基于石墨烯固相萃取-二维高效液相色谱串联质谱检测化妆品中9种β受体阻滞剂

doi:10.3969/j.issn.2097-2806.2026.04.015

Abstract

Abstract:

This study established a method for the determination of nine β-blockers, including atenolol, in cosmetics using magnetic graphene solid-phase extraction coupled with two-dimensional high performance liquid chromatography tandem mass spectrometry. The samples were extracted with acetonitrile solution, and the targets were adsorbed with magnetic graphene as the solid phase extraction adsorbent. The samples were analyzed by two-dimensional liquid chromatography-tandem mass spectrometry （2D-LC-MS/MS）, and quantified by the standard curve external standard method. The findings indicate that a dosage of 8 mg of magnetic graphene, in conjunction with an adsorption period of 20 minutes and the utilization of a 5 mL acetonitrile solution as the eluent, can effectively achieve the enrichment and purification of nine β-blockers. The targets exhibit satisfactory linearity across three distinct matrices: aqueous, emulsion, and cream, within the mass concentration ranges of 50-800 ng/mL and 100-1 600 ng/mL, with the correlation coefficients （r） all greater than 0.999 1. The mean recoveries is found to range from 90.32% to 100.11%, 90.26% to 102.22%, and 90.42% to 102.02%, respectively. The method is characterized by high specificity, high sensitivity, and good reproducibility, and is suitable for the determination of nine β-blockers in complex cosmetic systems.

Key words: graphene solid-phase extraction, two-dimensional high-performance liquid chromatography-triple quadrupole mass spectrometry method, complex cosmetic systems, β-blocker

CLC Number:

TQ658

Yiqing Liu, Hongyan Chen, Ming Wei, Yilin Xu. Detection of nine β-blockers in cosmetics via graphene-based solid-phase extraction coupled with two-dimensional high-performance liquid chromatography-tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2026, 56(4): 545-550.

Figures/Tables 7

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Fig.2

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References 15

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禁用物质名称	母离子（m/z）	子离子（m/z）	锥孔电压/V	碰撞气能量/V
阿替洛尔	267.2	145.1^＊；190.2	80	32；24
拉贝洛尔	329.1	311.2^＊；162.0	70	26；27
比索洛尔	326.3	116.2^＊；74.1	80	26；28
索他洛尔	273.0	132.8^＊；212.8	80	20；20
普萘洛尔	260.1	116.1^＊；56.1	80	17；33
美托洛尔	268.2	116.1^＊；98.1	80	23；25
阿罗洛尔	372.1	316.1^＊；298.9	70	17；25
塞利洛尔	380.2	74.1^＊；251.0	70	25；33
贝凡洛尔	346.2	165.1^＊；150.0	40	37；22

禁用物质	基质	线性范围/（ng/mL）	线性方程	相关系数	检出限/（mg/kg）	定量限/（mg/kg）
阿替洛尔	膏霜	50.02~800.3	y=343.9x+3 361.7	0.999 8	0.05	0.14
	乳液		y=257.4x+3 762.1	0.999 1
	水剂		y=231.94x+2 360	0.999 8
普萘洛尔	膏霜	50.03~800.5	y=52.843x+73.5	0.999 5	0.12	0.40
	乳液		y=58.628x+1 483.6	0.999 7
	水剂		y=64.736x+1 347.1	0.999 5
美托洛尔	膏霜	50.41~806.6	y=157.73x-1 326.7	0.999 6	0.08	0.25
	乳液		y=121.37x+1 565.8	0.999 5
	水剂		y=171.57x+1 414.6	0.999 9
比索洛尔	膏霜	50.00~800.0	y=264.64x+288.75	0.999 8	0.02	0.06
	乳液		y=605.19x+9 667.5	0.999 4
	水剂		y=643.62x+4 807.5	0.999 8
拉贝洛尔	膏霜	50.56~809.0	y=248.9x+5 755.8	0.999 2	0.08	0.24
	乳液		y=440.02x+22 097	0.999 6
	水剂		y=550.89x+13 335	0.999 8
贝凡洛尔	膏霜	50.08~801.3	y=2 090.7x+18 667	0.999 9	0.15	0.48
	乳液		y=2 284x+45 150	0.999 5
	水剂		y=2 121.88x+21 416.62	0.999 9
阿罗洛尔	膏霜	49.86~797.8	y=512.05x-1 502.5	0.999 9	0.03	0.10
	乳液		y=328.41x+3 018.3	0.999 5
	水剂		y=525.63x+3 729.2	0.999 7
塞利洛尔	膏霜	50.03~800.5	y=22.556x+302.04	0.999 4	0.01	0.04
	乳液		y=32.072x+1 122.4	0.999 5
	水剂		y=37.087x+712.21	0.999 3
索他洛尔	膏霜	100.2~1603	y=76.589x+300.25	0.999 6	0.25	0.08
	乳液		y=67.583x+1 904.6	0.999 3
	水剂		y=65.423x+371.54	0.999 3

化合物名称	加标量/ng	回收率（RSD）/%
化合物名称	加标量/ng	水剂	乳液类	膏霜类
阿替洛尔	500.2	92.74（2.3）	94.80（4.3）	96.19（3.1）
	1004.0	96.41（1.6）	101.12（2.7）	94.90（2.4）
	5 002.0	92.22（5.8）	95.03（4.0）	95.65（3.8）
普萘洛尔	500.3	97.15（3.6）	94.70（4.8）	90.42（2.4）
	1 006.0	100.11（2.6）	99.87（3.2）	98.61（4.1）
	5 003.0	97.54（2.0）	97.19（3.4）	94.99（4.0）
美托洛尔	504.1	93.26（4.3）	100.4（3.9）	94.30（3.2）
	1 082.0	98.34（2.4）	101.30（5.5）	97.50（2.5）
	2 016.0	92.64（1.9）	96.54（2.2）	100.73（3.7）
比索洛尔	500.0	94.52（2.7）	93.99（5.2）	92.04（4.3）
	1 000.0	90.79（5.8）	93.51（3.2）	94.44（2.7）
	2 000.0	95.13（3.0）	95.32（2.8）	101.61（4.7）
拉贝洛尔	505.6	92.10（1.1）	90.26（1.3）	95.6（1.5）
	1 011.0	96.23（5.6）	96.93（4.6）	102.02（4.5）
	2 022.0	97.22（5.6）	92.95（1.4）	94.93（2.1）
贝凡洛尔	500.8	90.32（3.2）	102.22（2.5）	94.21（1.2）
	1 016.0	94.53（2.3）	93.73（3.2）	96.34（2.1）
	2 032.0	94.63（3.5）	97.34（4.1）	96.24（2.8）
阿罗洛尔	498.6	97.26（1.3）	96.51（3.6）	92.15（2.9）
	997.2	95.84（3.4）	97.32（2.8）	100.21（2.7）
	1 994.0	97.94（1.6）	90.86（3.3）	98.96（1.8）
塞利洛尔	500.3	96.03（3.6）	97.79（3.9）	100.30（1.5）
	1 006.0	98.70（1.8）	99.90（2.1）	97.74（2.2）
	2 001.0	93.88（2.2）	95.13（1.6）	92.99（3.2）
索他洛尔	1 002.0	96.26（3.3）	102.21（1.8）	96.29（2.6）
	2 003.0	94.93（4.1）	96.15（3.9）	97.21（4.9）
	4 006.0	99.95（2.4）	94.27（3.7）	96.39（3.0）

Detection of nine β-blockers in cosmetics via graphene-based solid-phase extraction coupled with two-dimensional high-performance liquid chromatography-tandem mass spectrometry

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