高效液相色谱法同时测定化妆品中24种香豆素类化合物及质谱确证

doi:10.3969/j.issn.2097-2806.2024.01.016

Abstract

Abstract:

An analytical method for simultaneous determination of 24 coumarin compounds in cosmetics was established by high performance liquid chromatography. Samples with certain fluidity, such as lotions, creams, and water-based samples, were directly extracted with methanol by ultrasonic treatment, while solid samples （lipsticks, pressed powders, etc.） were ultrasonically extracted with mixed solvent of tetrahydrofuran-methanol （1∶1）. The compounds were separated on a CAPCELL CORE MGII C₁₈ （4.6×250 mm, 5 μm） column, and gradient elution was carried out with methanol and 0.02 mol/L sodium dihydrogen phosphate buffer （pH 3.5） as the mobile phase. The flow rate was 1.0 mL/min. The quantification was done by external standard method, with PDA detector at multi-wavelength, and the suspected positive samples were confirmed by liquid chromatography-tandem mass spectrometry. The results showed that the 24 coumarin compounds showed good linearity, with correlation coefficient≥0.999 6 in their respective mass concentration range. The limits of detection and limits of quantification were 2-19 mg/kg and 5-63 mg/kg, respectively. At the three spiked levels of low, medium and high, the average recoveries ranged from 94.4% to 106.4%, and the relative standard deviations were between 0.5% and 3.3%. This method was simple, accurate and suitable for the determination of 24 coumarin compounds in cosmetics.

Key words: coumarin, cosmetic, high performance liquid chromatography, liquid chromatography-tandem mass spectrometry

CLC Number:

TQ658

Huiduan Long, Yixiang Lu, Jianglan Qin, Keming Zhang. Simultaneous determination of 24 coumarin compounds in cosmetics by high performance liquid chromatography and verification by liquid chromatography-tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2024, 54(1): 114-122.

Figures/Tables 6

Tab. 1

Tab. 2

Tab. 3

Fig. 1

Tab. 4

Tab. 5

Results of recovery test and RSD （n = 6） of 24 coumarin compounds"

