UPLC-Q-TOF-MS法测定化妆品和消毒产品中108种非法添加化合物

doi:10.3969/j.issn.2097-2806.2024.10.016

摘要/Abstract

摘要：

建立了超高效液相色谱-四极杆-飞行时间质谱（UPLC-Q-TOF-MS）进行筛查和确证化妆品和消毒产品中108种非法添加化合物的方法。样品采用饱和氯化钠溶液涡旋分散后，加入含0.05%（体积分数）甲酸的乙腈溶液超声提取，冷冻离心，X-Bridge C₁₈色谱柱（4.6 mm×100 mm，3.5 μm）分离。在电喷雾离子源、正负离子扫描模式下，通过宽谱碰撞诱导解离（bbCID）模式采集待测物的质谱信息，构建108种非法添加化合物的筛查数据库。实验比较了提取溶剂的影响，优化了色谱条件和质谱条件，考察了凝胶剂、膏霜剂和粉剂的基质效应和回收率。结果表明，108种化合物的检出限为0.05~2.25 mg/kg，定量限为0.15~7.50 mg/kg，线性关系良好，相关系数（R²）均不低于0.99，3个浓度水平的加标回收率为60.0%~122.1%、相对标准偏差（RSD）为1.2%~23.3%。应用该方法对83份化妆品和50份消字号抑菌制剂进行分析，最终从两份消毒产品中确证检出林可霉素和利多卡因，其含量分别为5 024.4和2.2 mg/kg。该方法操作简便，准确性好，适用于化妆品和消毒产品中多类非法添加化合物的筛查确证和定量分析，具有较强的应用价值。

关键词: 飞行时间质谱, 非法添加化合物, 化妆品, 消毒产品

Abstract:

An ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry method （UPLC-Q-TOF-MS） was established to identify 108 illegally added compounds in cosmetic and disinfectants. Samples were dispersed in a saturated sodium chloride solution, extracted by sonication with acetonitrile solution containing 0.05% formic acid, and frozen at 0 ℃ while centrifuged. Chromatographic separation was performed on a X-Bridge C₁₈ column （4.6 mm×100 mm, 3.5 μm） with gradient elution using 0.1% （volume fraction） acetic acid aqueous solution and acetonitrile as the mobile phases. The mass spectrum information of the tested compounds was collected by broadband collision-induced dissociation （bbCID） mode under the electrospray ion source and positive and negative ion scanning mode, and a screening database of 108 illegally added compounds was constructed. The effect of extraction solvent was investigated and the chromatographic and mass spectrometry conditions were optimized. The matrix effects and recovery of gel-, cream-, and powder-based cosmetics were also investigated. The results show that the detection limit of 108 compounds is 0.05-2.25 mg/kg, and the limit of quantification is 0.15-7.50 mg/kg. The correlation coefficient （R²） are greater than 0.99 in the corresponding liner concentration range. Average recoveries are in the range of 60.0%-122.1% at three spiked levels, and the relative standard deviations （RSDs） are 1.2%-23.3%. A total of 83 cosmetics and 50 antibacteriostatic samples are analyzed by this established method. Finally, lincomycin and lidocaine are detected in two batches of disinfection products. The contents of lincomycin and lidocaine are 5 024.4 mg/kg and 2.2 mg/kg, respectively. The optimized method is simple, accurate and suitable for rapid screening and simultaneous quantitative analysis of various illegally added compounds in cosmetics and disinfectants.

Key words: time of flight mass spectrometry, illegally added compounds, cosmetics, disinfectants

中图分类号:

TQ658

刘雪年, 鲁毅翔, 张科明, 焦爱军. UPLC-Q-TOF-MS法测定化妆品和消毒产品中108种非法添加化合物[J]. 日用化学工业（中英文）, 2024, 54(10): 1276-1288.

Xuenian Liu, Yixiang Lu, Keming Zhang, Aijun Jiao. Determination of 108 illegally added compounds in cosmetics and disinfectants by UPLC-Q-TOF-MS[J]. China Surfactant Detergent & Cosmetics, 2024, 54(10): 1276-1288.

图/表 4

表1

108种化合物的来源、纯度和质谱参数信息"

