超高效液相色谱-串联质谱法同时测定化妆品中83种糖皮质激素

doi:10.3724/SP.J.1123.2023.04009

摘要/Abstract

摘要：

近年来化妆品中非法添加糖皮质激素的恶性事件常有发生,因此建立一个高通量且简便高效的检测方法,对保障消费者的用妆安全具有现实意义。研究建立了超高效液相色谱-串联质谱法同时测定化妆品中83种糖皮质激素的分析方法。以化妆品中常用的水、乳液、膏霜(o/w型)3种基质为研究对象,对样品前处理和色谱-质谱条件进行优化,最终确定样品经乙腈涡旋分散、超声提取、过滤后,采用Thermo Accucore PFP色谱柱(100 mm×2.1 mm, 2.6 μm)分离,以0.1%(v/v)乙酸乙腈和0.1%(v/v)乙酸水溶液为流动相梯度洗脱,在电喷雾正离子模式(ESI⁺)下以动态多反应监测(MRM)方式测定,外标法定量。结果表明,83种糖皮质激素在2~200 μg/L范围内线性关系良好,相关系数(r)均大于0.995,在3个不同添加水平下,平均回收率为74.5%~112.4%,相对标准偏差(RSD, n=6)为0.8%~9.9%,方法的检出限(LOD, S/N≥3)和定量限(LOQ, S/N≥10)分别为0.001~0.023 μg/g和0.002~0.076 μg/g。采用该方法对市售的41批化妆品进行83种糖皮质激素筛查,共发现4批阳性样品,分别检出氟轻松、倍氯米松双丙酸酯、醋酸地索奈德及地索奈德,含量范围为0.53~634.27 μg/g,其中醋酸地索奈德尚未列入法定检测标准的筛查范畴。该方法简便快捷,灵敏度高,重复性好,是对现行检测标准的补充,适用于多种基质类型化妆品中83种糖皮质激素的快速定性定量筛查,为化妆品质量的日常监督提供可靠的技术支持。

关键词: 超高效液相色谱-串联质谱, 糖皮质激素, 化妆品, 非法添加

Abstract:

Glucocorticoids, which are a class of steroidal hormones secreted by the adrenal cortex, have significant anti-inflammatory, immunosuppressive, and anti-allergic effects. Thus, these compounds are widely used in clinical practice. However, the long-term use of cosmetics containing glucocorticoids can lead to serious consequences, such as hormone-dependent dermatitis, hypertension, and other serious injuries. The Safety and Technical Specification for Cosmetics (2015 edition) and Regulation (EC) No. 1223/2009 of the European Parliament and Council on cosmetic products list glucocorticoids as prohibited raw materials. According to the National Medical Products Administration, reports on the illegal addition of glucocorticoids to cosmetics by manufacturers have increased in recent years. Therefore, establishing high-throughput screening methods to ensure the quality and safety of cosmetics is imperative. In this study, a comprehensive analytical method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the rapid screening of 83 glucocorticoids in cosmetics. A series of conditions were optimized using three matrices that are commonly used in cosmetics: water, lotion, and cream (o/w-type). Four mobile-phase systems and three chromatographic columns were then optimized to achieve the best separation effects. Various MS parameters, such as the capillary voltages, cone voltages, desolvation gas flow rates, and collision energies of the ion pairs of the target compounds, were also optimized. Furthermore, pretreatment was essential for glucocorticoid determination owing to the complex matrix effects of cosmetics. The analytes were divided into two groups, with lg K_ow=4 as the limit, to compare the effects of the extraction solvent on recoveries. The extraction recoveries of target analytes with six extraction methods, namely, extraction with acetonitrile, extraction with acetone, extraction with ethyl acetate, dispersion in saturated sodium chloride solution followed by extraction with acetonitrile, dispersion in saturated sodium chloride solution followed by extraction with acetone, and dispersion in saturated sodium chloride solution followed by extraction with ethyl acetate, were compared. The recoveries from QuEChERS and solid-phase extraction (SPE) purification were also compared. Based on the experimental results, the final sample pretreatment method included acetonitrile vortex dispersion, ultrasonic extraction, and sample loading after filtration. The 83 target compounds were separated on a Thermo Accucore PFP column (100 mm×2.1 mm, 2.6 μm) with 0.1% (v/v) acetic acid in acetonitrile and 0.1% (v/v) acetic acid in water as the mobile phases. The analytes were determined by dynamic multiple-reaction monitoring (MRM) in electrospray positive ionization mode (ESI⁺) and quantified using the external standard method. Matrix standard curves were used to reduce matrix effects. The calibration curves of the 83 target compounds were linear in the mass concentration range of 2-200 μg/L (r>0.995). At three levels of addition, the recoveries were 74.5%-112.4%, and the relative standard deviations (RSDs, n=6) were 0.8%-9.9%. The limits of detection (LODs, S/N≥3) were 0.001-0.023 μg/g, and the limits of quantification (LOQs, S/N≥10) were 0.002-0.076 μg/g. The developed method was used to detect glucocorticoids in 41 cosmetic samples. Fluocinolone acetonide, beclomethasone dipropionate, desonide 21-acetate, and desonide were detected in four samples. The content range of glucocorticoids in the positive samples was 0.53-634.27 μg/g. Notably, desonide 21-acetate, which is not included in the scope of the statutory detection method, was detected in two batches of samples. In conclusion, the proposed method is simple, sensitive, reliable, and suitable for the high-throughput analysis of the 83 glucocorticoids in cosmetics with different matrices. This method could provide reliable technical support for the daily supervision of cosmetics and serve as a supplement to current glucocorticoid standards.

Key words: ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), glucocorticoids, cosmetics, illegal addition

中图分类号:

O658

赵倩茹, 刘骅, 孟雅萍, 李翔, 高瑞芳, 李祥胜. 超高效液相色谱-串联质谱法同时测定化妆品中83种糖皮质激素[J]. 色谱, 2023, 41(12): 1084-1094.

ZHAO Qianru, LIU Hua, MENG Yaping, LI Xiang, GAO Ruifang, LI Xiangsheng. Simultaneous determination of 83 glucocorticoids in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(12): 1084-1094.