序号	名称	添加量/μg	乳液		霜膏		水基		固态基
序号	名称	添加量/μg	回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %
1	6-羟基-7-甲氧基香豆素	21.68	97.7	1.7	103.7	1.5	104.4	1.4	98.4	2.2
		43.36	97.9	2.2	105.3	2.3	102.1	1.6	101.1	1.8
		216.8	99.9	1.8	103.7	1.2	104.4	1.4	101.1	2.1
2	7-羟基-6-甲氧基香豆素	22.14	101.8	2.1	106.3	1.9	100.3	2.2	103.9	1.3
		44.28	105.6	2.0	99.4	1.9	107.4	3.0	102.3	2.3
		221.4	102.6	1.8	102.1	2.8	104.3	1.6	104.8	2.2
3	7-羟基香豆素	20.45	103.2	1.4	107.2	1.4	100.9	0.9	99.9	1.7
		40.90	100.4	1.2	106.8	1.9	101.8	2.1	102.4	2.4
		204.5	103.1	1.1	101.6	1.4	100.9	2.0	103.9	1.1
4	6，7-二甲氧基香豆素	30.60	98.5	2.7	105.6	1.1	100.7	0.9	99.9	1.7
		61.24	100.1	1.0	105.8	1.0	105.6	1.3	97.2	2.5
		306.0	96.9	2.3	101.8	1.8	100.7	0.9	101.1	2.1
5	香豆素	11.26	96.2	1.6	100.3	1.3	99.4	0.9	98.6	1.8
		22.52	101.6	0.8	101.8	1.9	102.6	1.2	100.4	2.2
		112.6	99.7	2.1	102.7	2.0	102.9	1.1	102.2	1.6
6	二氢香豆素	229.9	97.6	2.2	102.3	2.7	99.2	2.0	98.3	1.5
		459.7	100.9	1.7	103.7	2.5	104.5	3.3	105.3	2.5
		2 299	103.4	2.4	100.2	1.1	105.0	2.0	101.3	2.3
7	羟甲基香豆素	27.16	101.0	1.7	103.0	2.4	103.5	2.2	101.9	1.6
		54.32	97.3	0.9	108.2	1.1	98.8	2.4	102.4	2.7
		271.6	99.0	1.2	103.0	1.2	103.5	2.2	101.9	1.4
8	7-甲氧基香豆素	21.09	103.7	1.6	104.1	1.1	102.9	2.0	100.2	1.6
		42.18	100.4	1.9	97.6	0.9	101.4	1.7	101.7	1.9
		210.9	104.8	2.2	102.3	1.7	105.3	0.9	102.0	2.1
9	六氢香豆素	217.4	102.3	2.2	102.3	2.7	99.2	2.0	98.3	1.5
		434.8	99.2	2.0	102.0	2.2	102.8	1.5	98.4	1.9
		2 174	103.2	2.0	100.5	2.2	98.2	1.9	102.9	1.3
10	补骨脂素	22.14	107.2	1.0	102.2	1.9	100.4	1.6	105.3	0.8
		44.28	102.3	1.3	101.4	0.9	99.9	1.6	101.4	1.0
		221.4	103.3	1.4	102.6	2.0	101.7	2.0	100.9	1.4
11	7-甲基香豆素	23.07	104.1	2.0	103.6	1.1	104.4	1.6	102.6	2.0
		46.14	102.2	1.6	101.7	1.8	97.8	2.0	103.9	1.7
		230.7	99.6	1.8	100.6	0.9	101.3	1.6	104.4	1.8
12	6-甲基香豆素	31.84	101.2	1.2	100.3	1.6	101.2	1.5	100.4	0.9
		63.68	100.7	1.4	104.2	2.2	101.8	1.5	102.2	1.1
		318.4	98.6	1.9	102.5	2.1	103.3	2.1	99.3	1.4
13	异补骨脂素	13.34	103.4	2.3	99.5	2.4	103.9	1.9	102.5	2.0
		26.68	100.3	1.9	104.9	1.6	103.0	2.5	104.2	2.1
		133.4	101.3	2.3	98.5	1.6	103.6	1.4	101.7	2.4
14	8-甲氧基补骨脂素	31.88	102.6	1.0	99.7	1.1	104.6	1.4	103.6	2.0
		63.76	103.4	1.4	100.4	1.0	103.2	1.3	101.8	1.3
		318.8	101.8	1.6	102.6	1.9	101.8	2.6	100.5	2.4
15	7-甲氧基-5，11，12-三羟基香豆素	32.14	104.9	1.7	101.3	1.6	98.3	1.4	106.3	1.7
		64.28	103.0	0.9	98.6	1.6	103.2	1.2	102.6	1.9
		321.4	102.5	1.6	100.4	2.1	101.5	1.9	103.3	1.2
16	5-甲氧基补骨脂素	12.84	102.9	1.7	106.0	2.5	103.2	1.7	101.2	2.0
		25.67	97.9	1.1	105.5	1.5	102.1	1.6	103.7	3.4
		128.4	99.5	1.1	103.6	2.1	103.2	1.7	100.3	1.8
17	7-乙氧基-4-甲基香豆素	11.47	102.6	1.1	96.8	2.6	102.6	1.8	102.5	2.3
		22.93	97.8	1.1	102.0	2.1	103.3	1.4	103.7	1.1
		114.7	98.4	1.4	102.8	2.2	102.6	1.8	99.2	1.4
18	醋硝香豆素	11.29	99.2	2.2	106.2	3.5	102.7	2.0	103.0	2.9
		22.58	95.6	1.2	103.0	1.0	99.3	2.2	103.0	1.5
		112.9	99.0	1.8	103.5	2.5	102.7	2.0	100.2	1.8
19	双香豆素	15.48	104.3	2.4	100.3	2.1	103.3	2.1	102.5	1.5
		30.96	103.9	3.2	103.5	1.5	102.4	1.9	100.7	2.3
		154.8	95.8	1.9	101.2	2.3	104.3	2.5	105.4	2.1
20	苯丙香豆素	10.21	103.9	2.1	106.4	2.2	102.7	2.1	101.6	2.0
		20.42	99.6	2.4	105.2	1.1	103.5	2.3	101.6	2.5
		102.1	97.0	2.4	101.8	1.3	102.7	2.1	104.2	1.5
21	欧前胡素	10.33	99.3	3.2	99.0	2.5	98.7	2.8	101.5	2.3
		20.66	100.4	2.6	105.3	3.0	98.5	2.4	103.5	2.6
		103.3	98.0	1.1	96.8	1.5	98.7	2.8	99.4	3.3
22	三甲沙林	8.753	102.4	2.2	107.0	0.7	102.9	2.3	103.5	2.4
		17.51	103.0	2.7	107.5	1.7	103.5	2.3	102.4	1.4
		87.53	98.1	1.2	102.4	1.9	102.9	2.4	99.3	1.1
23	异欧前胡素	11.63	93.8	1.7	94.4	2.3	100.0	2.4	96.4	2.6
		23.27	97.1	2.1	93.0	1.4	98.4	2.1	95.8	2.0
		116.3	94.0	1.0	100.4	1.8	103.2	1.6	97.5	2.7
24	4，6-二甲基-8-特丁香豆素	21.96	102.9	1.5	98.0	2.6	102.7	1.7	102.5	1.5
		43.92	100.8	1.2	94.8	1.9	100.4	2.5	103.3	1.3
		219.6	98.4	1.7	102.3	1.3	102.7	1.7	99.8	0.9