序号	化合物	类别	分子式	保留时间/min	母离子（m/z）	碎片离子1 （m/z）	碎片离子2 （m/z）	品牌	纯度/%
1	曲安西龙	糖皮质激素	C₂₁H₂₇FO₆	13.32	395.186 7	375.178 4	357.168 1	NIFDC	99.6
2	泼尼松龙	糖皮质激素	C₂₁H₂₈O₅	15.16	361.201 2	343.182 7	325.172 8	NIFDC	99.5
3	泼尼松	糖皮质激素	C₂₁H₂₆O₅	15.35	359.185 9	341.171 2	265.155 8	NIFDC	99.7
4	异氟泼尼松	糖皮质激素	C₂₁H₂₇FO₅	15.29	379.191 8	359.183 6	341.173 7	CATO	96.2
5	氢化可的松	糖皮质激素	C₂₁H₃₀O₅	15.35	363.217 1	327.192 3	267.173 0	NIFDC	99.7
6	可的松	糖皮质激素	C₂₁H₂₈O₅	15.67	361.201 2	163.111 7	145.099 8	NIFDC	97.2
7	甲基泼尼松龙	糖皮质激素	C₂₂H₃₀O₅	17.04	375.216 9	357.204 6	339.194 1	NIFDC	99.0
8	倍他米松	糖皮质激素	C₂₂H₂₉FO₅	17.44	393.207 5	373.197 6	355.182 1	NIFDC	99.3
9	地塞米松	糖皮质激素	C₂₂H₂₉FO₅	17.57	393.207 3	373.190 8	355.182 5	NIFDC	99.8
10	氟米松	糖皮质激素	C₂₂H₂₈F₂O₅	17.83	411.198 2	371.184 5	335.160 3	NIFDC	99.8
11	倍氯米松	糖皮质激素	C₂₂H₂₉ClO₅	18.03	409.178 0	391.163 9	373.197 0	NIFDC	99.8
12	曲安奈德	糖皮质激素	C₂₄H₃₁FO₆	18.68	435.218 2	397.197 7	225.125 9	NIFDC	99.3
13	地索奈德	糖皮质激素	C₂₄H₃₂O₆	18.71	417.227 6	399.207 6	341.166 5	CATO	99.0
14	氟尼缩松	糖皮质激素	C₂₄H₃₁FO₆	19.06	435.218 3	339.154 0	321.143 4	CATO	100.0
15	氟轻松	糖皮质激素	C₂₄H₃₀F₂O₆	19.38	453.208 8	437.234 4	337.141 1	First standard	99.9
16	曲安西龙双醋酸酯	糖皮质激素	C₂₅H₃₁FO₈	19.38	479.208 1	441.188 8	399.179 4	NIFDC	95.4
17	氟氢缩松	糖皮质激素	C₂₄H₃₃FO₆	19.51	437.233 7	285.163 5	225.126 1	CATO	99.8
18	泼尼松龙醋酸酯	糖皮质激素	C₂₃H₃₀O₆	19.64	403.211 7	385.191 5	325.172 6	NIFDC	97.6
19	氟米龙	糖皮质激素	C₂₂H₂₉FO₄	20.17	377.212 4	339.193 2	279.173 1	NIFDC	97.9
20	氢化可的松醋酸酯	糖皮质激素	C₂₃H₃₂O₆	19.97	405.227 4	327.192 7	309.183 4	NIFDC	99.5
21	氟氢可的松醋酸酯	糖皮质激素	C₂₃H₃₁FO₆	20.30	423.218 2	239.144 0	181.102 3	NIFDC	99.7
22	地夫可特	糖皮质激素	C₂₅H₃₁NO₆	20.43	442.223 4	312.193 0	142.048 7	NIFDC	98.7
23	泼尼松醋酸酯	糖皮质激素	C₂₃H₂₈O₆	20.68	401.196 1	313.173 0	295.163 0	NIFDC	99.7
24	可的松醋酸酯	糖皮质激素	C₂₃H₃₀O₆	21.09	403.212 0	343.188 2	163.110 9	NIFDC	99.1
25	卤美他松	糖皮质激素	C₂₂H₂₇ClF₂O₅	21.09	445.158 8	427.147 3	403.210 1	TRC	98.5
26	甲基泼尼松龙醋酸酯	糖皮质激素	C₂₄H₃₂O₆	18.80	417.227 1	399.208 1	339.187 1	NIFDC	99.1
27	倍他米松醋酸酯	糖皮质激素	C₂₄H₃₁FO₆	21.93	435.218 2	397.192 2	355.181 0	NIFDC	99.1
28	地塞米松醋酸酯	糖皮质激素	C₂₄H₃₁FO₆	22.71	435.217 9	397.191 3	319.162 3	NIFDC	99.1
29	布地奈德	糖皮质激素	C₂₅H₃₄O₆	22.30	431.242 9	413.229 9	341.173 0	NIFDC	99.5
30	氢化可的松丁酸酯	糖皮质激素	C₂₅H₃₆O₆	22.84	433.258 7	309.182 3	267.172 7	NIFDC	99.7
31	氟米龙醋酸酯	糖皮质激素	C₂₄H₃₁FO₅	23.62	419.223 2	339.193 7	321.183 3	USP	99.2
32	氢化可的松戊酸酯	糖皮质激素	C₂₆H₃₈O₆	25.44	447.274 6	345.204 8	309.182 3	NIFDC	98.9
33	曲安奈德醋酸酯	糖皮质激素	C₂₆H₃₃FO₇	25.32	477.228 9	457.220 6	439.211 4	NIFDC	98.4
34	二氟拉松双醋酸酯	糖皮质激素	C₂₆H₃₂F₂O₇	25.83	495.219 7	335.157 6	317.147 2	NIFDC	98.6
35	氟轻松醋酸酯	糖皮质激素	C₂₆H₃₂F₂O₇	25.83	495.219 7	357.144 2	337.138 7	NIFDC	99.4
36	倍他米松戊酸酯	糖皮质激素	C₂₇H₃₇FO₆	27.47	477.265 0	457.220 6	439.211 4	NIFDC	99.5
