全自动固相萃取-LC/MS/MS法测定化妆品中76种糖皮质激素

doi:10.3969/j.issn.1001-1803.2021.05.016

摘要/Abstract

摘要：

建立了全自动固相萃取-超高效液相色谱-串联质谱法（UPLC-MS/MS）同时快速测定化妆品中76种糖皮质激素的分析方法。质谱仪采用电喷雾离子化源、正离子多反应检测模式。实验对液态水基类、乳液类、膏霜类三种不同基质类别的化妆品进行考察。样品以饱和氯化钠溶液分散,乙腈进行提取,并选择全自动固相萃取仪进行净化过程。结果表明,76种糖皮质激素的检出限（LODs）为0.004~0.024 μg/g;在10~100 ng/mL范围内线性关系良好（r>0.99）;回收率为76.1%~120.8%,相对标准偏差（RSD）为0.4%~13.0%。该方法简便高效,灵敏可靠,适用于各种不同类别的化妆品中76种糖皮质激素的检测。

关键词: 化妆品, 糖皮质激素类药物, 全自动固相萃取, 超高效液相色谱-三重四极杆质谱

Abstract:

A automatic solid-phase extraction- ultra-performance liquid chromatography-tandem mass spectrometric （UPLC-MS/MS） method was established for the determination of 76 glucocorticoids in cosmetics. The mass spectrometer was operated by electrospray ionization and positive multiple reaction monitoring. The cosmetics with liquid water-based, emulsion and cream were investigated. The samples were dispersed in saturated sodium chloride solution, extracted with acetonitrile, and purified by automatic solid-phase extraction apparatus. The results show that the limits of detection （LODs） for 76 glucocorticoids are in the range of 0.004-0.024 μg/g. Good linear relationship exists between peak area and mass concentration of 10-100 ng/mL with correlation coefficients higher than 0.99. The average recoveries are in the range of 76.1%-120.8%, with relative standard deviations （RSDs） of 0.4%-13.0%．The method is simple, efficient, sensitive, reliable,and is suitable for the general detection of 76 glucocorticoids in various kinds of cosmetics.

Key words: cosmetics, glucocorticoids, automatic solid-phase extraction, ultra-performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）

中图分类号:

TQ658

杨飘飘,刘红,李丽霞. 全自动固相萃取-LC/MS/MS法测定化妆品中76种糖皮质激素[J]. 日用化学工业, 2021, 51(5): 468-476.

YANG Piao-piao,LIU Hong,LI Li-xia. Detection of 76 glucocorticoids in cosmetics by automatic solid-phase extraction and LC/MS/MS[J]. China Surfactant Detergent & Cosmetics, 2021, 51(5): 468-476.

图/表 5

表 1

表 2

76种分析物的保留时间和质谱参数"