Tab. 5

References 23

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序号	名称	保留时间/min	母离子（m/z）	去簇电压/V	子离子（m/z）	碰撞电压/V
1	6-羟基-7-甲氧基香豆素	6.57	193.0	80	178.1^*/132.8	29/26
2	7-羟基-6-甲氧基香豆素	6.46	193.0	90	133.0^*/150.1	23/36
3	7-羟基香豆素	7.12	163.0	80	106.9^*/ 90.8	29/26
4	6，7-二甲氧基香豆素	8.54	207.1	80	151.1^*/163.1	28/31
5	香豆素²	8.68	147.1	60	90.9^*/102.8	28/22
6	二氢香豆素¹	11.28	149.0	120	107.0^*/ 79.1	23/32
7	羟甲基香豆素	8.78	176.9	100	77.1^*/105.0	48/26
8	7-甲氧基香豆素¹	10.40	177.1	80	121.1^*/132.9	29/24
9	六氢香豆素¹	12.46	153.0	65	93.1^*/ 77.2	18/40
10	补骨脂素	10.91	187.1	160	131.0^*/115.1	33/29
11	7-甲基香豆素¹	11.87	161.1	80	104.9^*/ 91.0	29/30
12	6-甲基香豆素	12.02	161.1	80	104.9^*/ 91.0	28/27
13	异补骨脂素	12.30	187.1	160	131.0^*/115.1	30/29
14	8-甲氧基骨补脂素	11.87	217.0	90	201.9^*/174.1	27/37
15	7-甲氧基-5，11，12-三羟基香豆素	13.66	315.1	120	161.0^*/297.0	48/32
16	5-甲氧基骨补脂素	14.49	217.0	80	201.9^*/174.1	29/37
17	7-乙氧基-4-甲基香豆素¹	16.26	205.1	80	177.0^*/120.8	25/34
18	醋硝香豆素¹	17.82	354.2	100	162.9^*/295.9	22/27
19	双香豆素¹	18.86	335.1	-20	160.9^*/117.0	-18/-56
20	苯丙香豆素¹	19.12	281.1	100	203.2^*/174.9	24/33
21	欧前胡素¹	18.73	271.0	105	203.1^*/147.0	16/42
22	三甲沙林	19.60	229.1	120	142.0^*/173.0	30/30
23	异欧前胡素	20.02	271.0	80	203.1^*/147.0	14/41
24	4，6-二甲基-8-特丁香豆素¹	20.29	231.0	100	215.0^*/174.8	42/27