37	哈西奈德	糖皮质激素	C₂₄H₃₂ClFO₅	27.99	455.199 6	181.099 6	143.084 6	NIFDC	99.5
38	泼尼卡酯	糖皮质激素	C₂₇H₃₆O₈	28.11	489.248 9	471.237 1	381.204 7	USP	99.2
39	氯替泼诺	糖皮质激素	C₂₄H₃₁ClO₇	28.31	467.183 2	449.168 3	359.137 1	Yuanye	98.0
40	阿氯米松双丙酸酯	糖皮质激素	C₂₈H₃₇ClO₇	28.70	521.230 3	319.164 6	301.154 6	USP	99.7
41	安西奈德	糖皮质激素	C₂₈H₃₅FO₇	28.64	503.243 4	483.237 3	399.179 2	USP	99.7
42	卤倍他索丙酸酯	糖皮质激素	C₂₅H₃₁ClF₂O₅	28.31	485.190 0	373.130 8	353.123 2	CATO	99.4
43	氯倍他索丙酸酯	糖皮质激素	C₂₅H₃₂ClFO₅	28.58	467.199 1	373.153 5	355.145 5	NIFDC	99.2
44	氟替卡松丙酸酯	糖皮质激素	C₂₅H₃₁F₃O₅S	28.58	501.190 0	467.164 2	200.986 4	NIFDC	99.8
45	莫米他松糠酸酯	糖皮质激素	C₂₇H₃₀Cl₂O₆	28.87	521.149 3	503.134 8	373.152 9	NIFDC	99.9
46	倍他米松双丙酸酯	糖皮质激素	C₂₈H₃₇FO₇	28.64	505.260 2	411.215 3	319.168 0	NIFDC	99.2
47	倍氯米松双丙酸酯	糖皮质激素	C₂₈H₃₇ClO₇	29.30	521.230 7	319.170 3	301.157 4	NIFDC	98.8
48	双氟可龙戊酸酯	糖皮质激素	C₂₇H₃₆F₂O₅	28.91	479.260 9	355.189 8	337.179 0	Bepure	99.4
49	氯倍他松丁酸酯	糖皮质激素	C₂₆H₃₂ClFO₅	29.83	479.200 3	375.194 9	355.188 5	NIFDC	99.3
50	环索奈德	糖皮质激素	C₃₂H₄₄O₇	31.37	541.316 2	523.305 3	393.205 2	Yuanye	99.0
51	睾酮	性激素	C₁₉H₂₈O₂	21.63	289.216 1	141.069 2	117.069 1	CATO	98.5
52	孕三烯酮	性激素	C₂₁H₂₄O₂	23.35	309.185 3	262.135 2	241.158 7	NIFDC	99.8
53	甲基睾丸酮	性激素	C₂₀H₃₀O₂	23.62	303.232 0	285.219 1	109.064 0	NIFDC	99.5
54	炔诺孕酮	性激素	C₂₁H₂₈O₂	25.70	313.216 2	245.187 5	145.100 2	NIFDC	99.4
55	醋酸甲地孕酮	性激素	C₂₄H₃₂O₄	28.64	385.237 6	282.196 8	267.173 4	NIFDC	99.0
56	黄体酮	性激素	C₂₁H₃₀O₂	28.83	315.231 8	123.079 8	109.064 2	NIFDC	99.7
57	醋酸甲羟孕酮	性激素	C₂₄H₃₄O₄	28.83	387.253 1	327.230 8	285.220 1	NIFDC	99.6
58	己酸羟孕酮	性激素	C₂₇H₄₀O₄	32.16	429.300 7	271.203 7	253.192 4	NIFDC	99.8
59	雌三醇^*	性激素	C₁₈H₂₄O₃	14.37	287.165 3	255.132 5	195.076 0	NIFDC	98.4
60	雌二醇^*	性激素	C₁₈H₂₄O₂	28.95	271.169 7	223.108 1	182.936 1	NIFDC	96.3
61	雌酮^*	性激素	C₁₈H₂₂O₂	23.97	269.154 8	183.075 3	159.076 1	NIFDC	99.5
62	己烯雌酚^*	性激素	C₁₈H₂₀O₂	25.34	267.139 3	251.099 7	237.084 1	NIFDC	99.5
63	氧氟沙星	喹诺酮	C₁₈H₂₀FN₃O₄	10.53	362.151 8	318.162 1	276.151 4	NIFDC	99.7
64	环丙沙星	喹诺酮	C₁₇H₁₈FN₃O₃	10.72	332.140 9	245.106 3	231.054 5	NIFDC	83.1
65	依诺沙星	喹诺酮	C₁₅H₁₇FN₄O₃	10.01	321.136 8	232.048 0	204.054 0	NIFDC	91.5
66	沙拉沙星	喹诺酮	C₂₀H₁₇F₂N₃O₃	12.68	386.132 4	368.121 7	342.140 8	NIFDC	100.0
67	培氟沙星	喹诺酮	C₁₇H₂₀FN₃O₃	10.59	334.156 4	245.105 8	231.054 4	NIFDC	71.3
68	氟罗沙星	喹诺酮	C₁₇H₁₈F₃N₃O₃	10.72	370.138 1	326.146 8	269.089 9	NIFDC	99.2
69	双氟沙星	喹诺酮	C₂₁H₁₉F₂N₃O₃	12.94	400.148 2	382.136 7	356.157 1	CATO	96.9
70	莫西沙星	喹诺酮	C₂₁H₂₄FN₃O₄	13.07	402.183 8	205.038 5	217.037 9	NIFDC	95.6
71	诺氟沙星	喹诺酮	C₁₆H₁₈FN₃O₃	10.40	320.141 1	232.050 6	205.073 7	NIFDC	99.6
72	恩诺沙星	喹诺酮	C₁₉H₂₂FN₃O₃	11.57	360.172 6	316.181 4	245.108 5	NIFDC	100.0
