UPLC-MS/MS法测定不同基质祛痘化妆品中17种磺胺类药物

doi:10.3969/j.issn.1001-1803.2023.04.017

摘要/Abstract

摘要：

建立同时测定不同基质祛痘化妆品中17种磺胺类药物含量的超高效液相色谱-串联三重四极杆质谱法（UPLC-MS/MS）。样品经50%甲醇水溶液超声提取后，用Waters ACQUITY UPLC^® BEH C₁₈色谱柱（100 mm×2.1 mm，1.7 μm），以不同体积分数的甲醇和0.1%（体积分数）甲酸水溶液的混合液为流动相进行梯度洗脱分离。质谱分析中采用电喷雾离子源和正离子多反应监测模式检测，外标法定量。结果显示样品基质效应较小，可不予考虑。17种磺胺类药物在质量浓度为0.5~100 ng/mL范围内与其对应的响应值呈线性关系，相关系数均大于0.999，检出限为0.002~0.028 μg/g，定量限为0.006~0.094 μg/g。按标准物质加入法进行回收试验，添加含量为0.25~2.5 μg/g时，回收率为97.5%~118.3%，相对标准偏差为0.74%~6.37%。按此方法分析了10批市售祛痘化妆品，均未检出17种磺胺类药物成分。

关键词: 超高效液相色谱-串联三重四极杆质谱, 磺胺类, 祛痘, 化妆品

Abstract:

Simultaneous determination of 17 sulfonamides in cosmetics by ultra high performance liquid chromatography tandem triple quadrupole mass spectrometry （UPLC-MS/MS） was established. The samples were dissolved in 50% methanol aqueous solutions by ultrasonic extraction, and the Waters ACQUITY UPLC^® BEH C₁₈ column （100 mm×2.1 mm, 1.7 μm） was used. The mixture of methanol and 0.1% （volume fraction） formic acid aqueous solutions with different volume fraction was used as the mobile phase for gradient elution, measured with liquid chromatography tandem mass spectrometry in electrospray ion mode and positive ion multiple reaction monitoring （ESI⁺）, and quantification by external standard method. The results show that the matrix effects of the sample are small and can be ignored. There is a good linear relationship for 17 sulfonamides at the mass concentrations of 0.5-100 ng/mL, and the correlation coefficients are greater than 0.999. The detection limits are 0.002-0.028 μg/g, and the quantitation limits are 0.006-0.094 μg/g. The average recovery is 97.5%-118.3% with the standard references added at the content of 0.25-2.5 μg/g in blank samples, and the relative standard deviations （n=6） are 0.74%-6.37%. According to this method, 10 batches of anti-acne cosmetics are analyzed, and none is detected with 17 sulfonamides.

Key words: UPLC-MS/MS, sulfonamides, anti-acne, cosmetics

中图分类号:

TQ658

陈桂娟, 邢海艳, 姚欣悦, 韩永红, 陶娟. UPLC-MS/MS法测定不同基质祛痘化妆品中17种磺胺类药物[J]. 日用化学工业（中英文）, 2023, 53(4): 487-492.

Chen Guijuan, Xing Haiyan, Yao Xinyue, Han Yonghong, Tao Juan. Determination of 17 sulfonamides in anti-acne cosmetics with different substrates by UPLC-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2023, 53(4): 487-492.

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参考文献 14

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名称	缩写	ρ/ （μg/mL）	纯度/%	厂家
磺胺嘧啶	SD	100	99.9	阿尔塔科技有限公司
磺胺二甲基嘧啶	SM2	100	99.9
磺胺噻唑	ST	100	99.9
磺胺吡啶	SF4	100	99.9
磺胺甲基嘧啶	SM1	100	99.5
磺胺甲氧哒嗪	SMP	100	99.6
磺胺二甲异嘧啶	SF1	100	99.8
磺胺甲噻二唑	SF2	100	99.9	阿尔塔科技有限公司
甲氧苄啶	TMP	100	99.8
磺胺间甲氧嘧啶	SMM	100	99.9
磺胺氯哒嗪	SCP	100	99.9
磺胺甲恶唑	SMZ	100	99.9
磺胺对甲氧基嘧啶	SM3	100	99.8
磺胺邻二甲氧嘧啶	SDX	100	99.9
磺胺二甲异噁唑	SFX	100	99.9
磺胺间二甲氧嘧啶	SDM	100	99.6
磺喹恶啉	SQX	100	98.1

化合物	保留时间/min	定量离子对/（m/z）	定性离子对/（m/z）	锥孔电压/V	碰撞电压/eV
SD	3.40	251.2>155.9	251.2>108.2	74	22，31
SM2	3.66	279.2>124.2	279.2>185.8	90	23，30
ST	4.37	256.1>156.1	256.1>108.1	76	24，24
SF4	4.60	250.1>156.1	250.1>184.0	75	24，22
SM1	5.13	265.0>155.9	265.0>171.9	80	25，25
SMP	6.96	281.0>155.9	281.0>126.1	80	21，38
SF1	7.04	279.2>155.9	249.2>186.0	85	25，24
SF2	7.47	271.1>156.2	271.1>108.1	40	36，24
TMP	7.54	291.2>230.2	291.2>261.2	101	33，34
SMM	8.17	281.1>155.9	281.1>126.1	80	27，26
SCP	8.95	285.1>156.1	285.1>108.2	45	33，20
SMZ	9.69	254.1>156.0	254.1>108.2	78	19，40
SM3	9.91	281.1>156.1	281.1>215.0	76	24，24
SDX	10.48	311.1>156.0	311.1>108.2	78	24，38
SFX	11.16	268.1>155.9	268.1>108.2	67	19，31
SDM	13.53	311.1>156.0	311.1>108.2	78	24，38
SQX	13.91	301.0>155.9	301.0>108.1	78	22，35

