超高效液相色谱-三重四极杆/线性离子阱质谱法测定化妆品中16种荧光增白剂

doi:10.3969/j.issn.2097-2806.2025.02.014

Abstract

Abstract:

A method for the determination of 16 fluorescent whitening agents （FWAs） in cosmetics by ultra performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry （UPLC-QTRAP-MS/MS） was established. The sample was extracted by methanol, filtered by microporous polytetrafluoroethylene （PTFE） filter membrane after ultrasonic vortex. The separation was performed on ACE Excel 2 C₁₈ （50 mm×2.1 mm, 2 μm） column. Gradient elution was carried out with acetonitrile and 5 mmoL/L ammonium acetate solution as mobile phases. In positive and negative ionization modes of electrospray ionization source （ESI）, multiple reaction monitoring （MRM） mode combined with enhanced product ion （EPI） mode were used for detection. The external standard calibration was used for quantification, based on the retention time and abundance ratio of characteristic ions, and compound-specific fragment information was obtained through EPI to further qualify and confirm the target components. The precision and accuracy of the method were investigated using liquid-based, emulsion-based and cream-based cosmetic as matrices. The results show that 16 FWAs have good linear relationship within their respective mass concentration ranges, with the correlation coefficients greater than 0.995. The detection limits are 0.005 9-5.6 μg/g, and the quantification limits are 0.015-14 μg/g. At the two spiked levels, the average recoveries are 72.1%-115.8%, and the average relative standard deviations are 0.5%-12.6% （n=6）. Using this method, 82 batches of whitening cosmetics collected are analyzed, and 6 batches are detected with FWAs. This method is simple, fast, accurate, and suitable for the detection of 16 FWAs in cosmetics, providing technical support for cosmetic risk monitoring and quality supervision.

Key words: fluorescent whitening agents （FWAs）, UPLC-QTRAP-MS/MS, enhanced product ion scan （EPI）, cosmetic

CLC Number:

TQ658

Xu Gong,Xuejing Liu,Shu Shang,Jianhua Xiang,Li Wu,Youlong Feng,Fang Fang. Determination of 16 fluorescent whitening agents in cosmetics by ultra performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2025, 55(2): 244-252.

Figures/Tables 7

Tab. 1

Fig. 1

Fig. 2

Fig. 3

Tab. 2

Linear equations，linear ranges，correlation coefficients，detection limits and quantification limits of 16 FWAs"

序号	化合物	线性回归方程			线性范围/ （ng/mL）	相关系数r	检出限/（μg/g）	定量限/（μg/g）
序号	化合物	水剂	乳剂	膏霜	线性范围/ （ng/mL）	相关系数r	检出限/（μg/g）	定量限/（μg/g）
1	FWA162	y=9.95×10⁵x-5.76×10⁴	y=4.42×10⁵x-2.59×10⁴	y=3.33×10⁵x-1.12×10⁴	0.571 0~11.42	0.999 6	0.011	0.029
2	FWA140	y=1.36×10⁶x-7.17×10⁴	y=2.51×10⁵x-2.17×10⁴	y=5.77×10⁵x-3.3×10⁴	0.584 4~11.69	0.999 4	0.012	0.029
3	FWA135	y=7.70×10⁵x-4.90×10⁴	y=1.07×10⁵x-1.49×10⁴	y=2.58×10⁵x-3.81×10⁴	0.579 4~11.59	0.999 6	0.012	0.029
4	FWA185	y=9.74×10⁵x-5.68×10⁴	y=1.38×10⁵x-2.12×10⁴	y=2.22×10⁵x-3.84×10⁴	0.588 6~11.77	0.999 4	0.012	0.029
5	FWA393	y=1.33×10⁶x-4.04×10⁴	y=6.09×10⁵x-9.54×10⁴	y=2.45×10⁵x+5.82×10³	1.493~29.85	0.998 7	0.030	0.075
6	FWA367	y=1.05×10⁶x-2.75×10⁴	y=3.81×10⁵x-4.50×10⁴	y=2.84×10⁵x-4.96×10⁴	0.564 4~11.29	0.999 6	0.011	0.028
7	FWAKS-N	y=1.09×10⁶x-7.58×10⁴	y=5.69×10⁵x-1.47×10⁴	y=3.64×10⁵x+2.06×10⁴	1.111~22.22	0.999 5	0.022	0.056
8	FWA184	y=1.61×10⁶x-5.64×10⁴	y=9.36×10⁴x-3.56×10³	y=5.36×10⁴x-3.16×10³	0.294 1~5.882	0.999 0	0.005 9	0.015
9	FWA220	y=4.49×10³x-2.77×10²	y=4.67×10³x+1.90×10²	y=6.53×10³x+12.4	139.2~2 784	0.999 8	2.8	7.0
10	FWA263	y=2.16×10⁴x+8.47×10²	y=1.55×10⁴x-7.62×10²	y=1.69×10⁴x-6.46×10²	59.20~1 184	0.999 6	1.2	3.0
11	FWA210	y=2.33×10⁴x+4.90×10³	y=1.68×10⁴x-1.15×10³	y=2.16×10⁴x-1.16×10³	111.5~2 229	0.998 4	2.2	5.6
12	FWA85	y=5.68×10³x-7.84×10²	y=4.37×10³x-2.67×10²	y=4.64×10³x-6.52	277.9~5 559	0.999 3	5.6	14
13	FWA28	y=6.93×10⁴x-2.25×10³	y=6.34×10⁴x-9.60×10²	y=7.81×10⁴x+4.17×10³	28.87~577.4	0.999 2	0.58	1.4
14	FWA351	y=7.20×10⁵x+2.38×10²	y=7.17×10³x-2.22×10²	y=7.03×10³x+8.73×10²	0.646 1~12.92	0.999 0	0.013	0.032
15	FWA90	y=1.13×10⁴x-4.51×10²	y=8.68×10³x+42	y=8.36×10³x-51.7	5.669~113.4	0.996 9	0.11	0.28
16	FWA71	y=1.26×10⁴x-6.91×10²	y=1.28×10⁴x-1.39×10²	y=9.01×10³x+5.12×10²	14.46~289.2	0.999 8	0.29	0.72

