超高效液相色谱-串联质谱法测定运动营养食品中60种类固醇激素

doi:10.3724/SP.J.1123.2024.03020

摘要/Abstract

摘要：

基于QuEChERS,结合超高效液相色谱-串联质谱(UPLC-MS/MS)技术,建立了一种同时测定运动营养食品中60种类固醇激素的分析方法。样品以1.0%(v/v)甲酸乙腈提取,氯化钠进行分层,150 mg PSA和150 mg C₁₈粉末净化,净化液经氮气吹至近干后用50%甲醇水溶液复溶,在Waters Acquity UPLC HSS T₃分析柱上,以0.1%(v/v)甲酸水溶液(含10 mmol/L乙酸铵)-甲醇为流动相,电喷雾离子源(ESI)正离子模式下进行UPLC-MS/MS多反应监测(MRM)测定。在最优的仪器参数及前处理条件下进行方法验证,60种类固醇激素在1.0~100 ng/mL范围内具有良好的线性关系,相关系数(r)均大于0.99;方法的检出限(LOD)和定量限(LOQ)分别为0.2~0.8 μg/kg和0.6~2.4 μg/kg。以乳清蛋白粉(固体)、果胶蛋白肽(半固体)、运动营养液(液体)为空白基质,进行3个水平的加标回收试验(n=6), 60种类固醇激素的平均回收率为73.7%~112.7%,相对标准偏差(RSD)为3.2%~10.1%。将新开发的方法应用于13批次实际样品的测定,在其中1份样品中检出禁用药物(勃地酮),含量为14.6 μg/kg,说明运动营养食品中确有非法添加类固醇激素的现象,后续应加强对运动营养食品中该类固醇类激素的监控。该方法简单高效,灵敏度高,重复性好,适用于运动营养食品中类固醇激素的快速筛查和定量分析,为运动营养食品中类固醇激素的日常监督提供技术支撑。

关键词: 超高效液相色谱-串联质谱, QuEChERS, 类固醇激素, 运动营养食品

Abstract:

Recent societal developments and improving living standards have witnessed a growing enthusiasm for sport and fitness along with a boom in sports nutrition foods. However, rapid industrial development has led to product quality and safety issues becoming increasingly important. Steroid hormones exhibit physiological effects that include promoting protein synthesis, increasing muscle mass, and reducing body fat. Driven by vested interests, some unscrupulous traders illegally add steroid hormones to sports nutrition foods to improve sports performance and relieve muscle pain, which poses a potential threat to human health. Therefore, establishing a method for determining steroid hormones in sports nutrition foods is of great practical importance.

In this study, an analytical method for the simultaneous determination of 60 steroid hormones in sports nutrition foods was developed using QuEChERS combined with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The MS parameters and chromatographic conditions were optimized for the 60 steroid hormones, and the extraction solvents and purification methods were systematically optimized to facilitate rapid screening and accurate quantitative analysis of these hormones in sports nutrition foods. Samples were extracted with 1.0% formic acid in methanol, partitioned with sodium chloride, and purified using 150 mg of PSA and 150 mg of C₁₈ powder. The clean-up solution was evaporated to near dryness under a stream of nitrogen and the residue was reconstituted with 50% methanol aqueous solution. The 60 target compounds were separated on a Waters Acquity UPLC HSS T₃ column (100 mm×2.1 mm, 1.8 μm) with 0.1% (v/v) formic acid aqueous solution (containing 10 mmol/L ammonium acetate) and methanol as the mobile phases. The analytes were determined by multiple reaction monitoring (MRM) in positive electrospray ionization mode (ESI⁺) and quantified using the external standard method. The method was validated under the optimized conditions, with the 60 steroid hormones found to exhibit good linearities in the 1.0-100 ng/mL range with correlation coefficients (r) greater than 0.99. The limits of detection (LODs) and limits of quantification (LOQs) were 0.2-0.8 μg/kg and 0.6-2.4 μg/kg, respectively. At three spiked levels on whey protein powder (solid), pectin protein peptide (semi-solid) and energy drink (liquid) as blank matrix, the mean recoveries of the 60 steroid hormones were 73.7%-112.7% with relative standard deviations (RSDs) of 3.2%-10.1% (n=6). Thirteen batches of commercially available sports nutrition products were screened using the newly developed method, with five positive samples detected. Progesterone (an endogenous hormone) was detected at levels of 12.6-25.4 μg/kg in four samples of whey protein powder, and boldenone (which is a prohibited drug for athletes) was detected at 14.6 μg/kg in one sports nutrition liquid, confirming that illegal steroid hormones are indeed added to sports nutrition foods; consequently, relevant national departments need to strengthen their monitoring of such substances in such foods. The developed method is simple, efficient, sensitive, reproducible, and suitable for the rapid screening and quantitative analysis of steroid hormones in sports nutrition foods, thereby providing technical support for the daily supervision of steroid hormones in these foods.