图/表 5

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No.		Analyte	t_R/ min		Parent ion (m/z)		Product ions (m/z)		Cone voltage/V		Collision energies/eV				lg K_ow
1		triamcinolone (曲安西龙)	4.07		395.2		375.2^*/357.2		2		6/		12		0.83
2		prednisolone (泼尼松龙)	5.69		361.2		147.1^*/325.2		4		28/		8		1.50
3		hydrocortisone (氢化可的松)	5.68		363.2		121.1^*/327.2		30		24/		16		1.43
4		prednisone (泼尼松)	7.10		359.2		313.2^*/147.1		34		10/		24		1.57
5		cortisone (可的松)	6.79		361.2		163.1^*/121.1		10		22/		32		1.44
6		methylprednisolone (甲基泼尼松龙)	8.99		375.2		161.1^*/339.2		18		18/		6		1.99
7		betamethasone (倍他米松)	9.68		393.2		373.2^*/355.2		10		4/		10		1.87
8		dexamethasone (地塞米松)	10.29		393.2		355.2^*/337.2		2		10/		12		1.87
9		flumethasone (氟米松)	13.14		411.2		253.2^*/121.1		28		14/		36		1.84
10		beclomethasone (倍氯米松)	24.14		409.2		373.2^*/147.0		12		10/		32		4.59
11		triamcinolone acetonide (曲安奈德)	17.60		435.2		397.2^*/339.2		4		14/		14		2.50
12		fludroxycortide (氟氢缩松)	16.84		437.3		91.1^*/105.1		4		62/		44		2.50
13		triamcinolone diacetate (曲安西龙双醋酸酯)	19.11		479.3		441.2^*/321.2		6		10/		14		2.16
14		prednisolone 21-acetate (泼尼松龙醋酸酯)	15.29		403.2		147.1^*/325.2		4		22/		10		2.58
15		fluoromethalone (氟米龙)	15.65		377.2		279.2^*/339.2		32		14/		10		2.02
16		hydrocortisone 21-acetate (氢化可的松醋酸酯)	14.86		405.3		309.2^*/121.1		2		14/		30		2.51
17		deflazacort (地夫可特)	19.20		442.2		142.0^*/124.0		68		36/		44		2.02
18		fludrocortisone 21-acetate (氟氢可的松醋酸酯)	17.23		423.2		239.2^*/325.2		64		24/		20		2.32
19		prednisone 21-acetate (泼尼松醋酸酯)	20.03		401.2		295.2^*/147.1		6		14/		24		2.66
20		cortisone 21-acetate (可的松醋酸酯)	19.40		403.2		163.1^*/343.2		2		26/		18		2.53
21		methylprednisolone 21-acetate (甲基泼尼松龙醋酸酯)	20.63		417.3		339.2^*/321.2		12		8/		12		3.08
22		betamethasone 21-acetate (倍他米松醋酸酯)	21.51		435.2		397.2^*/319.2		2		8/		12		2.96
23		budesonide (布地奈德)	22.15		431.3		147.1^*/323.2		2		28/		10		3.14
24		hydrocortisone 17-butyrate (氢化可的松丁酸酯)	22.14		433.3		345.2^*/121.1		26		12/		28		2.81
25		dexamethasone 21-acetate (地塞米松醋酸酯)	21.91		435.2		397.2^*/337.2		24		10/		10		2.96
26		fluorometholone 17-acetate (氟米龙醋酸酯)	24.00		419.2		279.2^*/321.2		2		14/		12		2.57
27		hydrocortisone 17-valerate (氢化可的松戊酸酯)	24.09		447.3		345.2^*/121.0		2		12/		28		3.52
28		triamcinolone acetonide 21-acetate (曲安奈德醋酸酯)	24.70		477.3		339.2^*/439.2		4		14/		14		3.61
29		fluocinonide (氟轻松醋酸酯)	25.18		495.2		337.2^*/121.1		2		16/		40		3.36
30		diflorasone diacetate (二氟拉松双醋酸酯)	25.59		495.2		317.2^*/279.2		24		12/		14		3.10
31		betamethasone 17-valerate (倍他米松戊酸酯)	25.26		477.3		355.2^*/279.2		4		16/		14		3.78
32		prednicarbate (泼尼卡酯)	25.88		489.3		381.2^*/115.0		22		8/		16		4.02
33		halcinonide (哈西奈德)	25.52		455.2		359.2^*/105.1		70		22/		58		3.31
34		alclomethasone dipropionate (阿氯米松双丙酸酯)	26.26		521.3		301.1^*/319.2		10		16/		14		3.94
35	amcinonide (安西奈德)			25.88		503.3		399.2^*/339.2		2		10/		14		3.52
36	clobetasol 17-propionate (氯倍他索丙酸酯)			26.48		467.2		373.1^*/355.1		2		10/		14		3.98
37	fluticasone propionate (氟替卡松丙酸酯)			27.63		501.2		313.2^*/293.2		38		10/		14		3.73
38	mometasone furoate (莫米他松糠酸酯)			26.85		521.2		355.1^*/263.2		6		16/		22		4.27
39	betamethasone dipropionate (倍他米松双丙酸酯)			26.91		505.2		279.1^*/319.2		6		16/		14		4.42
40	beclomethasone dipropionate (倍氯米松双丙酸酯)			27.31		521.3		319.2^*/411.2		6		14/		10		4.59
41	clobetasone 17-butyrate (氯倍他松丁酸酯)			28.40		479.2		343.1^*/279.1		8		16/		18		4.82
