超高效液相色谱-三重四极杆质谱法同时测定面膜中26种禁用物质

doi:10.3969/j.issn.1001-1803.2021.11.015

摘要/Abstract

摘要：

建立了超高效液相色谱-三重四极杆质谱法（UPLC-MS/MS）同时分离测定市售面膜中包括喹诺酮类、咪唑类及糖皮质激素等26种禁用成分。样品经饱和氯化钠溶液分散后乙腈提取,并利用亚铁氰化钾和乙酸锌沉淀大分子基质和固相萃取净化后,以0.1%醋酸乙腈-0.1%醋酸水溶液二元梯度洗脱,采用多反应监测进行分析。结果显示,26种化合物在各自浓度范围内线性关系良好,相关系数均不低于0.995,检出限为1~80 ng/g,定量限为4~380 ng/g,平均回收率为86.4%~115.2%。本法简单准确,灵敏度高,可用于市售面膜中禁用物质的定量分析。

关键词: 超高效液相色谱-三重四极杆质谱, 面膜, 糖皮质激素, 喹诺酮类, 咪唑类

Abstract:

An ultra performance liquid chromatography-triple quadrupole mass spectrometric （UPLC-MS/MS） method was developed for simultaneous separation and determination of 26 prohibited substances in commercially available masks, which contained glucocorticoid, quinolones and imidazole derivatives. The samples were dispersed in saturated sodium chloride solution and were extracted with acetonitrile. After removal of macromolecular matrix by potassium ferrocyanide and zinc acetate, the samples were purified by solid phase extraction. The binary gradient elution was performed with acetonitrile （containing 0.1% acetic acid）-0.1% acetic acid solution, and the multi-reaction monitoring was used for analysis. All the 26 compounds show a good linear relationship in their respective concentration ranges, and the correlation coefficients （r） are no less than 0.995. The limits of detection （LODs） range from 1 to 80 ng/g. The limits of quantification （LOQs） are in the range of 4-380 ng/g. The average recoveries of 26 prohibited substances in masks range from 86.4% to 115.2%. The method is simple, accurate and sensitive. It can be used for quantitative analysis of prohibited substances in commercially available masks.

Key words: ultra performance liquid chromatography-triple quadrupole mass spectrometry, mask, glucocorticoid, quinolones, imidazole derivatives

中图分类号:

TQ658

杜晖,任静. 超高效液相色谱-三重四极杆质谱法同时测定面膜中26种禁用物质[J]. 日用化学工业, 2021, 51(11): 1142-1149.

Du Hui,Ren Jing. Simultaneous determination of 26 prohibited substances in masks by ultra performance liquid chromatography-triple quadrupole mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2021, 51(11): 1142-1149.

图/表 7

表 1

表 2

图 1

图 2

图 3

表 3

26种化合物的线性方程、线性范围、相关系数、检出限和定量限"

序号	名称	线性方程	线性范围/（μg·g^-1）	r	LOD/（ng·g^-1）	LOQ/（ng·g^-1）
1	氟康唑	y=4.254×10⁵x+2.256×10⁴	0.96~28.95	0.999 8	2	10
2	酮康唑	y=7.017×10⁴x-7.178×10³	0.95~28.50	0.999 4	76	380
3	萘替芬	y=3.106×10⁶x-1.151×10⁵	1.00~30.06	0.999 9	1	4
4	联苯苄唑	y=2.150×10⁶x+2.940×10⁴	0.97~28.99	0.999 9	1	4
5	克霉唑	y=1.863×10⁶x+7.755×10⁴	0.98~29.46	0.999 9	4	20
6	益康唑	y=1.776×10⁶x+5.196×10⁴	0.96~28.84	0.999 9	1	4
7	咪康唑	y=1.031×10⁶x+3.125×10⁴	1.00~29.91	0.999 9	8	20
8	灰黄霉素	y=3.540×10⁵x-2.646×10³	0.96~28.88	1.000 0	8	20
9	依诺沙星	y=5.274×10⁵x-4.251×10⁴	1.00~19.90	0.998 5	80	320
10	氟罗沙星	y=3.804×10⁵x-1.199×10⁴	1.00~20.07	0.999 7	16	40
11	氧氟沙星	y=5.383×10⁵x+2.571×10⁴	1.05~21.09	0.999 6	8	16
12	诺氟沙星	y=3.171×10⁵x+4.753×10³	1.03~20.55	0.997 0	16	40
13	培氟沙星	y=5.291×10⁵x-1.570×10⁴	1.02~20.48	0.999 3	8	16
14	环丙沙星	y=1.522×10⁵x-3.624×10³	1.03~20.62	0.999 2	16	80
15	恩诺沙星	y=1.032×10⁶x-4.904×10⁴	1.00~19.94	0.998 2	4	8
16	沙拉沙星	y=4.787×10⁴x-1.355×10³	0.97~19.46	0.999 8	40	160
17	双氟沙星	y=1.983×10⁵x+2.240×10⁴	1.00~19.91	0.999 6	8	16
18	莫西沙星	y=1.959×10⁵x-1.650×10⁴	1.01~20.22	0.999 9	8	16
19	氟轻松	y=6.377×10⁶x-1.382×10⁴	1.08~21.64	0.996 8	42	84
20	曲安奈德	y=1.672×10⁶x-6.890×10³	0.98~19.68	0.999 8	50	100
21	倍他米松	y=5.679×10⁵x-3.872×10³	0.99~19.88	0.999 4	20	50
22	地塞米松	y=3.399×10⁵x+1.388×10⁴	1.00~20.08	0.999 5	20	50
23	地塞米松醋酸酯	y=5.360×10⁵x+2.012×10⁴	1.00~19.96	0.999 8	25	100
24	倍他米松醋酸酯	y=6.887×10⁵x+1.382×10⁴	1.01~20.26	0.999 8	25	100
25	倍他米松戊酸酯	y=4.568×10⁵x-8.382×10³	1.01~20.12	0.999 9	50	200
26	曲安奈德醋酸酯	y=3.398×10⁵x-1.223×10⁴	1.04~20.71	0.999 9	50	150