序号	糖皮质激素	保留时间t/min	母离子（m/z）	子离子（m/z）	子离子碰撞气能量E/eV
1	泼尼松龙	18.81	361.2	147.0*, 343.1	24, 10
2	氢化可的松	19.09	363.2	120.9*, 104.9	26, 52
3	泼尼松	18.72	359.2	147.0*, 341.1	30, 8
4	可的松	19.45	361.2	163.0*, 121.0	26, 28
5	甲基泼尼松龙	23.87	375.2	357.1*, 161.1	10, 18
6	倍他米松	24.44	393.2	355.1*, 147.0	12, 34
7	地塞米松	24.86	393.2	355.1*, 147.0	12, 28
8	氟米松	25.00	411.2	253.1*, 121.0	14, 28
9	倍氯米松	26.20	409.3	391.1*, 147.0	11, 24
10	曲安奈德	27.10	435.2	339.1*, 397.2	16, 18
11	氟氢缩松	28.07	437.2	121.0*, 180.9	35, 25
12	曲安西龙双醋酸酯	28.23	479.2	321.1*, 441.2	18, 10
13	泼尼松龙醋酸酯	28.28	403.2	147.0*, 384.9	22, 14
14	氟米龙	29.09	377.2	279.2*, 321.2	16, 14
15	氢化可的松醋酸酯	28.80	405.3	309.2*, 121.0	14, 28
16	地夫可特	30.56	442.3	124.0*, 142.1	50, 34
17	氟氢可的松醋酸酯	29.21	423.2	239.1*, 121.0	30, 34
18	泼尼松醋酸酯	30.07	401.2	295.2*, 147.1	12, 26
19	可的松醋酸酯	30.75	403.2	163.1*, 343.1	24, 20
20	甲基泼尼松龙醋酸酯	32.54	417.2	399.2*, 253.2	10, 26
21	倍他米松醋酸酯	32.82	435.2	309.0*, 337.2	12, 16
22	氢化可的松丁酸酯	34.36	433.2	121.0*, 345.2	30, 12
23	地塞米松醋酸酯	34.01	435.2	309.2*, 337.2	16, 10
24	氟米龙醋酸酯	35.49	419.2	279.1*, 321.1	16, 12
25	氢化可的松戊酸酯	38.43	447.2	121.0*, 345.2	28, 12
26	曲安奈德醋酸酯	38.36	477.3	321.2*, 339.2	16, 12
27	氟轻松醋酸酯	39.28	495.2	121.0*, 337.1	36, 16
28	二氟拉松双醋酸酯	39.64	495.2	317.1*, 279.1	12, 16
29	倍他米松戊酸酯	41.34	477.2	355.2*, 279.1	10, 16
30	泼尼卡酯	42.39	489.3	115.0*, 381.2	16, 10
31	哈西奈德	42.04	455.2	121.0*, 105.0	62, 58
32	阿氯米松双丙酸酯	42.88	521.3	301.1*, 279.0	15, 14
33	安西奈德	42.66	503.2	321.1*, 339.1	18, 16
34	氯倍他索丙酸酯	42.93	467.2	373.1*, 355.0	10, 14
35	氟替卡松丙酸酯	43.39	501.2	293.2*, 313.1	14, 12
36	莫米他松糠酸酯	43.49	521.1	503.0*, 263.0	18, 30
37	倍他米松双丙酸酯	43.71	505.3	279.2*, 319.1	16, 14
38	倍氯米松双丙酸酯	44.47	521.3	319.2*, 503.0	12, 10
39	氯倍他松丁酸酯	44.99	479.2	343.1*, 279.1	18, 18
40	氟轻松	28.37	453.2	337.1*, 121.2	18, 44
41	氢化可的松环戊丙酸酯	45.37	487.4	107.2*, 327.1	43, 26
42	氟可龙	28.73	377.2	303.2*, 171.1	30, 20
43	莫米松	38.00	429.1	411.2*, 237.1	12, 30
44	地索奈德	26.89	417.2	147.0*, 173.0	44, 34
45	22（R）-布地奈德	33.96	431.1	413.0*, 147.0	16, 44
46	22（S）-布地奈德	34.54	431.1	413.0*, 147.0	16, 44
47	去羟米松	29.38	377.2	303.1*, 171.0	20, 27
48	双氟拉松	24.36	411.1	121.1*, 253.1	35, 25
49	氟尼缩松	27.30	435.1	339.1*, 321.1	20, 23
50	帕拉米松乙酸酯	33.64	435.1	417.0*, 319.1	11, 22
51	双氟美松醋酸酯	34.07	453.1	433.1*, 253.1	11, 24
52	地塞米松戊酸酯	39.90	477.3	355.2*, 279.1	15, 35
53	地塞米松特戊酸酯	43.64	477.3	355.2*, 237.1	17, 38
54	异氟泼尼龙	18.81	379.2	147.1*,341.1	38, 26
55	16α-羟基泼尼松龙醋酸酯	21.38	419.2	323.2*, 226.0	18, 27
56	6α-氟-异氟泼尼龙	18.94	397.1	253.1*, 121.0	27, 27
57	倍他米松苯甲酸酯	41.54	497.1	355.1*, 279.1	13, 25
58	双氟可龙戊酸酯	44.92	479.2	85.1*, 375.1	28, 15
59	地塞米松异烟酸酯	36.17	498.1	106.0*, 478.2	50, 17
60	氟可龙特戊酸酯	44.93	461.1	341.1*, 303.1	17, 18
61	氟米松特戊酸酯	43.50	495.1	253.0*, 373.0	25, 18
62	氟氢可的松	19.32	381.2	239.1*, 181.0	37, 44
63	瑞美松龙	43.28	371.2	353.2*, 121.1	13, 39
64	己曲安奈德	46.20	533.3	415.2*, 397.2	19, 20
65	甲基泼尼松龙醋丙酸酯	41.68	473.3	381.2*, 161.2	13, 32
66	异氟泼尼龙醋酸酯	28.43	421.0	305.2*, 147.1	19, 40
67	甲泼尼松	24.86	373.2	355.1*, 337.0	17, 18
68	氟泼尼龙	18.59	379.2	323.2*, 171.1	15, 37
69	卤贝他索	35.39	429.0	253.0*, 121.1	28, 41
70	卤贝他索丙酸酯	42.91	485.2	261.0*, 121.0	29, 51
71	卤美他松	30.85	445.1	155.1*, 169.1	40, 34
72	氯泼尼醇	26.56	392.9	205.1*, 271.1	30, 25
73	泼尼松龙特戊酸酯	41.31	445.1	307.1*, 325.2	19, 19
74	双氟泼尼酯	41.63	509.0	303.0*, 279.1	18, 18
75	替可的松特戊酸酯	42.91	463.3	57.2*, 343.1	26, 25
76	依碳氯替泼诺	42.56	467.2	359.0*, 265.0	14, 25