42	fluocinolone acetonide (氟轻松)			19.73		453.2		121.1^*/433.3		26		34/		8		2.24
43	flumethasone 21-pivalate (双氟美松叔戊酸酯)			26.35		495.2		477.5^*/253.1		18		8/		16		3.44
44	diflucortolone (双氟可龙)			20.75		395.1		355.2^*/121.0		42		10/		30		2.72
45	fluticasone (氟替卡松)			24.97		445.1		405.1^*/121.1		24		10/		40		3.73
46	clocortolone pivalate (新戊酸氯可托龙)			28.16		495.3		457.2^*/337.1		32		10/		12		4.36
47	mometasone (莫美他松)			24.14		427.0		237.1^*/373.1		30		22/		14		4.86
48	9-fluoro-16α,17-(isopropylidenedioxy) corticosterone			16.24		437.1		105.1^*/121.1		62		52/		36		2.36
	(氢化曲安奈德)
49	prednisolone valerate acetate (泼尼瓦酯)			26.71		487.2		367.1^*/289.1		4		10/		14		4.58
50	fluprednisolone (氟泼尼龙)			6.69		379.1		341.1^*/171.1		10		8/		28		1.51
51	deprodone (迪普罗酮)			10.54		345.1		309.1^*/147.0		20		8/		22		3.55
52	isoflupredone acetate (9-氟泼尼松龙醋酸酯)			16.94		421.2		383.2^*/295.2		26		8/		12		2.46
53	hydrocortisone hemisuccinate hydrate (氢化可的松半琥酯)			12.24		463.2		327.2^*/309.2		8		12/		14		2.13
54	isoflupredone (异氟泼尼龙)			6.12		379.2		341.2^*/237.1		24		10/		18		1.38
55	methylprednisolone aceponate (甲基泼尼松龙乙丙酸酯)			25.77		473.1		381.2^*/321.1		18		8/		14		4.01
56	diflucortolone valerate (双氟可龙戊酸酯)			28.02		479.2		355.2^*/375.2		6		14/		12		4.65
57	flumethasone acetate (双氟美松醋酸酯)			22.78		453.2		253.1^*/433.2		48		18/		8		2.41
58	fludrocortisone (氟氢可的松)			6.43		381.2		239.1^*/181.1		12		22/		30		1.23
59	halometasone (卤米松)			21.14		445.1		155.0^*/287.1		8		32/		10		2.33
60	paramethasone (帕拉米松)			11.27		393.2		337.2^*/355.2		30		10/		30		1.75
61	desonide 21-acetate (醋酸地索奈德)			24.63		459.2		323.2^*/147.0		2		14/		34		2.89
62	ciclesonide (环索奈德)			28.82		541.3		323.2^*/147.0		40		16/		42		4.70
63	desonide (地索奈德)			15.62		417.2		323.2^*/147.0		12		10/		30		2.62
64	flunisolide (氟尼缩松)			20.71		435.2		321.1^*/339.1		14		12/		14		2.27
65	desoximetasone (去羟米松)			17.41		377.3		339.2^*/357.2		4		12/		10		2.20
66	halobetasol propionate (卤贝他索丙酸酯)			27.11		485.2		391.1^*/121.0		28		10/		34		4.05
67	epi hydrocortisone 21-acetate (表氢化可的松醋酸酯)			11.53		405.1		241.0^*/105.0		60		12/		28		2.35
68	fluocortolone (氟可龙)			18.99		377.2		303.2^*/321.2		4		14/		8		1.86
69	methylprednisolone hemisuccinate (琥珀酸甲泼尼龙)			17.81		475.3		321.2^*/339.2		20		12/		12		2.69
70	16α-hydroxyprednisolone (16a-羟基泼尼松龙)			3.75		377.2		323.2^*/147.0		6		8/		24		0.95
71	loteprednol etabonate (氯替泼诺)			26.06		467.1		359.2^*/265.1		22		10/		18		3.17
72	diflorasone (二氟拉松)			12.07		411.2		371.2^*/253.1		2		10/		16		1.61
73	16α-hydroxy prednisolone acetate (16α-羟基泼尼松龙醋酸酯)			9.64		419.2		323.2^*/147.0		26		12/		14		1.09
74	paramethasone acetate (醋酸帕拉米松)			22.77		435.2		319.2^*/337.2		8		10/		10		2.32
75	16-meprednisone acetate (16-甲基泼尼松龙醋酸酯)			22.96		415.2		309.2^*/355.2		24		12/		10		3.40
76	meprednisone (甲基泼尼松)			11.35		373.2		147.0^*/171.0		24		24/		30		2.06
77	prednisolone 21-trimethylacetate (泼尼松龙戊酸酯)			24.91		445.3		307.2^*/325.2		10		14/		21		3.15
78	difluprednate (双氟泼尼酯)			26.34		509.3		303.2^*/321.2		8		14/		14		3.67
79	ulobetasol (卤倍他索)			23.67		429.2		90.7^*/121.0		2		52/		44		3.09
80	hydrocortisone cypionate (氢化可的松环戊丙酸酯)			26.84		487.4		78.9^*/107.0		10		50/		32		4.30
81	6α-fluoro-isoflupredone (6α-氟-异氟泼尼龙)			8.38		397.2		253.1^*/121.0		12		16/		34		1.12
82	triamcinolone hexacetonide (己曲安奈德)			28.24		533.4		71.0^*/99.0		2		26/		26		4.41
83	rimexolone (利美索龙)			25.91		371.3		295.2^*/121.0		2		10/		42		4.01

