UPLC-MS/MS法测定化妆品中14种噻嗪类药物

doi:10.3969/j.issn.2097-2806.2025.01.015

Abstract

Abstract:

A new method for the simultaneous and rapid determination of 14 thiazides in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） was established. The cosmetic samples were dispersed with methanol and ultrasonic extraction, and the filtrate was analyzed by a Agilent RRHD Eclipse Plus Zorbax C₁₈ chromatographic column （3.0 mm×100 mm, 1.8 μm）, with 0.2% formic acid aqueous solution and methanol as mobile phases under gradient elution. The condition of mass spectrometry was negative ions scanning with multiple reaction monitor mode （MRM） under the electrospray ionization source. For the representative matrix samples （including water aqua, gel, lotion, cream, powder and essential oil）, thiazides tested show the correlation coefficients for linear calibration curves are in the range of 0.990 7-0.999 6 in the corresponding concentration range. The limits of detections （LODs） of 14 thiazides are in the range of 0.004 0-0.100 0 μg/g, and the limits of quantitations （LOQs） are in the range of 0.008 0-0.400 0 μg/g. The recoveries of low, medium and high concentrations ranged 85.9%-114.4%, with the relative standard deviations （n=6） ranged 0.8%-11.8%. The established method is simple, effective, high sensitive, good repeatability, qualitatively reliable, quantitatively accurate, and is suitable for the determination of 14 thiazides in different matrixes of cosmetics.

Key words: UPLC-MS/MS, cosmetics, illegally added, thiazides, risk substances

CLC Number:

TQ658

Qiuyan Zhang, Juntao Liao, Weiwei Liang, Fang Huang, Huiqin Wu, Huitai Luo. Determination of 14 thiazides in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2025, 55(1): 117-124.

Figures/Tables 6

Fig. 1

Tab. 1

Fig. 2

Tab. 2

Tab. 3

Tab. 4

Recoveries and precisions （RSD） of 14 thiazides in different matrix （n=6）"