表 2

图 1

表 3

表 4

76种化合物在三种不同基质中的线性相关系数、线性方程、回收率、精密度、检出限和定量限"

序号	水剂类				乳液类				膏霜类				检出限/ （μg·g^-1）	定量限/ （μg·g^-1）
序号	相关系数	线性方程	回收率/%	精密度/%	相关系数	线性方程	回收率/%	精密度/%	相关系数	线性方程	回收率/%	精密度/%	检出限/ （μg·g^-1）	定量限/ （μg·g^-1）
1	0.992 6	Y=823.4X+1 992.8	79.3	5.7	0.997 9	Y=1 681.7X+2 061.5	98.8	3.6	0.994 0	Y=735.3X-422.4	98.7	4.3	0.013	0.05
2	0.993 4	Y=2 501.5X+2 014.4	85.1	4.6	0.998 8	Y=6 258.5X+1 967.6	98.8	2.6	0.999 3	Y=879.4X+438	92.5	5.6	0.012	0.05
3	0.991 8	Y=2 037.5X+4 953.2	78.5	4.3	0.999 2	Y=3 375.2X+1 508.7	98.3	2.8	0.993 8	Y=1 299X-1 010.5	101.5	4.4	0.012	0.05
4	0.994 9	Y=4 337.3X+2 596.6	87.8	5.0	0.999 3	Y=7 710.1X+358.1	97.0	3.5	0.996 9	Y=5 064.6X+729.6	97.8	4.5	0.013	0.05
5	0.998 7	Y=3 983.3X+3 739.4	93.5	3.1	0.998 4	Y=4 311.1X+369.2	97.2	2.5	0.997 8	Y=2 887X+205.1	104.8	4.0	0.012	0.05
6	0.998 3	Y=1 400.4X+1 532.9	93.1	3.3	0.996 7	Y=1 543.7X+1 877.9	97.7	4.3	0.998 8	Y=615.8X+147	100.3	5.0	0.012	0.05
7	0.999 1	Y=1 658.5X+1 667.9	95.7	3.9	0.998 1	Y=1 667.1X+1 799	96.2	3.8	0.998 8	Y=1 083X+396.4	99.8	6.0	0.013	0.05
8	0.997 3	Y=2 227.3X+2 401.3	97.2	3.5	0.998 1	Y=2 228.9X+2 659	95.6	4.7	0.997 8	Y=1 603.3X+648	98.8	4.4	0.012	0.05
9	0.998 5	Y=4 611.6X+5 072.9	99.2	2.7	0.998 2	Y=4 650.7X+4 867	97.9	5.1	0.996 7	Y=4 347.7X+2 893	107.5	3.6	0.012	0.05
10	0.996 2	Y=1 699.8X+2 145	96.3	4.0	0.999 1	Y=1 663.5X+744.3	98.5	3.8	0.996 2	Y=1 437.3X+1 587.8	100.6	4.0	0.012	0.05
11	0.998 8	Y=958.5X+192.5	97.5	3.6	0.997 5	Y=876.3X+869	94.7	6.7	0.993 0	Y=849.1X-193.1	102.7	4.6	0.012	0.05
12	0.997 7	Y=1 420.3X+1 901.9	96.6	5.9	0.997 8	Y=1 465.6X+1 169.3	97.8	4.0	0.995 1	Y=1 290.5X+1 923.2	105.9	5.7	0.012	0.05
13	0.997 8	Y=1 334.5X+732.6	95.3	3.8	0.998 6	Y=1 318.6X+62.2	99.8	4.2	0.995 1	Y=1 240.1X+382.8	103.4	5.0	0.013	0.05
14	0.998 6	Y=3 661.4X+3 572.5	100.0	2.5	0.997 3	Y=3 631.3X+1 948.4	98.4	4.4	0.995 8	Y=3 419.1X+2 212.2	102.4	6.1	0.012	0.05
15	0.999 3	Y=1 490.9X+827.5	98.3	6.0	0.999 0	Y=1 470X+387.1	97.7	6.3	0.992 1	Y=1 467.7X-1 034.9	104.8	4.7	0.012	0.05