No.		Analyte	t_R/ min		Parent ion (m/z)		Product ions (m/z)		Cone voltage/V		Collision energies/eV				lg K_ow
1		triamcinolone (曲安西龙)	4.07		395.2		375.2^*/357.2		2		6/		12		0.83
2		prednisolone (泼尼松龙)	5.69		361.2		147.1^*/325.2		4		28/		8		1.50
3		hydrocortisone (氢化可的松)	5.68		363.2		121.1^*/327.2		30		24/		16		1.43
4		prednisone (泼尼松)	7.10		359.2		313.2^*/147.1		34		10/		24		1.57
5		cortisone (可的松)	6.79		361.2		163.1^*/121.1		10		22/		32		1.44
6		methylprednisolone (甲基泼尼松龙)	8.99		375.2		161.1^*/339.2		18		18/		6		1.99
7		betamethasone (倍他米松)	9.68		393.2		373.2^*/355.2		10		4/		10		1.87
8		dexamethasone (地塞米松)	10.29		393.2		355.2^*/337.2		2		10/		12		1.87
9		flumethasone (氟米松)	13.14		411.2		253.2^*/121.1		28		14/		36		1.84
10		beclomethasone (倍氯米松)	24.14		409.2		373.2^*/147.0		12		10/		32		4.59
11		triamcinolone acetonide (曲安奈德)	17.60		435.2		397.2^*/339.2		4		14/		14		2.50
12		fludroxycortide (氟氢缩松)	16.84		437.3		91.1^*/105.1		4		62/		44		2.50
13		triamcinolone diacetate (曲安西龙双醋酸酯)	19.11		479.3		441.2^*/321.2		6		10/		14		2.16
14		prednisolone 21-acetate (泼尼松龙醋酸酯)	15.29		403.2		147.1^*/325.2		4		22/		10		2.58
15		fluoromethalone (氟米龙)	15.65		377.2		279.2^*/339.2		32		14/		10		2.02
16		hydrocortisone 21-acetate (氢化可的松醋酸酯)	14.86		405.3		309.2^*/121.1		2		14/		30		2.51
17		deflazacort (地夫可特)	19.20		442.2		142.0^*/124.0		68		36/		44		2.02
18		fludrocortisone 21-acetate (氟氢可的松醋酸酯)	17.23		423.2		239.2^*/325.2		64		24/		20		2.32
19		prednisone 21-acetate (泼尼松醋酸酯)	20.03		401.2		295.2^*/147.1		6		14/		24		2.66
20		cortisone 21-acetate (可的松醋酸酯)	19.40		403.2		163.1^*/343.2		2		26/		18		2.53
21		methylprednisolone 21-acetate (甲基泼尼松龙醋酸酯)	20.63		417.3		339.2^*/321.2		12		8/		12		3.08
22		betamethasone 21-acetate (倍他米松醋酸酯)	21.51		435.2		397.2^*/319.2		2		8/		12		2.96
23		budesonide (布地奈德)	22.15		431.3		147.1^*/323.2		2		28/		10		3.14
24		hydrocortisone 17-butyrate (氢化可的松丁酸酯)	22.14		433.3		345.2^*/121.1		26		12/		28		2.81
25		dexamethasone 21-acetate (地塞米松醋酸酯)	21.91		435.2		397.2^*/337.2		24		10/		10		2.96
26		fluorometholone 17-acetate (氟米龙醋酸酯)	24.00		419.2		279.2^*/321.2		2		14/		12		2.57
27		hydrocortisone 17-valerate (氢化可的松戊酸酯)	24.09		447.3		345.2^*/121.0		2		12/		28		3.52
28		triamcinolone acetonide 21-acetate (曲安奈德醋酸酯)	24.70		477.3		339.2^*/439.2		4		14/		14		3.61
29		fluocinonide (氟轻松醋酸酯)	25.18		495.2		337.2^*/121.1		2		16/		40		3.36
30		diflorasone diacetate (二氟拉松双醋酸酯)	25.59		495.2		317.2^*/279.2		24		12/		14		3.10
31		betamethasone 17-valerate (倍他米松戊酸酯)	25.26		477.3		355.2^*/279.2		4		16/		14		3.78
32		prednicarbate (泼尼卡酯)	25.88		489.3		381.2^*/115.0		22		8/		16		4.02
33		halcinonide (哈西奈德)	25.52		455.2		359.2^*/105.1		70		22/		58		3.31
34		alclomethasone dipropionate (阿氯米松双丙酸酯)	26.26		521.3		301.1^*/319.2		10		16/		14		3.94
35	amcinonide (安西奈德)			25.88		503.3		399.2^*/339.2		2		10/		14		3.52
36	clobetasol 17-propionate (氯倍他索丙酸酯)			26.48		467.2		373.1^*/355.1		2		10/		14		3.98
37	fluticasone propionate (氟替卡松丙酸酯)			27.63		501.2		313.2^*/293.2		38		10/		14		3.73
38	mometasone furoate (莫米他松糠酸酯)			26.85		521.2		355.1^*/263.2		6		16/		22		4.27
39	betamethasone dipropionate (倍他米松双丙酸酯)			26.91		505.2		279.1^*/319.2		6		16/		14		4.42
40	beclomethasone dipropionate (倍氯米松双丙酸酯)			27.31		521.3		319.2^*/411.2		6		14/		10		4.59
41	clobetasone 17-butyrate (氯倍他松丁酸酯)			28.40		479.2		343.1^*/279.1		8		16/		18		4.82
42	fluocinolone acetonide (氟轻松)			19.73		453.2		121.1^*/433.3		26		34/		8		2.24
43	flumethasone 21-pivalate (双氟美松叔戊酸酯)			26.35		495.2		477.5^*/253.1		18		8/		16		3.44
44	diflucortolone (双氟可龙)			20.75		395.1		355.2^*/121.0		42		10/		30		2.72
45	fluticasone (氟替卡松)			24.97		445.1		405.1^*/121.1		24		10/		40		3.73
46	clocortolone pivalate (新戊酸氯可托龙)			28.16		495.3		457.2^*/337.1		32		10/		12		4.36
47	mometasone (莫美他松)			24.14		427.0		237.1^*/373.1		30		22/		14		4.86
48	9-fluoro-16α,17-(isopropylidenedioxy) corticosterone			16.24		437.1		105.1^*/121.1		62		52/		36		2.36
	(氢化曲安奈德)
49	prednisolone valerate acetate (泼尼瓦酯)			26.71		487.2		367.1^*/289.1		4		10/		14		4.58
50	fluprednisolone (氟泼尼龙)			6.69		379.1		341.1^*/171.1		10		8/		28		1.51
51	deprodone (迪普罗酮)			10.54		345.1		309.1^*/147.0		20		8/		22		3.55
52	isoflupredone acetate (9-氟泼尼松龙醋酸酯)			16.94		421.2		383.2^*/295.2		26		8/		12		2.46
53	hydrocortisone hemisuccinate hydrate (氢化可的松半琥酯)			12.24		463.2		327.2^*/309.2		8		12/		14		2.13
54	isoflupredone (异氟泼尼龙)			6.12		379.2		341.2^*/237.1		24		10/		18		1.38
55	methylprednisolone aceponate (甲基泼尼松龙乙丙酸酯)			25.77		473.1		381.2^*/321.1		18		8/		14		4.01
56	diflucortolone valerate (双氟可龙戊酸酯)			28.02		479.2		355.2^*/375.2		6		14/		12		4.65
57	flumethasone acetate (双氟美松醋酸酯)			22.78		453.2		253.1^*/433.2		48		18/		8		2.41
58	fludrocortisone (氟氢可的松)			6.43		381.2		239.1^*/181.1		12		22/		30		1.23
59	halometasone (卤米松)			21.14		445.1		155.0^*/287.1		8		32/		10		2.33
60	paramethasone (帕拉米松)			11.27		393.2		337.2^*/355.2		30		10/		30		1.75
61	desonide 21-acetate (醋酸地索奈德)			24.63		459.2		323.2^*/147.0		2		14/		34		2.89
62	ciclesonide (环索奈德)			28.82		541.3		323.2^*/147.0		40		16/		42		4.70
63	desonide (地索奈德)			15.62		417.2		323.2^*/147.0		12		10/		30		2.62
64	flunisolide (氟尼缩松)			20.71		435.2		321.1^*/339.1		14		12/		14		2.27
65	desoximetasone (去羟米松)			17.41		377.3		339.2^*/357.2		4		12/		10		2.20
66	halobetasol propionate (卤贝他索丙酸酯)			27.11		485.2		391.1^*/121.0		28		10/		34		4.05
67	epi hydrocortisone 21-acetate (表氢化可的松醋酸酯)			11.53		405.1		241.0^*/105.0		60		12/		28		2.35
68	fluocortolone (氟可龙)			18.99		377.2		303.2^*/321.2		4		14/		8		1.86
69	methylprednisolone hemisuccinate (琥珀酸甲泼尼龙)			17.81		475.3		321.2^*/339.2		20		12/		12		2.69
70	16α-hydroxyprednisolone (16a-羟基泼尼松龙)			3.75		377.2		323.2^*/147.0		6		8/		24		0.95
71	loteprednol etabonate (氯替泼诺)			26.06		467.1		359.2^*/265.1		22		10/		18		3.17
72	diflorasone (二氟拉松)			12.07		411.2		371.2^*/253.1		2		10/		16		1.61
73	16α-hydroxy prednisolone acetate (16α-羟基泼尼松龙醋酸酯)			9.64		419.2		323.2^*/147.0		26		12/		14		1.09
74	paramethasone acetate (醋酸帕拉米松)			22.77		435.2		319.2^*/337.2		8		10/		10		2.32
75	16-meprednisone acetate (16-甲基泼尼松龙醋酸酯)			22.96		415.2		309.2^*/355.2		24		12/		10		3.40
76	meprednisone (甲基泼尼松)			11.35		373.2		147.0^*/171.0		24		24/		30		2.06
77	prednisolone 21-trimethylacetate (泼尼松龙戊酸酯)			24.91		445.3		307.2^*/325.2		10		14/		21		3.15
78	difluprednate (双氟泼尼酯)			26.34		509.3		303.2^*/321.2		8		14/		14		3.67
79	ulobetasol (卤倍他索)			23.67		429.2		90.7^*/121.0		2		52/		44		3.09
80	hydrocortisone cypionate (氢化可的松环戊丙酸酯)			26.84		487.4		78.9^*/107.0		10		50/		32		4.30
81	6α-fluoro-isoflupredone (6α-氟-异氟泼尼龙)			8.38		397.2		253.1^*/121.0		12		16/		34		1.12
82	triamcinolone hexacetonide (己曲安奈德)			28.24		533.4		71.0^*/99.0		2		26/		26		4.41
83	rimexolone (利美索龙)			25.91		371.3		295.2^*/121.0		2		10/		42		4.01