73	地氯雷他定	抗过敏	C₁₉H₁₉ClN₂	13.70	311.131 5	294.104 0	282.103 8	NIFDC	99.9
74	曲吡那敏	抗过敏	C₁₆H₂₁N₃	14.22	256.181 2	211.121 6	191.970 8	NIFDC	100.0
75	溴苯那敏	抗过敏	C₁₆H₁₉BrN₂	17.83	319.080 9	276.019 4	274.021 5	TMstandard	99.6
76	羟嗪	抗过敏	C₂₁H₂₇ClN₂O₂	17.04	375.184 3	201.046 4	173.127 9	NIFDC	98.6
77	西替利嗪	抗过敏	C₂₁H₂₅ClN₂O₃	19.13	389.163 5	201.046 3	187.107 1	NIFDC	99.6
78	氯丙嗪	抗过敏	C₁₇H₁₉ClN₂S	17.83	319.103 7	246.014 1	274.045 2	NIFDC	99.7
79	氯雷他定	抗过敏	C₂₂H₂₃ClN₂O₂	26.81	383.153 3	337.110 5	267.080 9	NIFDC	99.9
80	特非那定	抗过敏	C₃₂H₄₁NO₂	22.85	472.322 8	454.309 8	436.299 3	NIFDC	99.3
81	赛庚啶	抗过敏	C₂₁H₂₁N	17.36	288.175 0	215.086 0	191.086 7	NIFDC	92.2
82	普鲁卡因胺	局部麻醉药	C₁₃H₂₁N₃O	5.12	236.176 2	173.987 2	163.086 2	Stanford Chemicals	99.8
83	普鲁卡因	局部麻醉药	C₁₃H₂₀N₂O₂	8.31	237.160 0	164.067 7	120.042 0	Stanford Chemicals	99.3
84	氯普鲁卡因	局部麻醉药	C₁₃H₁₉ClN₂O₂	10.72	271.120 7	198.020 8	154.002 5	USP	99.6
85	苯佐卡因	局部麻醉药	C₉H₁₁NO₂	17.38	166.086 4	138.054 6	120.043 9	NIFDC	99.9
86	利多卡因	局部麻醉药	C₁₄H₂₂N₂O	12.08	235.180 9	150.969 7	132.958 4	Stanford Chemicals	99.4
87	丁卡因	局部麻醉药	C₁₅H₂₄N₂O₂	15.38	265.191 4	220.131 3	176.105 8	Dr. Ehrenstorfer	99.9
88	辛可卡因	局部麻醉药	C₂₀H₂₉N₃O₂	17.98	344.233 9	271.144 0	228.100 8	Stanford Chemicals	99.3
89	磺胺吡啶	磺胺类	C₁₁H₁₁N₃O₂S	10.46	250.064 7	184.087 5	156.011 7	NIFDC	99.3
90	磺胺甲嘧啶	磺胺类	C₁₁H₁₂N₄O₂S	10.72	265.075 5	190.028 1	156.011 5	Dr. Ehrenstorfer	99.2
91	磺胺甲二唑	磺胺类	C₉H₁₀N₄O₂S₂	11.76	271.031 7	156.010 9	116.028 0	NIFDC	99.7
92	磺胺甲氧嗪	磺胺类	C₁₁H₁₂N₄O₃S	11.96	281.070 7	156.009 0	126.064 0	NIFDC	99.8
93	磺胺氯哒嗪	磺胺类	C₁₀H₉ClN₄O₂S	13.39	285.020 6	156.010 9	130.015 6	NIFDC	99.6
94	磺胺甲噁唑	磺胺类	C₁₀H₁₁N₃O₃S	14.17	254.059 4	156.008 3	147.074 6	CATO	99.8
95	多西环素	四环素	C₂₂H₂₄N₂O₈	13.29	445.161 0	428.125 4	410.115 1	NIFDC	83.6
96	米诺环素	四环素	C₂₃H₂₇N₃O₇	11.18	458.192 5	441.167 0	423.158 1	Yuanye	98.0
97	四环素	四环素	C₂₂H₂₄N₂O₈	11.31	445.160 9	428.129 3	410.118 8	NIFDC	98.4
98	土霉素	四环素	C₂₂H₂₄N₂O₉	10.72	461.156 0	444.119 9	426.109 8	NIFDC	88.8
99	金霉素	四环素	C₂₂H₂₃ClN₂O₈	13.66	479.122 5	462.095 8	444.085 1	NIFDC	94.1
100	氟康唑	抗真菌	C₁₃H₁₂F₂N₆O	12.08	307.111 7	238.074 3	220.063 9	NIFDC	99.8
101	螺内酯	抗真菌	C₂₄H₃₂O₄S	24.74	417.207 5	399.214 8	341.172 7	NIFDC	99.9
102	灰黄霉素	抗真菌	C₁₇H₁₇ClO₆	21.09	353.079 0	285.051 1	215.009 4	NIFDC	99.0
103	克林霉素	林可酰胺	C₁₈H₃₃ClN₂O₅S	12.62	445.161 0	428.125 4	410.115 1	NIFDC	83.6
104	林可霉素	林可酰胺	C₁₈H₃₄N₂O₆S	9.30	458.192 5	441.167 0	423.158 1	Yuanye	98.0
105	甲硝唑	硝基咪唑	C₆H₉N₃O₃	8.50	172.071 9	150.968 2	132.958 0	NIFDC	100
106	呋喃它酮	硝基呋喃	C₁₃H₁₆N₄O₆	9.67	325.114 6	281.122 9	252.096 8	Sigma-Aldrich	99.8
107	氯霉素^*	酰胺醇	C₁₁H₁₂Cl₂N₂O₅	15.51	321.005 5	257.017 0	176.026 7	NIFDC	99.8
108	他扎罗汀	维甲酸	C₂₁H₂₁NO₂S	30.90	352.138 0	324.105 8	294.057 3	NIFDC	100.0