16	0.998 6	Y=4 534.8X+346.1	96.7	4.7	0.999 2	Y=4 635.6X-1 646.2	98.8	5.9	0.994 8	Y=4 373.2X-146.3	103.7	4.9	0.012	0.05
17	0.998 4	Y=2 301.3X+2 026.8	102.1	4.3	0.998 5	Y=2 355.4X+499.8	97.9	4.1	0.992 6	Y=2 231.9X-70.7	101.4	5.5	0.012	0.05
18	0.998 7	Y=2 087.1X+836.6	98.3	5.3	0.998 3	Y=2 043.7X+768.6	97.5	3.2	0.992 5	Y=1 974.4X+171	101.1	3.7	0.012	0.05
19	0.999 0	Y=5 451.3X+377.8	99.9	3.8	0.999 1	Y=5 515.9X-1 480.3	98.6	4.0	0.995 2	Y=5 166.9X-143.1	101.0	4.5	0.013	0.05
20	0.998 0	Y=5 162.1X+4 577.5	95.0	2.5	0.998 7	Y=5 208.5X-691.9	98.6	4.2	0.993 9	Y=4 496.4X+1 261.9	103.9	4.1	0.012	0.05
21	0.997 5	Y=425.4X+303	95.0	7.5	0.998 6	Y=418.7X+305.5	91.2	5.4	0.995 4	Y=404.3X-94.7	101.6	5.0	0.012	0.05
22	0.998 6	Y=6 081.8X+2 430.6	96.0	3.1	0.998 3	Y=5 824.1X+2 672.8	96.8	5.1	0.995 0	Y=5 442.1X-499.7	103.2	3.4	0.012	0.05
23	0.995 2	Y=1 308.9X+2 894.5	96.3	3.6	0.998 0	Y=1 344X+1 413.2	95.8	6.4	0.994 3	Y=1 248.3X+1 157.9	103.7	4.7	0.012	0.05
24	0.997 1	Y=10 766.6X+9 555.1	102.1	2.6	0.999 0	Y=11 123.5X+3 202.6	97.5	2.4	0.994 9	Y=10 384X+5 641.6	101.0	4.6	0.013	0.05
25	0.998 2	Y=5 425.2X+2 410.5	96.2	3.4	0.999 6	Y=4 752.5X-1 174	98.4	3.0	0.994 8	Y=4 761.7X+1 837.9	102.1	4.5	0.013	0.05
26	0.998 1	Y=1 327.7X+980.3	98.0	4.8	0.997 7	Y=1 076.6X-58.2	95.2	5.1	0.995 9	Y=1 203.8X+275.4	100.4	5.0	0.012	0.05
27	0.997 1	Y=2 352.7X+1 821.7	96.1	2.6	0.998 5	Y=1 959.1X-167.7	97.5	4.7	0.995 1	Y=2 025.9X+481.8	104.3	5.7	0.012	0.05
28	0.998 4	Y=2 290.9X+1 460.4	95.6	6.2	0.999 4	Y=1 927.8X-923.9	94.5	6.1	0.995 6	Y=2 114X+314.7	97.8	4.3	0.012	0.05
29	0.996 3	Y=3 872.5X+6 197.9	98.9	5.0	0.996 3	Y=3 629.5X+5 741	96.6	6.0	0.999 1	Y=3 418.1X+186.2	104.8	5.2	0.013	0.05
30	0.996 0	Y=3 849.3X+2 562.3	94.7	3.9	0.998 6	Y=3 451.4X+1 497.3	97.5	5.9	0.993 9	Y=3 271.9X-2 121.7	105.4	5.3	0.012	0.05
31	0.992 1	Y=1 528.3X+1 949.3	99.4	4.9	0.999 1	Y=1 036.8X-1 076.7	102.0	4.4	0.992 6	Y=1 159.2X+196	107.0	4.6	0.012	0.05