No.	Linear equation	r	LOD/(μg/g)	LOQ/(μg/g)	Recoveries/% (n=6)	RSDs/% (n=6)	ME/%
1	y=1.06×10³x+2.34×10³	0.9962	0.009	0.030	99.4, 102.2, 101.7	6.2, 3.5, 5.4	9.95
2	y=4.28×10³x-2.50×10³	0.9957	0.006	0.020	103.0, 99.9, 100.2	5.5, 2.9, 5.6	19.73
3	y=1.38×10⁴x-1.06×10⁴	0.9968	0.001	0.003	105.4, 105.4, 104.1	3.4, 3.2, 4.0	20.84
4	y=6.85×10³x-3.28×10³	0.9987	0.005	0.017	96.2, 101.7, 101.2	2.3, 3.0, 2.3	10.80
5	y=2.26×10⁴x-8.00×10³	0.9973	0.002	0.007	95.0, 105.7, 106.4	3.0, 2.8, 2.4	12.38
6	y=3.15×10³x-2.22×10³	0.9980	0.003	0.010	100.3, 110.2, 106.9	2.6, 4.9, 1.6	14.78
7	y=4.13×10³x-8.46×10³	0.9981	0.010	0.033	98.8, 105.8, 110.0	2.6, 5.5, 2.0	19.25
8	y=2.80×10³x-1.65×10³	0.9983	0.006	0.020	97.6, 105.9, 112.3	3.0, 8.2, 1.8	14.77
9	y=6.59×10³x-9.97×10³	0.9960	0.002	0.007	99.0, 95.4, 94.9	2.3, 8.0, 1.3	15.94
10	y=1.45×10³x+3.11×10³	0.9998	0.001	0.003	97.0, 103.3, 111.3	3.7, 7.6, 2.1	20.13
11	y=5.19×10³x-8.46×10³	0.9988	0.002	0.007	100.4, 99.8, 104.5	4.9, 5.6, 3.4	8.52
12	y=3.46×10³x+1.47×10³	0.9989	0.004	0.013	105.6, 109.7, 103.6	3.3, 7.7, 2.5	12.46
13	y=6.18×10³x-5.73×10³	0.9973	0.002	0.007	101.4, 98.7, 88.8	6.3, 7.6, 3.3	22.16
14	y=4.33×10³x+1.91×10³	0.9971	0.003	0.010	91.2, 101.0, 104.2	5.2, 6.0, 4.1	16.60
15	y=4.24×10³x-1.20×10³	0.9981	0.002	0.007	104.6, 100.3, 100.4	5.2, 5.0, 2.8	13.26
16	y=1.17×10⁴x-1.08×10⁴	0.9980	0.005	0.017	102.4, 101.9, 98.7	5.3, 6.9, 3.4	18.23
17	y=1.99×10⁴x-1.88×10⁴	0.9987	0.001	0.003	89.6, 99.8, 90.4	4.8, 5.6, 2.9	4.37
18	y=5.23×10³x-2.78×10³	0.9972	0.003	0.010	92.8, 94.0, 88.8	4.2, 4.0, 2.6	14.04
19	y=1.15×10⁴x-1.15×10⁴	0.9978	0.002	0.007	103.8, 106.6, 104.0	6.9, 9.9, 4.2	24.82
20	y=2.52×10⁴x-1.20×10⁴	0.9970	0.001	0.003	105.4, 105.3, 100.5	7.4, 9.2, 2.4	28.22
21	y=5.28×10³x-2.96×10³	0.9981	0.009	0.030	102.4, 96.8, 94.4	5.5, 5.2, 2.4	25.13
22	y=4.97×10³x-3.30×10²	0.9983	0.005	0.017	93.0, 91.5, 90.2	5.5, 3.9, 1.6	22.34
23	y=5.08×10³x-1.50×10³	0.9971	0.001	0.003	96.0, 99.7, 100.0	4.2, 5.3, 1.6	19.28
24	y=1.38×10⁴x-5.82×10³	0.9968	0.001	0.002	103.2, 102.7, 98.5	4.1, 4.9, 1.7	16.34
25	y=4.89×10³x-7.30×10³	0.9974	0.005	0.017	102.8, 94.4, 91.8	7.8, 6.8, 2.1	22.18
26	y=3.33×10⁴x-7.33×10³	0.9981	0.001	0.003	98.0, 100.5, 97.1	6.1, 4.8, 1.4	14.97
27	y=1.96×10⁴x-7.77×10³	0.9972	0.001	0.003	95.6, 101.2, 93.2	5.1, 4.9, 2.8	17.04
28	y=1.18×10⁴x-4.86×10²	0.9970	0.001	0.003	98.2, 97.0, 88.5	3.7, 2.6, 2.0	15.81
29	y=9.34×10³x-4.55×10³	0.9976	0.001	0.003	98.2, 99.0, 88.5	3.1, 2.3, 1.8	20.43
30	y=1.15×10⁴x-2.40×10³	0.9963	0.001	0.003	97.8, 97.8, 85.5	5.4, 3.1, 3.4	17.82
31	y=1.98×10³x-5.08×10²	0.9974	0.001	0.003	97.6, 92.8, 89.7	5.5, 4.2, 2.1	18.61
32	y=1.54×10⁴x+2.07×10³	0.9964	0.001	0.003	100.0, 93.5, 78.1	5.0, 4.7, 6.0	20.40
33	y=4.52×10³x+7.06×10²	0.9962	0.001	0.003	95.0, 92.5, 88.5	5.1, 5.9, 5.1	11.06
34	y=6.36×10³x-1.95×10³	0.9954	0.002	0.007	78.5, 98.0, 79.8	5.4, 2.1, 4.4	18.56
35	y=1.29×10⁴x+1.96×10³	0.9967	0.001	0.003	95.8, 89.9, 82.6	3.5, 3.0, 1.8	21.08
36	y=1.38×10⁴x+3.87×10²	0.9968	0.002	0.007	85.8, 82.5, 80.2	6.3, 5.2, 1.8	20.19
37	y=1.83×10⁴x-1.25×10⁴	0.9951	0.002	0.007	85.6, 75.0, 86.0	5.1, 2.3, 6.3	28.10
38	y=5.57×10³x-6.29×10³	0.9956	0.007	0.023	77.8, 76.8, 81.5	5.4, 4.9, 3.1	22.88
39	y=9.24×10³x-4.82×10³	0.9952	0.001	0.003	75.4, 79.0, 74.5	3.5, 2.7, 1.7	14.77
40	y=6.05×10³x-7.46×10³	0.9958	0.001	0.003	79.8, 77.5, 78.9	6.9, 1.8, 7.9	29.92
41	y=1.30×10⁴x+2.91×10²	0.9958	0.001	0.003	98.4, 79.2, 78.4	7.0, 8.1, 9.9	27.47