表1

图1

表2

108种化合物的基质效应"

序号	化合物	线性方程			基质效应/%
序号	化合物	凝胶	霜	爽身粉	凝胶	霜	爽身粉
1	曲安西龙	y=66.46x+513.24	y=102.89x+982.74	y=171.95x+415.71	43.46	12.46	46.29
2	泼尼松龙	y=179.65x+174.01	y=198.21x-269.69	y=231.99x-165.26	10.28	21.68	42.41
3	泼尼松	y=760.11x-1 889.26	y=447.06x+5 569.87	y=440.3x+9 564.82	95.15	14.78	13.04
4	异氟泼尼松	y=167.51x+717.82	y=164.93x+1 188.19	y=174.39x+2 063.53	1.16	0.40	5.31
5	氢化可的松	y=459.97x+3 496.44	y=385.87x+4 449.41	y=328.28x+8 138.34	29.06	8.27	7.89
6	可的松	y=499.70x+2 388.14	y=538.59x-188.79	y=461.55x+5 742.62	6.35	14.63	1.77
7	甲基泼尼松龙	y=211.13x+3 818.26	y=222.16x+3 366.1	y=239.63x+3 146.16	33.49	30.02	24.51
8	倍他米松	y=134.41x+499.72	y=248.15x+894.06	y=178.70x+2 039.76	29.91	139.85	72.72
9	地塞米松	y=258.81x+23.41	y=341.19x+2 318.27	y=181.64x+2 873.24	20.28	5.09	44.05
10	氟米松	y=142.01x+483.60	y=234.15x+360.39	y=214.39x+3 164.63	23.60	25.97	15.34
11	倍氯米松	y=21.98x+546.23	y=23.18x+749.39	y=22.65x+860.10	16.17	22.52	19.71
12	曲安奈德	y=267.82x+2 867.55	y=590.89x+3 456.63	y=242.96x+5 449.30	10.51	143.83	0.26
13	地索奈德	y=255.70x+894.05	y=100.83x+1 982.79	y=275.67x+5 922.67	6.14	62.99	1.19
14	氟尼缩松	y=254.49x+1 410.49	y=295.08x+3 929.69	y=252.73x+8 000.73	1.51	14.20	2.19
15	氟轻松	y=274.71x+1 850.41	y=343.77x-903.32	y=242.24x+2 959.76	33.61	16.92	41.46
16	曲安西龙双醋酸酯	y=177.10x+668.59	y=324.66x+299.82	y=195.93x+2 360.66	2.48	87.86	13.37
17	氟氢缩松	y=83.79x+1 103.78	y=154.99x+894.02	y=254.53x+5 542.68	71.30	46.92	12.83
18	泼尼松龙醋酸酯	y=202.45x+1 613	y=177.41x+2 104.77	y=370.95x+2 106.74	2.84	9.88	88.44
19	氟米龙	y=154.14x+1 403.91	y=167.61x+596.82	y=222.9x+5 033.81	22.63	15.87	11.88
20	氢化可的松醋酸酯	y=955.44x-968.77	y=522.37x+937.07	y=1 127.23x-5 016.57	99.95	9.32	135.91
21	氟氢可的松醋酸酯	y=316.32x+742.36	y=211.66x-177.33	y=370.22x+3 430.61	5.53	36.79	10.57
22	地夫可特	y=1 691.34x+170.67	y=1 834.03x+1 225.77	y=1 512.18x+6 854.12	1.56	6.74	11.99
23	泼尼松醋酸酯	y=411.31x+1 474.50	y=567.88x+2 160.32	y=880.05x-1 515.14	10.50	23.57	91.50
24	可的松醋酸酯	y=187.48x+614.62	y=148.63x+2 007	y=290.84x+2 446.49	52.43	62.29	26.20
25	卤美他松	y=50.01x+834.81	y=96.97x+1 250.52	y=47.83x+1 638.91	12.18	117.52	7.29
26	甲基泼尼松龙醋酸酯	y=281.50x+4 056.85	y=367.91x-909.04	y=32.35x+740.69	222.19	321.09	62.97
27	倍他米松醋酸酯	y=205.54x+1 162.29	y=232.40x+341.70	y=229.14x+2 923.13	13.16	27.95	26.16
28	地塞米松醋酸酯	y=223.44x+536.59	y=231.13x+560.08	y=199.43x+9 995.70	21.87	26.06	8.77
29	布地奈德	y=14.65x+423.02	y=176.26x+137.93	y=139.41x-375.50	89.36	28.05	1.28
30	氢化可的松丁酸酯	y=394.40x+361.99	y=308.51x+1 945.69	y=242.11x+2 196.20	54.20	20.62	5.34
31	氟米龙醋酸酯	y=362.94x+1 881.87	y=495.99x+2 715.27	y=372.13x+7 111.01	8.69	24.79	6.38
32	氢化可的松戊酸酯	y=165.31x+1 330	y=149.96x+1 599.23	y=425.40x+417.95	3.00	12.01	149.60
33	曲安奈德醋酸酯	y=176.61x+2 205.38	y=175.39x+1 413.26	y=215.63x+3 117.43	2.21	1.50	24.79
34	二氟拉松双醋酸酯	y=599.83x+5 602.91	y=664.50x+4 185.95	y=492.1x+8 364.53	6.54	18.02	12.60
35	氟轻松醋酸酯	y=599.83x+5 602.91	y=664.50x+4 185.95	y=492.1x+8 364.53	6.54	18.02	12.60
36	倍他米松戊酸酯	y=180.97x+1 292.54	y=321.23x-588.32	y=123.81x+3 639.05	28.51	128.11	12.08
37	哈西奈德	y=901.4x-1 334.46	y=572.28x-2 435.88	y=203.52x+8 809.85	123.10	41.64	49.63
38	泼尼卡酯	y=922.66x-1 342.59	y=396.29x-1 011.36	y=263.45x+1 989.15	297.54	70.75	13.51
39	氯替泼诺	y=224.99x+3 642.75	y=215.56x-553.54	y=320.59x+2 483.09	153.37	142.75	261.02
40	阿氯米松双丙酸酯	y=194.37x+3 681.68	y=158.58x+107.55	y=151.19x+1 987.76	192.29	138.47	127.35
41	安西奈德	y=297.34x+2 140.24	y=386.93x-1 032.1	y=66.39x+8 594.66	115.45	180.36	51.89
42	卤倍他索丙酸酯	y=109.71x+3 063.74	y=125.87x-306.55	y=33.77x+3 884.97	91.30	119.48	41.12
43	氯倍他索丙酸酯	y=310x+2 738.76	y=153.74x-379.46	y=293.20x+1 512.74	464.35	179.88	433.77
44	氟替卡松丙酸酯	y=568.84x+2 748.79	y=1 090.79x-5 002.03	y=746.32x+5 358.35	202.33	479.74	296.66
45	莫米他松糠酸酯	y=20.4x+354.26	y=58.14x+252.16	y=27.21x+1 060.60	40.07	70.80	20.06
46	倍他米松双丙酸酯	y=113.51x+2 783.33	y=402.24x-2 630.49	y=362.04x+2 140.38	107.86	636.57	562.96
47	倍氯米松双丙酸酯	y=433.47x+471.28	y=309.78x-1 498.62	y=186.12x+3 051.29	374.83	239.34	103.88
48	双氟可龙戊酸酯	y=220.39x+948.96	y=318.27x-530.70	y=226.14x+1 952.72	175.80	298.29	182.99
49	氯倍他松丁酸酯	y=639.14x+2 943.38	y=273x-1 130.98	y=392.65x+4 254.19	456.02	137.49	241.58
50	环索奈德	y=338.98x+2 250.70	y=274.95x	y=110.06x+3 800.63	17.44	33.04	73.20
51	睾酮	y=304.20x-249.82	y=996.99x+8 534.97	y=609.97x+558.17	2.26	235.13	105.04
52	孕三烯酮	y=1 168.46x+9 630.80	y=145.57x+4 817.89	y=1 272.47x-2 693.66	359.17	42.79	400.05
53	甲基睾丸酮	y=571.37x+1 481.35	y=7.62x+1 115.08	y=204.76x-640.13	12.52	98.50	59.68