序号	化合物名称	加标量/（μg/g）	水剂		凝胶		乳液		膏霜		粉剂		精油
序号	化合物名称	加标量/（μg/g）	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %	平均回收率/%	RSD/ %
1	精磺胺	1.0	102.2	2.6	101.9	1.4	91.6	2.1	102.3	3.1	90.0	6.2	105.3	3.3
		2.0	91.5	3.2	92.9	1.8	93.0	3.6	95.9	2.2	100.1	4.2	93.9	2.9
		10.0	102.9	1.2	104.3	1.8	102.4	0.8	104.5	1.2	104.1	5.6	108.2	4.7
2	氯噻嗪	0.040	99.2	3.1	98.3	3.9	100.1	3.7	104.4	5.0	94.1	6.2	109.4	3.5
		0.080	97.4	2.9	97.8	3.2	93.6	3.0	104.0	3.2	100.3	1.5	102.0	1.8
		0.40	113.8	3.2	102.0	4.1	104.1	2.9	109.7	2.4	101.0	6.8	108.3	4.5
3	氢氯噻嗪	0.20	97.7	4.3	107.9	5.5	101.9	4.5	100.8	5.1	91.3	8.1	109.5	5.5
		0.40	92.1	1.7	93.7	1.5	91.1	1.9	94.4	3.2	94.3	3.4	93.8	3.3
		2.0	103.4	1.4	105.3	2.9	100.1	1.3	102.7	1.1	106.9	6.5	106.9	5.7
4	氢氟噻嗪	0.10	99.1	4.6	104.6	3.5	98.0	5.8	101.9	3.6	98.1	7.6	109.0	4.4
		0.20	96.7	3.4	95.0	2.2	89.1	2.2	97.0	2.7	100.5	1.4	94.2	2.6
		1.0	108.6	1.9	104.4	2.0	98.9	1.0	103.2	1.0	108.0	7.4	108.7	5.7
5	氯噻酮	0.40	105.1	8.0	109.0	4.0	90.6	5.4	104.9	4.0	97.3	5.8	103.0	4.4
		0.80	94.2	3.6	100.6	7.6	90.8	4.8	100.9	3.9	101.9	3.7	90.8	3.9
		4.0	101.3	1.3	102.9	3.1	97.3	1.5	104.8	2.4	97.1	6.0	107.4	4.9
6	甲氯噻嗪	0.040	99.3	8.0	104.2	7.6	89.0	2.8	93.8	11.8	89.6	5.1	109.5	5.3
		0.080	104.7	4.7	95.5	3.9	94.7	6.6	93.8	6.4	96.5	1.5	104.4	5.7
		0.40	108.0	3.4	104.2	3.0	97.1	3.0	106.6	3.9	96.0	9.0	114.4	2.5
7	依匹噻嗪	0.10	98.5	8.9	94.9	4.0	97.3	8.3	105.6	7.4	93.7	6.0	110.3	8.0
		0.20	91.7	6.7	95.5	5.6	87.4	3.3	93.3	4.9	94.8	2.5	90.7	5.2
		1.0	96.0	3.6	100.5	2.6	89.4	4.3	102.3	3.6	90.0	6.2	97.3	2.6
8	布噻嗪	0.20	90.1	11.4	106.3	2.7	92.5	4.8	96.9	4.4	100.1	4.2	113.0	2.2
		0.40	85.9	5.1	105.3	4.4	87.5	5.1	93.1	2.6	104.1	5.6	91.2	3.6
		2.0	97.6	0.9	107.7	4.0	90.6	2.6	99.1	3.0	94.1	6.2	103.0	3.8
9	美托拉宗	0.20	98.5	8.1	104.6	6.4	101.4	4.8	103.8	5.2	100.3	1.5	103.5	4.7
		0.40	94.9	3.7	98.5	6.5	96.0	3.1	91.8	5.9	101.0	6.8	94.6	3.1
		2.0	100.1	2.6	109.9	3.0	96.9	2.4	99.7	2.1	91.3	8.1	106.4	3.7
10	苄氟噻嗪	0.040	89.5	6.5	89.1	7.8	100.4	3.4	103.6	3.3	94.3	3.4	114.4	5.5
		0.080	90.7	7.6	92.3	2.8	96.7	8.0	90.8	4.9	106.9	6.5	97.9	2.9
		0.40	99.5	4.0	107.7	4.1	93.6	2.6	101.8	2.7	98.1	7.6	105.2	3.3
11	泊利噻嗪	0.040	105.5	6.7	102.1	4.2	92.3	4.5	100.7	4.1	100.5	1.4	98.7	6.1
		0.080	100.5	6.5	98.2	5.5	97.4	6.6	104.5	4.7	108.0	7.4	92.5	5.2
		0.40	105.0	3.3	108.5	3.7	98.2	2.9	106.7	4.3	97.3	5.8	100.3	2.4
12	苄噻嗪	0.020	108.2	6.2	96.7	4.9	97.8	7.0	112.9	2.9	101.9	3.7	103.5	4.8
		0.040	99.8	7.1	92.5	2.0	89.7	3.3	106.0	4.3	97.1	6.0	94.0	3.5
		0.20	102.4	5.5	103.8	3.9	92.7	3.1	107.2	7.5	89.6	5.1	104.1	2.2
13	吲达帕胺	0.20	104.4	7.8	102.1	5.0	98.7	4.8	99.9	2.6	96.5	1.5	101.2	3.2
		0.40	92.5	3.7	103.0	5.5	91.2	4.1	92.4	3.1	96.0	9.0	94.1	2.2
		2.0	102.7	3.9	108.8	1.5	98.3	1.3	100.1	1.7	93.7	6.0	103.6	5.7
14	环戊噻嗪	0.20	101.1	8.6	98.5	8.1	87.6	7.2	89.5	6.3	94.8	2.5	102.4	6.0
		0.40	92.9	3.1	103.7	4.3	87.5	3.7	91.2	5.7	90.0	6.2	91.2	5.7
		2.0	95.2	2.5	109.6	3.4	94.1	2.7	99.5	1.7	100.1	4.2	106.0	5.6