42	y=9.06×10²x-1.40×10³	0.9951	0.001	0.003	99.0, 96.3, 93.3	4.9, 6.0, 2.3	29.28
43	y=4.36×10³x-2.50×10³	0.9974	0.012	0.040	76.4, 75.6, 81.4	2.1, 1.8, 1.4	20.30
44	y=2.49×10⁴x-1.04×10⁴	0.9972	0.007	0.023	100.4, 93.8, 100.1	6.1, 8.0, 1.3	28.48
45	y=1.22×10⁴x+6.19×10³	0.9989	0.009	0.030	95.8, 97.2, 96.0	5.1, 6.1, 2.0	15.98
46	y=4.74×10³x-1.06×10³	0.9967	0.005	0.016	78.7, 74.5, 75.8	5.8, 6.6, 8.3	23.25
47	y=3.44×10³x-2.02×10³	0.9995	0.019	0.063	90.0, 91.7, 91.2	4.1, 4.6, 1.9	17.81
48	y=3.44×10³x-5.47×10³	0.9950	0.018	0.059	104.2, 101.4, 103.4	4.8, 8.0, 2.5	11.41
49	y=1.32×10⁴x-4.77×10³	0.9964	0.005	0.017	76.8, 79.7, 78.4	5.6, 7.9, 4.0	25.62
50	y=1.42×10⁴x-5.82×10³	0.9976	0.004	0.013	97.0, 102.3, 92.9	3.8, 3.0, 2.3	12.89
51	y=2.37×10³x-2.49×10³	0.9988	0.016	0.053	97.0, 100.3, 92.9	2.2, 6.8, 1.6	-2.05
52	y=3.71×10³x-3.34×10²	0.9955	0.015	0.050	95.6, 97.7, 92.9	4.6, 3.9, 2.9	19.98
53	y=9.00×10³x-9.18×10³	0.9995	0.005	0.016	96.8, 97.4, 96.7	5.0, 5.0, 2.7	7.77
54	y=4.06×10³x-9.52×10²	0.9995	0.014	0.046	100.8, 103.1, 99.1	5.6, 9.2, 8.8	24.48
55	y=9.37×10³x-6.45×10³	0.9986	0.008	0.026	99.8, 92.6, 78.9	9.6, 3.5, 5.7	20.91
56	y=1.10×10⁴x-3.86×10³	0.9965	0.001	0.003	86.6, 79.2, 85.8	8.6, 3.3, 6.1	29.62
57	y=1.79×10⁴x+4.30×10²	0.9963	0.004	0.014	97.2, 95.5, 89.5	5.1, 4.1, 2.2	10.64
58	y=4.54×10³x+2.26×10³	0.9951	0.016	0.053	106.0, 100.9, 103.0	1.1, 7.5, 6.6	20.17
59	y=2.77×10³x-2.80×10³	0.9977	0.023	0.076	103.4, 96.6, 99.8	1.1, 6.1, 2.3	17.15
60	y=2.72×10³x+3.30×10³	0.9992	0.009	0.030	95.6, 98.0, 90.8	5.4, 8.5, 1.5	16.54
61	y=1.41×10⁴x-2.89×10³	0.9985	0.005	0.017	97.0, 95.8, 87.9	3.1, 2.8, 1.7	17.45
62	y=8.20×10³x-1.67×10³	0.9972	0.001	0.003	78.2, 77.5, 75.6	4.9, 6.1, 8.5	28.90
63	y=7.06×10³x-1.17×10⁴	0.9975	0.001	0.003	99.2, 99.7, 102.4	5.1, 6.2, 3.8	16.91
64	y=3.59×10³x-7.65×10³	0.9997	0.013	0.044	103.4, 98.6, 99.5	4.7, 7.2, 2.2	14.30
65	y=6.12×10³x-4.01×10³	0.9989	0.009	0.030	105.8, 108.3, 106.3	5.3, 6.1, 2.1	20.96
66	y=6.30×10³x+1.66×10³	0.9955	0.001	0.003	84.0, 74.8, 77.8	7.1, 2.2, 3.3	20.56
67	y=8.23×10²x+1.70×10³	0.9997	0.009	0.030	104.0, 101.7, 93.7	5.5, 7.0, 3.9	9.49
68	y=6.33×10³x-6.95×10³	0.9969	0.009	0.030	93.4, 97.4, 103.6	4.2, 7.2, 2.1	23.65
69	y=2.63×10³x-2.14×10³	0.9988	0.008	0.026	105.0, 104.8, 104.2	6.5, 4.0, 3.6	12.89
70	y=2.69×10⁴x+2.26×10⁴	0.9979	0.005	0.015	98.6, 107.8, 112.2	7.2, 4.7, 5.0	5.85
71	y=1.46×10⁴x-1.30×10⁴	0.9970	0.001	0.003	88.8, 84.3, 79.5	6.6, 3.8, 5.7	18.52
72	y=2.45×10³x-1.40×10³	0.9998	0.009	0.030	102.0, 100.3, 103.1	3.5, 8.4, 1.1	24.14
73	y=3.01×10³x+4.00×10²	0.9996	0.008	0.026	98.6, 107.7, 85.2	6.3, 6.6, 7.7	14.18
74	y=4.60×10³x-7.07×10³	0.9991	0.008	0.026	105.0, 97.1, 88.9	4.2, 5.5, 2.8	19.17
75	y=2.32×10⁴x-1.30×10⁴	0.9973	0.007	0.023	95.6, 104.4, 102.4	6.4, 6.6, 1.9	10.31
76	y=6.37×10³x-9.39×10³	0.9978	0.002	0.007	78.5, 84.3, 104.4	8.2, 1.8, 9.8	19.60
77	y=7.80×10³x-1.36×10³	0.9991	0.003	0.010	93.7, 103.1, 105.0	5.2, 2.0, 2.8	17.44
78	y=1.45×10⁴x-4.07×10³	0.9981	0.002	0.007	86.7, 91.2, 100.7	4.5, 5.3, 4.3	24.82
79	y=1.28×10³x-2.04×10³	0.9979	0.006	0.020	93.2, 106.7, 109.1	7.9, 7.4, 8.4	16.65
80	y=1.24×10⁴x-6.57×10³	0.9972	0.005	0.017	89.2, 102.2, 99.7	5.6, 5.7, 2.1	13.59
81	y=5.82×10³x-5.94×10²	0.9992	0.009	0.030	91.0, 107.2, 112.4	6.8, 5.0, 8.3	13.76
82	y=5.57×10³x+3.29×10³	0.9992	0.009	0.030	78.2, 89.7, 90.8	7.7, 1.0, 2.7	29.27
83	y=2.59×10³x-1.47×10³	0.9987	0.009	0.030	78.2, 79.6, 89.5	5.9, 7.4, 0.8	28.24