54	炔诺孕酮	y=1 170.72x-772.8	y=125.31x+417.63	y=377.86x+1 584.76	128.41	75.55	26.28
55	醋酸甲地孕酮	y=839.12x+13 289.95	y=585.38x-2 206.42	y=162.64x+22 245.24	9.90	23.33	78.70
56	黄体酮	y=176.52x+7 378.41	y=46.61x+479.34	y=323.20x+4 164.48	203.51	19.86	455.71
57	醋酸甲羟孕酮	y=107.53x+866.68	y=91.33x	y=135.33x+4 131.84	88.12	59.78	136.76
58	己酸羟孕酮	y=822.03x-2 712.74	y=141.95x+999.53	y=28.25x+3 660.39	611.78	22.91	75.54
59	雌三醇	y=93.78x+193.08	y=107.84x+295.30	y=98.02x+18.35	59.98	83.96	67.21
60	雌二醇	y=3.02x+347.62	y=2.01x+1 601.85	y=4.97x+235.23	70.88	80.62	52.07
61	雌酮	y=126.42x-383.70	y=123.30x+53.51	y=174x+18.58	41.23	42.68	19.11
62	己烯雌酚	y=1 344.40x+877.91	y=956.47x-3 221.04	y=1 080.25x-639.83	75.90	25.15	41.34
63	氧氟沙星	y=504.76x+578.91	y=581.86x+1 604.49	y=539.41x+330.38	43.07	34.37	39.16
64	环丙沙星	y=1 067.55x-1 367.96	y=2 148.14x-6 140.65	y=684.15x+5 669.93	7.59	85.94	40.78
65	依诺沙星	y=447.27x+1 410.48	y=400.95x+809.91	y=466.31x+151.11	13.95	22.86	10.29
66	沙拉沙星	y=117.11x-278.33	y=296.03x-125.79	y=225.69x+811.93	69.87	23.83	41.93
67	培氟沙星	y=521.23x+731.26	y=542.68x-113.67	y=537.47x+2 401.97	13.09	17.74	16.61
68	氟罗沙星	y=432.76x-1 184.45	y=494.47x+3 130.24	y=425.17x+3 438.16	0.18	14.46	1.58
69	双氟沙星	y=222.03x-555.22	y=406.28x-1 318.21	y=595.74x+2 627.50	58.93	24.85	10.20
70	莫西沙星	y=812.31x-3 382.45	y=972.05x-2 432.64	y=1 005.49x-1 775.76	9.48	8.32	12.04
71	诺氟沙星	y=651.33x+844.07	y=538.55x-1 838.30	y=540.93x+2 313.93	21.47	0.44	0.88
72	恩诺沙星	y=134.22x+6 386	y=1 001.31x-1 963.14	y=561.32x+887.52	85.32	9.53	38.60
73	地氯雷他定	y=5.05x+423.78	y=4.48x+253.13	y=7.25x+568.07	18.81	27.97	16.56
74	曲吡那敏	y=1 539.47x-6 860.3	y=1 605.66x-8 493.46	y=788.12x+3 988.10	2.62	1.57	50.15
75	溴苯那敏	y=436.02x-1 386.36	y=685.22x+214.88	y=435.81x+2 287.17	42.53	9.69	42.56
76	羟嗪	y=376.82x-1 162.17	y=208.72x+1 099.13	y=217.61x+2 828.60	27.53	29.36	26.35
77	西替利嗪	y=236.11x-215.94	y=272.53x+2 304.69	y=244.02x+825.43	6.49	22.91	10.05
78	氯丙嗪	y=285.63x-865.92	y=404.96x+10.09	y=367.81x-192.92	48.12	26.45	33.20
79	氯雷他定	y=2 860.53x+1 738.88	y=3 649.10x-7 009.32	y=2 662.09x+15 070.28	14.29	45.80	6.36
80	特非那定	y=21.56x+629.20	y=-11.37x+6 541.58	y=33.71x+1 379.43	22.15	164.42	90.99
81	赛庚啶	y=2 013.47x+2 407.17	y=2 155.1x-2 177.98	y=1 215.50x+28 964.21	17.49	11.69	50.19
82	普鲁卡因胺	y=303.31x-421.04	y=431.53x-580.45	y=385.76x+4 034.85	18.88	15.41	3.17
83	普鲁卡因	y=486.05x+286.63	y=530.04x+1 008.11	y=419.59x+6 132.04	34.32	28.37	43.30
84	氯普鲁卡因	y=334.77x+398.14	y=1 131.75x-2 217.64	y=1 069.75x-1 002.13	41.67	97.19	86.38
85	苯佐卡因	y=1 960.53x+687.43	y=817.65x-182.70	y=1 039.82x+14 359.93	103.29	15.22	7.82
86	利多卡因	y=111.68x+571.39	y=2 665.27x-7 772.63	y=1 238.01x-3 196.38	86.13	230.94	53.72
87	丁卡因	y=612.87x+10 017.87	y=693.40x+2 745.98	y=629.49x+12 879.96	1.00	14.27	3.74
88	辛可卡因	y=1 491.10x+827.28	y=1 141.26x-1 651.13	y=890.22x+6 159.70	38.87	6.29	17.09
89	磺胺吡啶	y=482.91x+7 119.99	y=578.96x+2 242.06	y=515.99x+5 008.30	6.21	12.44	0.21
90	磺胺甲嘧啶	y=621.69x+3 087.84	y=692.21x+966.67	y=670.81x+13 424.74	0.96	10.27	6.86
91	磺胺甲二唑	y=56.17x-223.02	y=213.23x+1 197.76	y=616.27x+125.5	72.02	6.21	206.97
92	磺胺甲氧嗪	y=165.93x+374.32	y=1 504.21x+6 979.13	y=2 781.15x-701.29	94.40	49.24	6.15
93	磺胺氯哒嗪	y=234.12x+1 068.03	y=325.11x+3 456.52	y=826.08x-642	54.56	36.89	60.35
94	磺胺甲噁唑	y=661.37x-298.51	y=626.23x+750.01	y=905.11x+1 325.94	0.22	5.10	37.16
95	多西环素	y=180.62x+1 822.83	y=146.10x+108.56	y=197.89x+324.74	56.56	64.86	52.40
96	米诺环素	y=3.77x+730.25	y=33.92x+822.54	y=9.57x+552.84	85.63	29.32	63.52
97	四环素	y=89.92x-260.92	y=80.74x+1 457.42	y=89.05x+1 536.97	50.92	35.52	49.46
98	土霉素	y=130.32x+58.03	y=276.06x-610.90	y=208.53x-429.20	2.35	106.86	56.26
99	金霉素	y=34.05x+591.33	y=98.70x+902.63	y=298.91x+543	25.23	116.73	556.37
100	氟康唑	y=85.66x+1 177.92	y=935.85x-566.38	y=1 215.34x+3 534.03	89.99	9.31	41.96
101	螺内酯	y=6.79x+374.07	y=7.11x+675.31	y=9.02x+575.41	6.76	11.79	41.82
102	灰黄霉素	y=383.47x+1 173.44	y=448.08x+562.81	y=422.82x+4 511.18	50.77	42.47	45.72
103	克林霉素	y=984.59x+833.52	y=691.10x+226.91	y=879.73x+12 913.07	10.72	37.33	20.23
104	林可霉素	y=677.19x-1 619.14	y=1 712.43x-6 844.12	y=644.63x+399.99	16.98	195.81	11.35
105	甲硝唑	y=190.66x+2 577.45	y=414.83x-885.07	y=289.29x+1 558.90	12.61	90.13	32.59
106	呋喃它酮	y=665.82x-676.77	y=357.36x-183.82	y=259.65x+3 975.26	58.74	14.80	38.10
107	氯霉素	y=1 656.33x-4 435.76	y=1 863.12x+3 108.02	y=0.12x+660.98	26.47	42.25	99.99
108	他扎罗汀	y=7 780.07x+33 718.89	y=6 043.39x-27 647.31	y=5 524.95x+21 184.57	-9.10	-29.43	-35.48