Tab. 4

References 21

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序号	化合物名称	CAS号	分子式	保留时间/min	母离子/（m/z）	子离子/（m/z）	碎裂电压/V	碰撞能量/V
1	精磺胺	121-30-2	C₆H₈ClN₃O₄S₂	3.60	283.9	205.2, 78.0^*	135, 135	24, 36
2	氯噻嗪	58-94-6	C₇H₆ClN₃O₄S₂	4.30	294.0	214.0^*, 179.0	130, 130	28, 46
3	氢氯噻嗪	58-93-5	C₇H₈ClN₃O₄S₂	4.54	296.0	269.0^*, 205.0	130, 130	22, 28
4	氢氟噻嗪	135-09-1	C₈H₈F₃N₃O₄S₂	5.70	330.0	303.0, 239.0^*	145, 145	20,28
5	氯噻酮	77-36-1	C₁₄H₁₁ClN₂O₄S	8.80	337.0	189.9^*, 146.0	95, 95	16, 20
6	甲氯噻嗪	135-07-9	C₉H₁₁Cl₂N₃O₄S₂	8.90	357.9	322.0^*, 258.0	125, 125	12, 16
7	依匹噻嗪	1764-85-8	C₁₀H₁₁ClF₃N₃O₄S₃	9.98	423.9	310.0, 300.0^*	175, 175	20, 20
8	布噻嗪	2043-38-1	C₁₁H₁₆ClN₃O₄S₂	10.73	352.0	269.1, 205.1^*	170, 170	20, 24
9	美托拉宗	17560-51-9	C₁₆H₁₆ClN₃O₃S	10.93	364.0	257.0^*, 231.0	150, 150	20, 24
10	苄氟噻嗪	73-48-3	C₁₅H₁₄F₃N₃O₄S₂	11.96	420.0	328.0, 289.1^*	170, 170	28, 24
11	泊利噻嗪	346-18-9	C₁₁H₁₃ClF₃N₃O₄S₃	12.09	438.0	398.0^*, 324.0	175, 175	12, 20
12	苄噻嗪	91-33-8	C₁₅H₁₄ClN₃O₄S₃	12.10	430.0	308.0^*, 228.0	135, 135	24, 44
13	吲达帕胺	26807-65-8	C₁₆H₁₆ClN₃O₃S	11.89	364.0	189.0^*, 132.1	175, 175	28, 24
14	环戊噻嗪	742-20-1	C₁₃H₁₈ClN₃O₄S₂	13.36	378.0	269.0, 205.0^*	180, 180	24, 28

序号	化合物名称	ME值
序号	化合物名称	水剂	凝胶	乳液	膏霜	粉剂	精油
1	精磺胺	1.16	0.96	1.14	1.01	1.00	1.03
2	氯噻嗪	1.18	0.85	1.06	0.93	0.81	0.78
3	氢氯噻嗪	1.12	0.91	1.38	0.99	0.95	0.98
4	氢氟噻嗪	1.12	0.90	1.26	1.03	0.91	0.95
5	氯噻酮	1.13	1.02	1.16	1.06	1.10	1.06
6	甲氯噻嗪	1.04	0.93	1.14	0.96	0.73	0.82
7	依匹噻嗪	0.90	1.00	0.88	0.86	0.73	0.94
8	布噻嗪	0.94	0.90	0.90	0.96	0.84	1.03
9	美托拉宗	1.05	0.96	1.09	1.05	0.94	1.09
10	苄氟噻嗪	1.00	0.85	0.86	0.94	0.86	0.89
11	泊利噻嗪	1.06	0.88	0.80	0.81	0.83	0.76
12	苄噻嗪	1.08	0.90	0.63	0.79	0.75	0.74
13	吲达帕胺	1.05	0.95	1.06	1.02	0.88	1.11
14	环戊噻嗪	0.94	0.92	0.79	1.01	0.91	1.04

序号	化合物名称	线性范围/（ng/mL）	相关系数（r²）	检出限/（μg/g）	定量限/（μg/g）
1	精磺胺	20~1 000	0.994 1~0.998 4	0.100 0	0.400 0
2	氯噻嗪	0.8~40	0.992 8~0.999 4	0.004 0	0.016 0
3	氢氯噻嗪	4~200	0.993 0~0.997 7	0.020 0	0.080 0
4	氢氟噻嗪	2~100	0.991 1~0.998 2	0.010 0	0.040 0
5	氯噻酮	8~400	0.992 0~0.997 8	0.040 0	0.160 0
6	甲氯噻嗪	0.8~40	0.994 3~0.999 2	0.008 0	0.016 0
7	依匹噻嗪	2~100	0.993 7~0.999 1	0.010 0	0.040 0
8	布噻嗪	4~200	0.994 0~0.999 6	0.040 0	0.080 0
9	美托拉宗	4~200	0.991 6~0.999 1	0.040 0	0.080 0
10	苄氟噻嗪	0.8~40	0.994 8~0.999 4	0.008 0	0.016 0
11	泊利噻嗪	0.8~40	0.992 6~0.999 3	0.008 0	0.016 0
12	苄噻嗪	0.4~20	0.990 7~0.999 2	0.004 0	0.008 0
13	吲达帕胺	4~200	0.991 8~0.999 1	0.040 0	0.080 0
14	环戊噻嗪	4~200	0.995 2~0.998 8	0.040 0	0.080 0

Determination of 14 thiazides in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry

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