No.	Linear equation	r	LOD/(μg/g)	LOQ/(μg/g)	Recoveries/% (n=6)	RSDs/% (n=6)	ME/%
1	y=1.06×10³x+2.34×10³	0.9962	0.009	0.030	99.4, 102.2, 101.7	6.2, 3.5, 5.4	9.95
2	y=4.28×10³x-2.50×10³	0.9957	0.006	0.020	103.0, 99.9, 100.2	5.5, 2.9, 5.6	19.73
3	y=1.38×10⁴x-1.06×10⁴	0.9968	0.001	0.003	105.4, 105.4, 104.1	3.4, 3.2, 4.0	20.84
4	y=6.85×10³x-3.28×10³	0.9987	0.005	0.017	96.2, 101.7, 101.2	2.3, 3.0, 2.3	10.80
5	y=2.26×10⁴x-8.00×10³	0.9973	0.002	0.007	95.0, 105.7, 106.4	3.0, 2.8, 2.4	12.38
6	y=3.15×10³x-2.22×10³	0.9980	0.003	0.010	100.3, 110.2, 106.9	2.6, 4.9, 1.6	14.78
7	y=4.13×10³x-8.46×10³	0.9981	0.010	0.033	98.8, 105.8, 110.0	2.6, 5.5, 2.0	19.25
8	y=2.80×10³x-1.65×10³	0.9983	0.006	0.020	97.6, 105.9, 112.3	3.0, 8.2, 1.8	14.77
9	y=6.59×10³x-9.97×10³	0.9960	0.002	0.007	99.0, 95.4, 94.9	2.3, 8.0, 1.3	15.94
10	y=1.45×10³x+3.11×10³	0.9998	0.001	0.003	97.0, 103.3, 111.3	3.7, 7.6, 2.1	20.13
11	y=5.19×10³x-8.46×10³	0.9988	0.002	0.007	100.4, 99.8, 104.5	4.9, 5.6, 3.4	8.52
12	y=3.46×10³x+1.47×10³	0.9989	0.004	0.013	105.6, 109.7, 103.6	3.3, 7.7, 2.5	12.46
13	y=6.18×10³x-5.73×10³	0.9973	0.002	0.007	101.4, 98.7, 88.8	6.3, 7.6, 3.3	22.16
14	y=4.33×10³x+1.91×10³	0.9971	0.003	0.010	91.2, 101.0, 104.2	5.2, 6.0, 4.1	16.60
15	y=4.24×10³x-1.20×10³	0.9981	0.002	0.007	104.6, 100.3, 100.4	5.2, 5.0, 2.8	13.26
16	y=1.17×10⁴x-1.08×10⁴	0.9980	0.005	0.017	102.4, 101.9, 98.7	5.3, 6.9, 3.4	18.23
17	y=1.99×10⁴x-1.88×10⁴	0.9987	0.001	0.003	89.6, 99.8, 90.4	4.8, 5.6, 2.9	4.37
18	y=5.23×10³x-2.78×10³	0.9972	0.003	0.010	92.8, 94.0, 88.8	4.2, 4.0, 2.6	14.04
19	y=1.15×10⁴x-1.15×10⁴	0.9978	0.002	0.007	103.8, 106.6, 104.0	6.9, 9.9, 4.2	24.82
20	y=2.52×10⁴x-1.20×10⁴	0.9970	0.001	0.003	105.4, 105.3, 100.5	7.4, 9.2, 2.4	28.22
21	y=5.28×10³x-2.96×10³	0.9981	0.009	0.030	102.4, 96.8, 94.4	5.5, 5.2, 2.4	25.13
22	y=4.97×10³x-3.30×10²	0.9983	0.005	0.017	93.0, 91.5, 90.2	5.5, 3.9, 1.6	22.34
23	y=5.08×10³x-1.50×10³	0.9971	0.001	0.003	96.0, 99.7, 100.0	4.2, 5.3, 1.6	19.28
24	y=1.38×10⁴x-5.82×10³	0.9968	0.001	0.002	103.2, 102.7, 98.5	4.1, 4.9, 1.7	16.34
25	y=4.89×10³x-7.30×10³	0.9974	0.005	0.017	102.8, 94.4, 91.8	7.8, 6.8, 2.1	22.18
26	y=3.33×10⁴x-7.33×10³	0.9981	0.001	0.003	98.0, 100.5, 97.1	6.1, 4.8, 1.4	14.97
27	y=1.96×10⁴x-7.77×10³	0.9972	0.001	0.003	95.6, 101.2, 93.2	5.1, 4.9, 2.8	17.04
28	y=1.18×10⁴x-4.86×10²	0.9970	0.001	0.003	98.2, 97.0, 88.5	3.7, 2.6, 2.0	15.81
29	y=9.34×10³x-4.55×10³	0.9976	0.001	0.003	98.2, 99.0, 88.5	3.1, 2.3, 1.8	20.43
30	y=1.15×10⁴x-2.40×10³	0.9963	0.001	0.003	97.8, 97.8, 85.5	5.4, 3.1, 3.4	17.82
31	y=1.98×10³x-5.08×10²	0.9974	0.001	0.003	97.6, 92.8, 89.7	5.5, 4.2, 2.1	18.61
32	y=1.54×10⁴x+2.07×10³	0.9964	0.001	0.003	100.0, 93.5, 78.1	5.0, 4.7, 6.0	20.40
33	y=4.52×10³x+7.06×10²	0.9962	0.001	0.003	95.0, 92.5, 88.5	5.1, 5.9, 5.1	11.06
34	y=6.36×10³x-1.95×10³	0.9954	0.002	0.007	78.5, 98.0, 79.8	5.4, 2.1, 4.4	18.56
35	y=1.29×10⁴x+1.96×10³	0.9967	0.001	0.003	95.8, 89.9, 82.6	3.5, 3.0, 1.8	21.08
36	y=1.38×10⁴x+3.87×10²	0.9968	0.002	0.007	85.8, 82.5, 80.2	6.3, 5.2, 1.8	20.19
37	y=1.83×10⁴x-1.25×10⁴	0.9951	0.002	0.007	85.6, 75.0, 86.0	5.1, 2.3, 6.3	28.10
38	y=5.57×10³x-6.29×10³	0.9956	0.007	0.023	77.8, 76.8, 81.5	5.4, 4.9, 3.1	22.88
39	y=9.24×10³x-4.82×10³	0.9952	0.001	0.003	75.4, 79.0, 74.5	3.5, 2.7, 1.7	14.77
40	y=6.05×10³x-7.46×10³	0.9958	0.001	0.003	79.8, 77.5, 78.9	6.9, 1.8, 7.9	29.92
41	y=1.30×10⁴x+2.91×10²	0.9958	0.001	0.003	98.4, 79.2, 78.4	7.0, 8.1, 9.9	27.47