表2

表3

108种化合物的线性关系、检出限和定量限"

序号	化合物	线性范围/（μg/L）	线性方程	相关系数	检出限/（mg/kg）	定量限/（mg/kg）
1	曲安西龙	30~3 000	y=117.54x+1 497.92	0.999 1	0.38	1.28
2	泼尼松龙	25~2 500	y=162.90x+583.72	0.999 9	0.38	1.25
3	泼尼松	10~1 000	y=389.50x+8 315.49	0.992 8	0.14	0.47
4	异氟泼尼松	15~1 500	y=165.59x+631.87	0.999 8	0.24	0.79
5	氢化可的松	15~1 500	y=356.40x+5 127.87	0.997 1	0.23	0.75
6	可的松	10~1 000	y=469.86x+1 454.52	0.999 7	0.14	0.48
7	甲基泼尼松龙	30~3 000	y=317.45x-3 288.48	0.998 6	0.39	1.29
8	倍他米松	100~10 000	y=103.46x+1 789.79	0.996 5	1.41	4.69
9	地塞米松	60~6 000	y=324.65x-1 305.49	0.999 2	0.64	2.12
10	氟米松	10~1 000	y=185.88x+1 556.31	0.999 5	0.15	0.49
11	倍氯米松	150~15 000	y=18.92x+479.23	0.998 3	2.25	7.50
12	曲安奈德	15~1 500	y=242.34x+5 236.92	0.995 0	0.25	0.84
13	地索奈德	20~2 000	y=272.43x+357.35	0.999 8	0.34	1.14
14	氟尼缩松	15~1 500	y=258.4x+1 343.56	0.999 7	0.25	0.84
15	氟轻松	10~1 000	y=413.78x-2 686.51	0.999 4	0.16	0.52
16	曲安西龙双醋酸酯	15~1 500	y=172.82x+693.69	0.999 9	0.23	0.75
17	氟氢缩松	6~600	y=291.98x+1 759.97	0.999 4	0.09	0.30
18	泼尼松龙醋酸酯	30~3 000	y=196.85x-110.84	0.998 8	0.38	1.27
19	氟米龙	20~2 000	y=199.23x+1 902.58	0.997 9	0.29	0.97
20	氢化可的松醋酸酯	15~1 500	y=477.83x+2 492.83	0.999 5	0.21	0.69
21	氟氢可的松醋酸酯	5~500	y=334.83x-324.45	0.999 9	0.07	0.22
22	地夫可特	3~300	y=1 718.2x-1 549.59	0.998 2	0.05	0.15
23	泼尼松醋酸酯	12~1 200	y=459.56x+4 023.56	0.999 2	0.17	0.57
24	可的松醋酸酯	10~1 000	y=394.08x+4 638.70	0.998 5	0.12	0.41
25	卤美他松	120~12 000	y=44.58x+973.23	0.996 7	1.80	6.00
26	甲基泼尼松龙醋酸酯	20~2 000	y=87.37x+2 596.28	0.996 3	0.33	1.10
27	倍他米松醋酸酯	15~1 500	y=181.63x+3 503.41	0.997 1	0.24	0.78
28	地塞米松醋酸酯	15~1 500	y=183.35x+2 686.79	0.995 6	0.25	0.84
29	布地奈德	30~3 000	y=137.65x+2 650.10	0.996 2	0.43	1.44
30	氢化可的松丁酸酯	5~500	y=255.77x+5 167.46	0.994 1	0.09	0.30
31	氟米龙醋酸酯	60~6 000	y=397.47x+3 719.45	0.998 7	0.69	2.31
32	氢化可的松戊酸酯	15~1 500	y=170.43x+932.54	0.991 5	0.21	0.71
33	曲安奈德醋酸酯	12~1 200	y=172.79x+1 561.69	0.993 7	0.20	0.65
34	二氟拉松双醋酸酯	5~500	y=563.03x+7 306.41	0.996 6	0.06	0.21
35	氟轻松醋酸酯	5~500	y=563.03x+7 306.41	0.996 6	0.06	0.21
36	倍他米松戊酸酯	15~1 500	y=140.82x+2 770.84	0.995 9	0.27	0.89
37	哈西奈德	30~3 000	y=404.04x+13 699.07	0.993 9	0.45	1.50
38	泼尼卡酯	30~3 000	y=232.09x+9 093.73	0.996 3	0.45	1.50
39	氯替泼诺	20~2 000	y=88.80x+6 172.42	0.994 7	0.30	1.00
40	阿氯米松双丙酸酯	30~3 000	y=66.50x+2 847.68	0.998 0	0.45	1.50
41	安西奈德	20~2 000	y=138.01x+8 286.32	0.991 5	0.30	1.00
42	卤倍他索丙酸酯	60~6 000	y=57.35x+3 997.11	0.995 1	0.90	3.00
43	氯倍他索丙酸酯	20~2 000	y=54.93x+3 540.20	0.997 0	0.30	1.00
44	氟替卡松丙酸酯	20~2 000	y=188.15x+11 845.03	0.998 2	0.30	1.00
45	莫米他松糠酸酯	60~6 000	y=34.04x+1 722.24	0.995 8	0.90	3.00
46	倍他米松双丙酸酯	30~3 000	y=54.61x+2 833.20	0.998 9	0.45	1.50
47	倍氯米松双丙酸酯	20~2 000	y=91.29x+4 083.54	0.999 0	0.30	1.00
48	双氟可龙戊酸酯	60~6 000	y=79.91x+3 996.22	0.997 8	0.90	3.00
49	氯倍他松丁酸酯	60~6 000	y=114.95x+6 027.09	0.999 7	0.90	3.00
50	环索奈德	150~15 000	y=410.6x+3 107.01	0.998 9	2.25	7.50
51	睾酮	5~500	y=297.49x+1 735.81	0.997 9	0.06	0.22
52	孕三烯酮	8~800	y=254.47x+3 482.93	0.992 7	0.12	0.40
53	甲基睾丸酮	6.7~670	y=507.80x+9 545.06	0.996 7	0.10	0.35