组分	k₁/k₂
组分	精华	凝胶	洗面奶	面霜
SD	1.01	1.09	0.98	1.00
SM2	1.12	1.15	0.98	1.09
ST	1.00	1.04	1.03	1.07
SF4	0.94	0.97	1.01	0.97
SM1	1.04	1.03	1.12	1.10
SMP	1.05	1.08	1.12	1.17
SF1	1.05	1.08	1.07	1.12
SF2	1.06	1.10	1.10	1.15
TMP	0.99	0.84	1.17	0.99
SMM	1.07	1.09	1.13	1.12
SCP	1.03	1.06	1.12	1.05
SMZ	1.02	1.02	1.05	1.07
SM3	1.05	1.11	1.07	1.12
SDX	1.07	1.05	1.07	1.07
SFX	1.06	1.09	1.10	1.10
SDM	1.03	1.03	1.05	1.05
SQX	1.05	1.09	1.07	1.08

组分	线性范围/（ng/mL）	线性回归方程	相关系数	检出限		定量限
组分	线性范围/（ng/mL）	线性回归方程	相关系数	ρ/ （ng/mL）	w/ （μg/g）	ρ/ （ng/mL）	w/ （μg/g）
SD	0.5~100	y=2.08×10⁴x+7.09×10²	0.999 7	0.09	0.011	0.28	0.036
SM2	0.5~100	y=3.34×10⁴x-2.43×10³	0.999 8	0.08	0.009	0.31	0.025
ST	0.5~100	y=2.92×10⁴x +1.11×10³	0.999 2	0.09	0.011	0.29	0.036
SF4	0.5~100	y=2.72 ×10⁴x-8.13×10²	0.999 9	0.04	0.005	0.14	0.017
SM1	0.5~100	y=2.28×10⁴x-2.41×10³	0.999 8	0.04	0.006	0.15	0.019
SMP	0.5~100	y=2.93×10⁴x+1.72×10⁴	0.999 8	0.04	0.005	0.13	0.016
SF1	0.5~100	y=1.72×10⁴x+2.34×10²	0.999 7	0.06	0.007	0.19	0.024
SF2	0.5~100	y=2.33×10⁴x+1.14×10⁴	0.999 9	0.13	0.016	0.44	0.054
TMP	0.5~100	y=6.75×10³x-6.50×10²	0.999 2	0.03	0.004	0.11	0.014
SMM	0.5~100	y=2.73×10⁴x+4.27×10³	0.999 9	0.01	0.002	0.05	0.006
SCP	0.5~100	y=3.02×10⁴x+2.25×10³	0.999 9	0.06	0.007	0.20	0.025
SMZ	0.5~100	y=1.27×10⁴x+5.41×10³	0.999 9	0.23	0.028	0.75	0.094
SM3	0.5~100	y=2.93×10⁴x+1.11×10⁴	0.999 3	0.08	0.009	0.25	0.032
SDX	0.5~100	y=6.22×10⁴x+1.13×10⁴	0.999 8	0.03	0.003	0.09	0.011
SFX	0.5~100	y=1.93×10⁴x-4.11×10³	0.999 4	0.17	0.021	0.56	0.070
SDM	0.5~100	y=5.36×10⁴x+2.30×10⁴	0.999 7	0.04	0.004	0.12	0.015
SQX	0.5~100	y=5.14×10⁴x+1.49×10³	0.999 4	0.06	0.008	0.21	0.026

组分	加标量/（μg/g）	平均回收率/%	RSD/%	组分	加标量/（μg/g）	平均回收率/%	RSD/%
SD	0.25	113.9	2.21	SF4	0.25	115.5	3.87
	0.5	109.6	3.17		0.5	110.9	4.42
	2.5	118.2	2.12		2.5	113.7	1.09
SM2	0.25	114.1	4.10	SM1	0.25	115.3	2.96
	0.5	112.9	3.54		0.5	110.4	4.29
	2.5	102.0	2.15		2.5	116.5	4.53
ST	0.25	111.9	1.93	SF4	0.25	115.5	3.87
	0.5	108.0	4.64		0.5	110.9	4.42
	2.5	116.4	2.69		2.5	113.7	1.09
SMP	0.25	106.8	5.43	SMZ	0.25	113.4	3.67
	0.5	109.0	3.95		0.5	110.5	3.45
	2.5	116.0	4.35		2.5	109.0	2.12
SF1	0.25	113.5	1.93	SM3	0.25	114.1	3.30
	0.5	108.7	4.72		0.5	109.2	4.26
	2.5	115.1	0.74		2.5	111.9	2.90
SF2	0.25	108.1	6.37	SDX	0.25	111.5	3.87
	0.5	109.2	3.58		0.5	108.2	5.37
	2.5	109.5	1.82		2.5	99.6	3.19
TMP	0.25	104.8	4.19	SFX	0.25	118.3	3.86
	0.5	110.2	3.63		0.5	112.6	4.60
	2.5	97.6	3.46		2.5	100.5	2.81
SMM	0.25	114.7	1.82	SDM	0.25	115.2	3.66
	0.5	110.4	4.77		0.5	110.8	4.52
	2.5	109.8	1.36		2.5	102.3	2.36
SCP	0.25	112.4	3.86	SQX	0.25	110.3	3.03
	0.5	111.5	4.33		0.5	109.2	4.12
	2.5	104.9	2.43		2.5	97.5	2.60