42	y=9.06×10²x-1.40×10³	0.9951	0.001	0.003	99.0, 96.3, 93.3	4.9, 6.0, 2.3	29.28
43	y=4.36×10³x-2.50×10³	0.9974	0.012	0.040	76.4, 75.6, 81.4	2.1, 1.8, 1.4	20.30
44	y=2.49×10⁴x-1.04×10⁴	0.9972	0.007	0.023	100.4, 93.8, 100.1	6.1, 8.0, 1.3	28.48
45	y=1.22×10⁴x+6.19×10³	0.9989	0.009	0.030	95.8, 97.2, 96.0	5.1, 6.1, 2.0	15.98
46	y=4.74×10³x-1.06×10³	0.9967	0.005	0.016	78.7, 74.5, 75.8	5.8, 6.6, 8.3	23.25
47	y=3.44×10³x-2.02×10³	0.9995	0.019	0.063	90.0, 91.7, 91.2	4.1, 4.6, 1.9	17.81
48	y=3.44×10³x-5.47×10³	0.9950	0.018	0.059	104.2, 101.4, 103.4	4.8, 8.0, 2.5	11.41
49	y=1.32×10⁴x-4.77×10³	0.9964	0.005	0.017	76.8, 79.7, 78.4	5.6, 7.9, 4.0	25.62
50	y=1.42×10⁴x-5.82×10³	0.9976	0.004	0.013	97.0, 102.3, 92.9	3.8, 3.0, 2.3	12.89
51	y=2.37×10³x-2.49×10³	0.9988	0.016	0.053	97.0, 100.3, 92.9	2.2, 6.8, 1.6	-2.05
52	y=3.71×10³x-3.34×10²	0.9955	0.015	0.050	95.6, 97.7, 92.9	4.6, 3.9, 2.9	19.98
53	y=9.00×10³x-9.18×10³	0.9995	0.005	0.016	96.8, 97.4, 96.7	5.0, 5.0, 2.7	7.77
54	y=4.06×10³x-9.52×10²	0.9995	0.014	0.046	100.8, 103.1, 99.1	5.6, 9.2, 8.8	24.48
55	y=9.37×10³x-6.45×10³	0.9986	0.008	0.026	99.8, 92.6, 78.9	9.6, 3.5, 5.7	20.91
56	y=1.10×10⁴x-3.86×10³	0.9965	0.001	0.003	86.6, 79.2, 85.8	8.6, 3.3, 6.1	29.62
57	y=1.79×10⁴x+4.30×10²	0.9963	0.004	0.014	97.2, 95.5, 89.5	5.1, 4.1, 2.2	10.64
58	y=4.54×10³x+2.26×10³	0.9951	0.016	0.053	106.0, 100.9, 103.0	1.1, 7.5, 6.6	20.17
59	y=2.77×10³x-2.80×10³	0.9977	0.023	0.076	103.4, 96.6, 99.8	1.1, 6.1, 2.3	17.15
60	y=2.72×10³x+3.30×10³	0.9992	0.009	0.030	95.6, 98.0, 90.8	5.4, 8.5, 1.5	16.54
61	y=1.41×10⁴x-2.89×10³	0.9985	0.005	0.017	97.0, 95.8, 87.9	3.1, 2.8, 1.7	17.45
62	y=8.20×10³x-1.67×10³	0.9972	0.001	0.003	78.2, 77.5, 75.6	4.9, 6.1, 8.5	28.90
63	y=7.06×10³x-1.17×10⁴	0.9975	0.001	0.003	99.2, 99.7, 102.4	5.1, 6.2, 3.8	16.91
64	y=3.59×10³x-7.65×10³	0.9997	0.013	0.044	103.4, 98.6, 99.5	4.7, 7.2, 2.2	14.30
65	y=6.12×10³x-4.01×10³	0.9989	0.009	0.030	105.8, 108.3, 106.3	5.3, 6.1, 2.1	20.96
66	y=6.30×10³x+1.66×10³	0.9955	0.001	0.003	84.0, 74.8, 77.8	7.1, 2.2, 3.3	20.56
67	y=8.23×10²x+1.70×10³	0.9997	0.009	0.030	104.0, 101.7, 93.7	5.5, 7.0, 3.9	9.49
68	y=6.33×10³x-6.95×10³	0.9969	0.009	0.030	93.4, 97.4, 103.6	4.2, 7.2, 2.1	23.65
69	y=2.63×10³x-2.14×10³	0.9988	0.008	0.026	105.0, 104.8, 104.2	6.5, 4.0, 3.6	12.89
70	y=2.69×10⁴x+2.26×10⁴	0.9979	0.005	0.015	98.6, 107.8, 112.2	7.2, 4.7, 5.0	5.85
71	y=1.46×10⁴x-1.30×10⁴	0.9970	0.001	0.003	88.8, 84.3, 79.5	6.6, 3.8, 5.7	18.52
72	y=2.45×10³x-1.40×10³	0.9998	0.009	0.030	102.0, 100.3, 103.1	3.5, 8.4, 1.1	24.14
73	y=3.01×10³x+4.00×10²	0.9996	0.008	0.026	98.6, 107.7, 85.2	6.3, 6.6, 7.7	14.18
74	y=4.60×10³x-7.07×10³	0.9991	0.008	0.026	105.0, 97.1, 88.9	4.2, 5.5, 2.8	19.17
75	y=2.32×10⁴x-1.30×10⁴	0.9973	0.007	0.023	95.6, 104.4, 102.4	6.4, 6.6, 1.9	10.31
76	y=6.37×10³x-9.39×10³	0.9978	0.002	0.007	78.5, 84.3, 104.4	8.2, 1.8, 9.8	19.60
77	y=7.80×10³x-1.36×10³	0.9991	0.003	0.010	93.7, 103.1, 105.0	5.2, 2.0, 2.8	17.44
78	y=1.45×10⁴x-4.07×10³	0.9981	0.002	0.007	86.7, 91.2, 100.7	4.5, 5.3, 4.3	24.82
79	y=1.28×10³x-2.04×10³	0.9979	0.006	0.020	93.2, 106.7, 109.1	7.9, 7.4, 8.4	16.65
80	y=1.24×10⁴x-6.57×10³	0.9972	0.005	0.017	89.2, 102.2, 99.7	5.6, 5.7, 2.1	13.59
81	y=5.82×10³x-5.94×10²	0.9992	0.009	0.030	91.0, 107.2, 112.4	6.8, 5.0, 8.3	13.76
82	y=5.57×10³x+3.29×10³	0.9992	0.009	0.030	78.2, 89.7, 90.8	7.7, 1.0, 2.7	29.27
83	y=2.59×10³x-1.47×10³	0.9987	0.009	0.030	78.2, 79.6, 89.5	5.9, 7.4, 0.8	28.24