54	炔诺孕酮	8.6~860	y=512.55x+5 512.18	0.999 6	0.13	0.43
55	醋酸甲地孕酮	15~1 500	y=763.53x+30 520.56	0.999 9	0.23	0.75
56	黄体酮	20~2 000	y=58.16x+5 400.91	0.997 5	0.30	1.00
57	醋酸甲羟孕酮	60~6 000	y=57.16x+3 092.49	0.998 2	0.90	3.00
58	己酸羟孕酮	60~6 000	y=115.49x+6 652.28	0.994 9	0.90	3.00
59	雌三醇	20~2 000	y=58.62x+498.23	0.999 8	0.30	1.00
60	雌二醇	150~15 000	y=10.37x+232.85	0.999 9	2.25	7.50
61	雌酮	30~3 000	y=215.10x-677.68	0.998 9	0.45	1.50
62	己烯雌酚	5~500	y=764.28x+6 194.82	0.999 3	0.08	0.25
63	氧氟沙星	5~500	y=886.61x-17 765.05	0.993 0	0.06	0.19
64	环丙沙星	7.5~750	y=1 155.26x+5 525.56	0.997 7	0.12	0.39
65	依诺沙星	20~2 000	y=519.80x-8 281.98	0.999 1	0.29	0.97
66	沙拉沙星	7~700	y=388.65x-4 698.74	0.995 9	0.11	0.36
67	培氟沙星	8~800	y=460.9x+470.94	0.997 9	0.12	0.41
68	氟罗沙星	5~500	y=431.99x-5 653.91	0.996 5	0.07	0.24
69	双氟沙星	5~500	y=540.60x-4 034.47	0.999 8	0.09	0.30
70	莫西沙星	15~1 500	y=897.40x-5 277.05	0.999 5	0.23	0.75
71	诺氟沙星	30~3 000	y=536.21x+1 616.20	0.998 8	0.45	1.50
72	恩诺沙星	5~500	y=914.16x-12 693.30	0.998 6	0.09	0.30
73	地氯雷他定	30~3 000	y=6.22x+526.08	0.996 8	0.45	1.50
74	曲吡那敏	20~2 000	y=1 580.90x-3 141.94	0.996 9	0.30	1.00
75	溴苯那敏	30~3 000	y=758.73x-12 333.57	0.998 5	0.45	1.50
76	羟嗪	30~3 000	y=295.47x-635.10	0.990 2	0.45	1.50
77	西替利嗪	50~5 000	y=221.73x+1 220.13	0.999 6	0.56	1.88
78	氯丙嗪	15~1 500	y=550.58x-10 224.37	0.997 9	0.23	0.75
79	氯雷他定	10~1 000	y=2 502.83x+25 862.72	0.999 4	0.13	0.43
80	特非那定	5~500	y=17.65x+874.52	0.997 2	0.08	0.25
81	赛庚啶	3.2~320	y=2 440.25x+14 837.66	0.998 2	0.05	0.16
82	普鲁卡因胺	15~1 500	y=373.90x-1 828.98	0.998 9	0.23	0.75
83	普鲁卡因	60~6 000	y=740.02x+7 291.41	0.993 3	0.90	3.00
84	氯普鲁卡因	7.5~750	y=573.95x+2 854.70	0.999 6	0.11	0.38
85	苯佐卡因	10~1 000	y=964.39x+637.31	0.999 8	0.15	0.50
86	利多卡因	10~1 000	y=805.37x+9 617.95	0.998 6	0.15	0.50
87	丁卡因	15~1 500	y=606.80x+14 815.34	0.995 0	0.23	0.75
88	辛可卡因	5~500	y=1 073.74x+11 552.87	0.994 2	0.08	0.25
89	磺胺吡啶	5~500	y=514.89x+10 917.27	0.993 0	0.07	0.22
90	磺胺甲嘧啶	5~500	y=627.74x+1 903.35	0.999 1	0.09	0.31
91	磺胺甲二唑	10~1 000	y=200.76x+826.95	0.999 9	0.16	0.52
92	磺胺甲氧嗪	20~2 000	y=2 963.37x-44 233.11	0.994 8	0.30	1.00
93	磺胺氯哒嗪	10~1 000	y=515.18x-2 050.84	0.999 3	0.13	0.44
94	磺胺甲噁唑	6.7~670	y=659.89x+1 945.44	0.999 9	0.10	0.33
95	多西环素	40~4 000	y=415.75x-282.17	0.999 9	0.64	2.14
96	米诺环素	150~15 000	y=26.23x+343.38	0.999 9	2.25	7.50
97	四环素	60~6 000	y=59.58x+446.17	0.999 2	0.90	3.00
98	土霉素	50~5 000	y=133.45x+2 685.95	0.990 8	0.75	2.50
99	金霉素	20~2 000	y=45.54x+590.15	0.998 9	0.30	1.00
100	氟康唑	5~500	y=856.12x-739.73	0.998 2	0.05	0.17
101	螺内酯	150~15 000	y=6.36x+420.88	0.998 2	2.25	7.50
102	灰黄霉素	20~2 000	y=778.90x-12 147.33	0.997 0	0.30	1.00
103	克林霉素	30~3 000	y=1 102.82x-12 105.43	0.998 3	0.45	1.50
104	林可霉素	10~1 000	y=578.9x+824.66	0.992 9	0.16	0.54
105	甲硝唑	120~12 000	y=218.18x-987.66	0.994 1	1.80	6.00
106	呋喃它酮	15~1 500	y=419.44x-1 627.99	0.999 0	0.23	0.75
107	氯霉素	6~600	y=1 309.17x-1 624.22	0.999 8	0.09	0.30
108	他扎罗汀	5~500	y=8 563.50x+182 379.65	0.996 1	0.08	0.25

表3

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