Tab. 2

Tab. 3

Fig. 4

References 17

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序号	化合物	扫描模式	保留时间/min	母离子（m/z）	子离子（m/z）	碰撞电压/eV	锥孔电压/V
1	FWA162	+	4.83	242.1	185.1*，227.1	30，33	60
2	FWA140	+	5.07	232.1	188.1*，203.0	46，26	20
3	FWA135	+	5.86	291.2	185.0*，157.9	37，45	20
4	FWA185	+	5.87	319.1	226.0*，65.3	47，58	20
5	FWA393	+	6.62	415.1	207.0*，321.8	46，45	20
6	FWA367	+	6.64	363.1	270.1*，244.0	52，51	20
7	FWA KS-N	+	6.91	429.2	321.1*，335.1	54，54	60
8	FWA184	+	7.71	431.1	414.9*，401.1	65，55	60
9	FWA220	-	3.36	268.1	221.8*，197.0	-25，-25	-68
10	FWA263	-	3.44	282.2	197.0*，231.1	-32，-25	-60
11	FWA210	-	3.45	259.1	215.8*，197.1	-23，-31	-60
12	FWA85	-	3.99	413.2	117.1*，271.1	-40，-37	-60
13	FWA28	-	4.02	457.1	333.1*，292.2	-36，-40	-60
14	FWA351	-	4.12	258.1	80.0*，226.1	-29，-25	-80
15	FWA90	-	4.13	384.2	117.1*，303.6	-32，-25	-60
16	FWA71	-	4.17	439.2	283.9*，324.1	-37，-38	-20

Determination of 16 fluorescent whitening agents in cosmetics by ultra performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry

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序号	化合物	添加水平/ （μg/g）	水剂		乳剂		膏霜
序号	化合物	添加水平/ （μg/g）	平均回收率/%	RSD/%	平均回收率/%	RSD/%	平均回收率/%	RSD/%
1	FWA162	0.057	100.5	0.7	109.7	2.2	104.3	3.5
1	FWA162	0.29	100.6	0.5	105.7	2.7	110.7	0.8
2	FWA140	0.058	109.8	1.1	113.5	2.2	108.0	1.8
2	FWA140	0.29	112.0	1.1	105.3	2.1	107.3	1.8
3	FWA135	0.058	102.2	4.1	110.5	5.4	114.7	2.7
3	FWA135	0.29	96.6	2.3	99.7	3.3	107.5	4.7
4	FWA185	0.059	99.5	3.1	108.5	9.9	100.2	9.7
4	FWA185	0.29	94.3	3.2	102.4	3.7	85.5	12.5
5	FWA393	0.15	106.4	3.7	111.3	8.9	85.4	12.6
5	FWA393	0.75	112.1	4.9	102.9	2.1	91.5	3.1
6	FWA367	0.056	105.3	3.8	106.4	7.2	115.8	5.9
6	FWA367	0.28	110.2	3.8	97.9	3.4	108.2	2.2
7	FWA KS-N	0.11	98.3	6.0	105.6	3.6	72.1	8.9
7	FWA KS-N	0.56	102.4	6.6	101.1	1.9	83.0	5.9
8	FWA184	0.029	90.9	5.3	103.8	3.5	108.4	6.3
8	FWA184	0.15	94.9	2.6	93.7	7.9	103.9	2.2
9	FWA220	14	102.1	3.7	100.6	4.7	94.5	5.6
9	FWA220	70	103.8	4.8	106.3	2.5	98.4	3.3
10	FWA263	5.9	96.0	3.4	110.4	3.4	95.6	4.8
10	FWA263	30	96.5	1.4	108.6	2.0	97.9	2.6
11	FWA210	11	105.5	6.0	111.7	3.6	96.8	4.9
11	FWA210	56	101.9	4.1	108.2	3.1	98.4	1.1
12	FWA85	28	105.5	4.7	107.2	4.4	104.4	4.0
12	FWA85	139	92.1	3.0	103.9	2.6	103.1	2.3
13	FWA28	2.9	91.6	4.2	108.3	3.8	108.2	3.5
13	FWA28	14	94.2	2.9	99.6	6.2	108.0	1.5
14	FWA351	0.063	104.1	8.7	110.0	6.5	92.7	4.2
14	FWA351	0.32	94.1	9.0	105.5	4.2	103.1	2.9
15	FWA90	0.57	91.3	3.8	104.3	7.4	103.5	3.7
15	FWA90	2.8	97.9	5.0	102.5	6.8	105.0	1.8
16	FWA71	1.4	103.0	2.7	109.5	8.1	113.9	5.7
16	FWA71	7.2	97.7	4.3	104.5	3.4	113.9	2.5

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