序号	名称	线性范围/（mg/L）	回归方程	相关系数	LOD/（mg/kg）	LOQ/（mg/kg）
1	6-羟基-7-甲氧基香豆素	2~160	Y=18 799X-5 482	0.999 8	7	21
2	7-羟基-6-甲氧基香豆素	2~160	Y=18 556X-1 895	0.999 9	6	18
3	7-羟基香豆素	2~160	Y=31 472X-5 022	0.999 9	6	18
4	6，7-二甲氧基香豆素	3~240	Y=12 707X+19 892	0.999 7	9	30
5	香豆素	1~80	Y=29 937X-4 469	0.999 9	3	9
6	二氢香豆素	20~1 600	Y=19 310X-7 654	0.999 7	67	209
7	羟甲基香豆素	2~160	Y=30 102X-12 972	0.999 8	7	23
8	7-甲氧基香豆素	2~160	Y=31 525X-24 107	0.999 7	7	23
9	六氢香豆素	20~1 600	Y=4 807X-524	0.999 7	71	224
10	补骨脂素	2~160	Y=27 116X-5 282	0.999 9	7	21
11	7-甲基香豆素	2~160	Y=37 836X-32 702	0.999 8	8	27
12	6-甲基香豆素	3~240	Y=19 722X-11 963	0.999 8	11	33
13	异补骨脂素	1~80	Y=29 500X-586	0.999 9	3	9
14	8-甲氧基补骨脂素	3~240	Y=34 568X-31 916	0.999 7	10	33
15	7-甲氧基-5，11，12-三羟基香豆素	3~240	Y=31 655X-12 251	0.999 9	11	33
16	5-甲氧基补骨脂素	1~80	Y=32 955X-2 520	0.999 9	3	9
17	7-乙氧基-4-甲基香豆素	1~80	Y=27 002X-514	0.999 9	3	9
18	醋硝香豆素	1~80	Y=29 121X-1 254	0.999 8	3	8
19	双香豆素	1.5~120	Y=12 414X-3 461	0.999 7	5	16
20	苯丙香豆素	1~80	Y=29 348X+2 129	0.999 9	3	8
21	欧前胡素	1~80	Y=29 343X-149	0.999 8	3	8
22	三甲沙林	1~80	Y=31 472X-12 188	0.999 7	3	9
23	异欧前胡素	1~80	Y=27 831X+694	0.999 9	3	9
24	4，6-二甲基-8-特丁香豆素	2~160	Y=12 145X-2 186	0.999 9	6	19

Simultaneous determination of 24 coumarin compounds in cosmetics by high performance liquid chromatography and verification by liquid chromatography-tandem mass spectrometry

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[14]	Liyuan Zhang, Qiaoyuan Cheng, Cen Chen, Zehua Li, Liuqian Huang, Lvye Qi. Determination of 3 kinds of α-hydroxy acids and their esters in cosmetics by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 102-106.
[15]	Linling Lu, Hui Lu, Chunyan Min, Yefei Qian. Determination of functional components of Glycyrrhizae, Ginseng and Scutellariae in facial masks by UHPLC-MS/MS [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 107-113.

时间/min	φ（A）/%	φ（B）/%
0	65	35
40	65	35
60	20	80
65	20	80
65.5	10	90
70	10	90
70.5	65	35
75	65	35

时间/min	φ（A）/%	φ（B）/%
0	65	35
16	30	70
18	5	95
21	5	95
22	65	35
25	65	35