8	0.009 8
7	壬二酸	y=60 951x+27 716	0.993 3	2.33~9.33	0.008 4	0.011 0	0.028 1	0.036 5
8	硫辛酸	y=31 606x+8 818.3	0.992 9	2.16~8.65	0.007 4	0.014 0	0.024 5	0.046 6

物质名称	质量浓度/ （μg/mL）	峰面积						平均值	RSD/%
乳糖酸	4.04	23 335	23 269	23 960	23 751	24 135	23 281	23 621.83	1.60
乳糖酸	10.10	56 223	55 836	55 136	53 670	54 657	53 375	54 816.17	2.09
L-乳酸	7.26	25 250	25 422	25 404	25 853	26 325	25 139	25 565.50	1.74
L-乳酸	18.16	58 472	57 646	54 905	57 010	55 151	58 951	57 022.50	2.95
柠檬酸	6.12	212 538	217 170	223 617	237 299	232 067	218 991	223 613.67	4.22
柠檬酸	15.30	620 061	611 290	619 066	586 854	615 125	606 304	609 783.33	2.02
琥珀酸	3.71	117 104	117 650	121 515	121 119	121 864	119 485	119 789.50	1.71
琥珀酸	9.26	284 346	287 989	280 902	281 478	275 181	277 416	281 218.67	1.64
DL-扁桃酸	3.89	82 679	84 015	86 676	88 699	87 879	85 188	85 856.00	2.70
DL-扁桃酸	9.73	224 699	225 558	225 922	222 531	218 985	222 878	223 428.83	1.15
阿魏酸	3.64	160 888	158 365	157 648	160 856	163 224	157 631	159 768.67	1.41
阿魏酸	9.11	378 154	374 072	375 576	376 649	373 125	369 739	374 552.50	0.79
壬二酸	3.77	287 926	283 524	280 223	288 268	299 152	290 992	288 347.50	2.26
壬二酸	9.42	653 660	651 432	637 448	645 377	647 311	643 942	646 528.33	0.89
硫辛酸	3.52	135 627	135 351	135 004	132 607	124 936	136 863	133 398.00	3.28
硫辛酸	8.79	302 356	308 517	310 340	316 360	300 700	315 477	308 958.33	2.10

物质名称	质量浓度/（μg/mL）	峰面积			平均值	RSD/%
乳糖酸	4.04	23 622	21 947	22 419	22 662	3.81
乳糖酸	10.10	54 816	48 748	47 483	50 349	7.79
L-乳酸	7.26	25 566	26 482	27 956	26 668	4.52
L-乳酸	18.16	57 023	57 371	53 265	55 886	4.07
柠檬酸	6.12	223 614	196 600	211 461	210 558	6.43
柠檬酸	15.30	609 783	596 426	618 120	608 110	1.80
琥珀酸	3.71	119 790	121 519	129 068	123 459	4.00
琥珀酸	9.26	281 219	294 584	308 674	294 826	4.66
DL-扁桃酸	3.89	85 856	84 187	91 294	87 112	4.27
DL-扁桃酸	9.73	223 429	217 739	234 690	225 286	3.83
阿魏酸	3.64	159 769	161 737	172 633	164 713	4.21
阿魏酸	9.11	374 553	380 324	400 487	385 121	3.54
壬二酸	3.77	288 348	292 393	302 310	294 350	2.44
壬二酸	9.42	646 528	649 198	668 620	654 782	1.84
硫辛酸	3.52	133 398	134 397	141 342	136 379	3.17
硫辛酸	8.79	308 958	306 267	316 565	310 597	1.72