32	0.995 5	Y=1 253.6X+2 447.4	95.8	4.2	0.996 7	Y=1 252X+1 590	94.4	8.1	0.996 5	Y=1 139.6X-148.3	104.3	4.4	0.012	0.05
33	0.997 2	Y=1 898.9X+2 599.4	96.4	5.5	0.998 9	Y=1 672.6X-39.7	97.2	6.0	0.991 8	Y=1 521.6X+96.4	100.9	6.7	0.012	0.05
34	0.999 0	Y=2 813.4X+3 539.3	101.9	4.4	0.999 3	Y=2 443.6X+1 727.3	100.0	7.5	0.991 4	Y=2 174.8X+2 313.1	104.4	3.9	0.012	0.05
35	0.997 4	Y=3 432.4X+3 867.5	102.9	3.5	0.999 6	Y=1 373X-1 417.1	99.7	3.1	0.995 7	Y=2 195.9X+805	101.0	5.6	0.013	0.05
36	0.994 4	Y=2 722.3X+6 990	101.2	5.4	0.999 1	Y=1 946.1X+509.4	92.8	4.2	0.997 1	Y=1 536.6X+5.4	104.5	6.1	0.012	0.05
37	0.997 2	Y=2 780.6X+4 170.9	94.4	4.5	0.998 7	Y=1 647.1X-492.9	100.0	2.7	0.996 8	Y=1 957.5X+410.7	101.1	4.6	0.012	0.05
38	0.998 1	Y=922.4X+956.7	99.5	5.0	0.998 8	Y=428.7X-117.8	89.1	3.7	0.992 1	Y=485X-948	103.9	6.8	0.012	0.05
39	0.999 4	Y=2 290.5X+307.1	91.2	3.3	0.998 7	Y=1 493.7X-399.4	96.5	3.3	0.995 3	Y=1 072.8X-1 577.4	107.2	7.1	0.012	0.05
40	0.998 2	Y=131.4X-168	96.4	7.1	0.995 4	Y=119.2X-269.9	99.7	7.1	0.996 8	Y=98.1X+189.8	93.0	5.0	0.013	0.05
41	0.994 8	Y=8 032.8X+8 536.1	98.7	2.0	0.999 2	Y=3 807.6X+2 265.2	94.7	6.9	0.997 1	Y=2 746.1X-1 053.9	106.7	7.4	0.010	0.04
42	0.997 1	Y=3 877.7X+5 190.2	94.1	4.9	0.998 9	Y=3 744X+1 386.9	98.3	3.7	0.997 3	Y=3 472X+2 685.5	102.8	3.7	0.013	0.05
43	0.998 4	Y=852.6X+713.4	96.1	3.9	0.997 8	Y=617.1X+23.1	94.7	5.8	0.996 4	Y=756.6X-289.6	109.9	4.7	0.012	0.05
44	0.999 7	Y=2 292.8X+30.1	94.7	4.7	0.997 7	Y=2 093.4X+1 350.2	92.8	3.6	0.996 3	Y=1 896.3X+114.8	102.8	2.2	0.012	0.05
45	0.995 6	Y=6 651.6X+35 451.3	97.9	4.7	0.998 4	Y=6 342.3X+10 845.5	98.4	4.1	0.995 9	Y=6 415.1X+23 571.8	102.9	2.7	0.024	0.10
46	0.997 6	Y=7 354.4X+2 672.7	94.5	5.9	0.998 0	Y=7 433.1X+1 408.8	96.5	3.6	0.997 7	Y=7 058.8X+1 539.4	98.1	4.1	0.005	0.02
47	0.998 2	Y=2 017.7X+367.6	95.5	7.1	0.999 6	Y=2 012.4X-140.4	95.8	2.5	0.993 1	Y=1 922X-57	101.4	5.7	0.004	0.02