表 3

表 4

参考文献 12

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序号	名称	CAS号	来源	批号	含量/%
1	氟康唑	86386-73-4	中国食品药品检定研究院	100314-201204	100.0
2	酮康唑	79156-75-5	中国食品药品检定研究院	100294-201904	99.8
3	盐酸萘替芬	65473-14-5	中国食品药品检定研究院	100823-200501	100.0
4	灰黄霉素	126-07-8	中国食品药品检定研究院	0426-9101	99.0
5	联苯苄唑	60628-96-8	Stanford Chemicals	ML190411-08	98.0
6	克霉唑	23593-75-1	Stanford Chemicals	BL190913-04	98.0
7	益康唑	27220-47-9	Mikromol	W993634	100.2
8	咪康唑	22916-47-8	Sigma-aldrich	LRAB5528	99.5
9	依诺沙星	74011-58-8	中国食品药品检定研究院	130453-201802	91.5
10	氟罗沙星	79660-72-3	中国食品药品检定研究院	130458-200902	99.2
11	甲磺酸培氟沙星	70458-95-6	中国食品药品检定研究院	130459-201402	71.3
12	氧氟沙星	82419-36-1	Stanford Chemicals	ML191030-15	99.0
13	诺氟沙星	70458-96-7	Stanford Chemicals	ML190609-10	99.0
14	盐酸环丙沙星	86393-32-0	Stanford Chemicals	AL190415-12	99.0
15	恩诺沙星	93106-60-6	Stanford Chemicals	TC180203-07	98.0
16	盐酸沙拉沙星	91296-87-6	Stanford Chemicals	AL190423-20	98.0
17	盐酸双氟沙星	91296-86-5	Dr.Ehrenstorfer GmbH	114618	96.0
18	盐酸莫西沙星	186826-86-8	European Pharmacopoeia Reference Standard	Y0000703	96.1
19	氟轻松	67-73-2	USP Reference Standard	R041G0	99.7
20	倍他米松	378-44-9	中国食品药品检定研究院	100118-201204	99.3
21	曲安奈德	76-25-5	中国食品药品检定研究院	100055-201804	98.8
22	地塞米松	50-02-2	Dr.Ehrenstorfer GmbH	12170400	99.1
23	地塞米松醋酸酯	1177-87-3	Dr.Ehrenstorfer GmbH	12170410	99.4
24	倍他米松醋酸酯	987-24-6	Dr.Ehrenstorfer GmbH	995870	99.6
25	倍他米松戊酸酯	2152-44-5	Dr.Ehrenstorfer GmbH	10575020	99.6
26	曲安奈德醋酸酯	3870-07-3	Cato Research Chemical Inc	13F-12-19	99.7

序号	名称	保留时间/min	母离子（m/z）	子离子（m/z）	碰撞电压/eV
1	氟康唑	2.4	307.20	238.15^*,20.15	-16.0,-17.0
2	酮康唑	12.0	531.25	489.20^*,255.05	-32.0,-36.0
3	萘替芬	11.8	288.20	117.15^*,141.15	-20.0,-23.0
4	联苯苄唑	13.8	311.20	243.15^*,165.15	-20.0,-36.0
5	克霉唑	13.6	277.15	165.15^*,241.20	-20.0,-27.0
6	益康唑	15.0	381.10	125.10^*,193.20	-30.0,-20.0
7	咪康唑	16.0	417.05	159.05^*,161.10	-29.0,-33.0
8	灰黄霉素	12.7	353.10	165.15^*,215.10	-20.0,-20.0
9	依诺沙星	1.1	321.15	303.15^*,204.05	-20.0,-40.0
10	氟罗沙星	1.4	370.20	326.15^*,269.10	-20.0,-27.0
11	氧氟沙星	1.3	362.25	318.20^*,261.15	-19.0,-28.0
12	诺氟沙星	1.3	320.15	302.15^*,276.10	-21.0,-17.0
13	培氟沙星	1.4	334.20	290.20^*,233.15	-18.0,-25.0
14	环丙沙星	1.5	332.15	288.15^*,245.10	-17.0,-24.0
15	恩诺沙星	2.0	360.20	316.20^*,245.15	-19.0,-27.0
16	沙拉沙星	2.9	386.15	342.10^*,299.10	-19.0,-27.0
17	双氟沙星	3.0	400.15	356.15^*,299.10	-18.0,-30.0
18	莫西沙星	3.7	402.20	358.20^*,384.20	-22.0,-20.0
19	氟轻松	12.1	453.20	337.10^*,121.10	-17.0,-36.0
20	曲安奈德	12.0	435.20	415.10^*,339.10	-10.0,-16.0
21	倍他米松	8.5	393.20	373.20^*,355.10	-9.0,-13.0
22	地塞米松	8.9	393.20	373.20^*,355.10	-9.0,-13.0
23	地塞米松醋酸酯	14.2	435.20	415.10^*,397.10	-9.0,-12.0
24	倍他米松醋酸酯	13.9	435.20	415.20^*,397.10	-9.0,-12.0
25	倍他米松戊酸酯	16.3	477.30	355.10^*,279.10	-12.0,-18.0
26	曲安奈德醋酸酯	15.6	477.20	339.10^*,439.20	-17.0,-15.0

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