48	0.997 9	Y=1 071.5X+2 249.7	95.0	5.4	0.998 8	Y=1 116.7X+885.4	99.4	5.2	0.995 6	Y=601.3X-370.5	94.2	6.6	0.014	0.05
49	0.998 6	Y=2 167.3X-833	101.3	4.4	0.997 8	Y=2 045.2X+800.3	97.3	4.6	0.992 5	Y=1 931.1X-525.4	97.5	5.1	0.010	0.04
50	0.998 0	Y=1 999.5X+835.7	95.5	5.5	0.998 4	Y=2 050.2X-34.2	99.2	4.1	0.996 4	Y=1 920.9X-111.9	105.6	5.8	0.005	0.02
51	0.996 6	Y=1 953.3X+1 249.7	94.7	4.9	0.999 5	Y=1 953.1X-14.8	97.6	4.7	0.994 3	Y=1 830.7X+287.7	103.5	4.5	0.005	0.02
52	0.996 7	Y=3 930.6X+3 667.6	89.5	6.1	0.998 0	Y=3 275.5X+542.3	96.4	6.8	0.997 9	Y=3 501.2X+1 535.7	103.2	6.3	0.013	0.05
53	0.997 5	Y=4 967.7X+10 078.2	96.6	4.7	0.998 9	Y=2 505.5X+496.1	96.0	2.1	0.995 7	Y=3 453.2X-727.3	106.9	5.5	0.013	0.05
54	0.994 8	Y=615.8X+736.4	91.5	4.6	0.998 3	Y=828X+991.7	99.6	3.8	0.995 9	Y=405.7X-354.4	101.3	3.0	0.012	0.05
55	0.994 4	Y=1 327.6X+1 744.8	85.9	4.1	0.999 3	Y=1 403X-548.6	97.8	3.8	0.995 9	Y=838.6X-1 226.5	108.6	8.3	0.011	0.05
56	0.998 3	Y=1 384.6X+1 102.8	100.0	4.1	0.998 8	Y=1 982.2X+1 005.1	97.5	3.1	0.994 5	Y=1 097.5X-308.4	96.1	5.8	0.011	0.05
57	0.997 3	Y=5 028.7X+11 197.2	95.2	2.6	0.999 6	Y=4 830.6X+2 722.8	95.9	6.9	0.994 7	Y=4 503X-5 453.9	106.3	4.8	0.014	0.06
58	0.997 9	Y=8 232.9X+14 627.9	93.1	3.8	0.996 5	Y=5 610.4X+6 342.5	94.7	4.2	0.997 5	Y=4 006.9X+3 157.3	103.3	6.1	0.012	0.05
59	0.992 3	Y=1 575.9X+1 621.2	94.5	3.6	0.998 7	Y=3 435.1X-1 707.4	95.6	4.1	0.993 4	Y=4 660.8X-3 793.3	107.8	4.6	0.012	0.05
60	0.998 0	Y=1 845.8X+2 218.9	93.0	3.6	0.999 5	Y=1 503.8X+597.5	95.8	4.8	0.997 2	Y=1 179.1X-915.8	104.3	5.7	0.012	0.05
61	0.994 9	Y=1 081.8X+2 146.8	97.3	7.4	0.995 6	Y=845.8X+834.5	91.6	7.0	0.995 3	Y=747.2X+481.9	94.7	6.9	0.012	0.05
62	0.993 7	Y=2 962.4X+5 978.3	88.1	3.9	0.998 6	Y=3 817.7X+2 820.1	98.6	2.9	0.996 7	Y=1 735.9X-1 432.5	102.1	5.8	0.011	0.04
63	0.996 5	Y=9 441.8X+12 309.6	95.7	4.0	0.999 3	Y=6 274.4X-258.3	99.6	4.0	0.996 8	Y=6 461.8X+8 217.6	107.8	4.7	0.012	0.05
64	0.997 6	Y=3 327.5X+4 092	91.1	3.6	0.999 8	Y=1 403.4X-840.8	92.9	3.3	0.991 8	Y=1 773.6X-2 915.7	106.6	5.5	0.012	0.05
65	0.997 8	Y=5 582.4X+12 249.6	95.6	4.8	0.999 6	Y=5 112.5X+1 618.4	98.9	3.5	0.995 2	Y=4 899.4X+1 427	103.5	3.7	0.014	0.05
66	0.998 0	Y=1 413.3X+373.9	91.8	7.1	0.996 8	Y=1 369.2X+501.2	93.5	5.2	0.996 9	Y=1 281.5X+535.6	96.8	5.4	0.005	0.02
67	0.998 1	Y=7 785.3X+3 967.7	94.9	4.5	0.998 6	Y=7 768X+1 207.6	99.2	2.9	0.998 8	Y=5 770.7X+1 618.9	100.0	5.7	0.005	0.02
68	0.998 7	Y=917.7X-104.8	96.3	5.5	0.999 1	Y=1 456.6X-6.5	96.3	2.3	0.998 6	Y=160.8X-2.8	92.6	5.4	0.012	0.05
69	0.998 3	Y=1 896.5X+1 169.4	101.0	4.5	0.998 3	Y=1 889.9X+835.8	96.6	5.4	0.995 4	Y=1 760.4X+1 240.2	100.5	4.8	0.011	0.05
70	0.997 0	Y=1 016X+1 814.3	101.8	5.2	0.996 8	Y=889.7X+1 421.9	97.5	4.1	0.994 2	Y=785.6X+691.7	104.4	7.7	0.012	0.05
71	0.999 4	Y=864.8X-208	95.2	4.0	0.998 1	Y=847.4X-83.2	95.6	6.8	0.996 7	Y=811.9X-557.5	100.4	5.5	0.011	0.05
72	0.997 5	Y=9 553.5X+5 864.9	97.7	4.3	0.999 2	Y=9 444X+3 901.3	99.2	3.5	0.997 4	Y=8 217.1X+4 570.5	100.7	4.5	0.009	0.04
73	0.995 4	Y=1 997.2X+2 929.8	95.8	6.2	0.997 6	Y=1 946.2X+732.6	96.3	4.1	0.994 1	Y=1 753X+459.5	97.9	6.3	0.012	0.05
74	0.995 2	Y=4 103.1X+7 604.5	95.5	3.6	0.997 3	Y=3 793.9X+2 320.6	95.2	3.4	0.996 5	Y=3 609.1X+2 201.7	101.1	4.6	0.011	0.04
75	0.996 9	Y=6 132.3X+8 028.8	102.2	3.5	0.996 9	Y=5 443.1X+9 992.7	96.5	5.8	0.994 3	Y=4 566.9X+4 932.2	102.0	6.2	0.012	0.05
76	0.997 2	Y=9 046.5X+10 992.3	94.2	4.2	0.997 0	Y=7 840.5X+3 119.0	98.7	5.7	0.995 3	Y=6 914.9X+3 436.0	101.5	6.0	0.012	0.05

表 4

参考文献 14

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命令	溶剂	流速/（mL·min^-1）	体积/mL	时间/min	排出
清洗管路	甲醇	60	30	4.7	废液
活化	甲醇	10	5	0.9	废液
活化	水	10	10	1.6	废液
上样		5	48	12.3	废液
清洗样品瓶	乙腈-水（1∶9,V/V）	5	15	7.4	废液
气推		10	5	1.1	废液
洗脱	甲醇	1	4	4.4	收集
气推		10	5	1.1	收集
结束				33.5

序号	上样速度/（mL·min^-1）	洗脱速度/（mL·min^-1）	时间/min
M1	1	1	85.9
M2	3	1	43.9
M3	5	1	33.5
M4	3	3	41.2
M5	3	5	40.7

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