Key words: ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), QuEChERS, steroid hormones, sports nutrition food

中图分类号:

O658

蔡小明, 吴少明, 余清, 黄何何, 郑秋萍, 何孟杭, 戴明, 欧阳立群. 超高效液相色谱-串联质谱法测定运动营养食品中60种类固醇激素[J]. 色谱, 2024, 42(12): 1173-1188.

CAI Xiaoming, WU Shaoming, YU Qing, HUANG Hehe, ZHENG Qiuping, HE Menghang, DAI Ming, OUYANG Liqun. Determination of 60 steroid hormones in sports nutrition foods by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2024, 42(12): 1173-1188.

图/表 11

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No.	Linear equation	r	LODs/(μg/kg)			LOQs/(μg/kg)
No.	Linear equation	r	Whey protein powder	Pectin protein peptide	Energy drink	Whey protein powder	Pectin protein peptide	Energy drink
1	y=2.69×10⁴x+3.40×10⁴	0.997	0.6	0.6	0.3	1.8	1.9	0.9
2	y=1.10×10⁵x+8.86×10⁴	0.993	0.8	0.6	0.4	2.4	1.8	1.2
3	y=2.81×10⁴x+5.80×10⁴	0.990	0.5	0.5	0.5	1.5	1.6	1.4
4	y=1.07×10⁴x+9.31×10⁴	0.997	0.6	0.6	0.5	1.8	1.9	1.5
5	y=8.98×10³x+1.39×10⁴	0.988	0.4	0.4	0.4	1.2	1.3	1.1
6	y=1.87×10⁴x+3.70×10⁵	0.993	0.6	0.6	0.6	1.8	1.9	1.7
7	y=1.17×10⁴x+1.08×10⁴	0.998	0.3	0.3	0.3	0.9	1.0	0.8
8	y=1.09×10⁴x+9.74×10⁴	0.995	0.4	0.4	0.4	1.2	1.3	1.1
9	y=1.66×10⁴x+6.96×10⁴	0.997	0.8	0.6	0.5	2.4	1.8	1.5
10	y=7.17×10⁴x+6.17×10⁴	0.994	0.2	0.2	0.2	0.6	0.6	0.6
11	y=7.61×10⁴x+4.71×10⁴	0.991	0.4	0.4	0.4	1.2	1.3	1.1
12	y=5.01×10⁴x+2.24×10⁴	0.991	0.4	0.4	0.4	1.2	1.3	1.1
13	y=1.77×10⁴x+2.27×10⁴	0.997	0.7	0.5	0.4	2.1	1.5	1.3
14	y=7.82×10⁴x+5.42×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
15	y=2.86×10⁴x+3.18×10⁴	0.996	0.3	0.3	0.3	0.9	1.0	0.8
16	y=7.67×10⁵x+3.41×10⁵	0.999	0.4	0.4	0.4	1.2	1.3	1.1
17	y=6.26×10⁵x+8.36×10⁴	0.995	0.5	0.5	0.5	1.5	1.6	1.4
18	y=3.81×10⁴x+6.41×10⁴	0.996	0.4	0.4	0.4	1.2	1.3	1.1
19	y=9.29×10⁴x+1.09×10⁵	0.993	0.5	0.5	0.5	1.5	1.6	1.4
20	y=1.72×10⁵x+3.52×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
21	y=2.34×10⁴x+1.33×10⁴	0.998	0.7	0.6	0.5	2.1	1.8	1.5
22	y=1.34×10⁵x+1.38×10⁴	0.995	0.6	0.6	0.6	1.8	1.9	1.7
23	y=6.42×10⁴x+6.68×10⁴	0.998	0.4	0.4	0.4	1.2	1.3	1.1
24	y=1.98×10⁴x+1.74×10⁴	0.996	0.6	0.5	0.4	1.8	1.5	1.3
25	y=8.79×10⁴x+1.52×10⁴	0.997	0.6	0.6	0.5	1.8	1.9	1.5
26	y=8.46×10⁴x+4.06×10⁴	0.999	0.6	0.4	0.3	1.8	1.2	1.0
27	y=3.22×10⁴x+1.09×10⁴	0.998	0.6	0.6	0.4	1.8	1.9	1.2
28	y=4.51×10⁴x+4.85×10⁴	0.993	0.5	0.5	0.5	1.5	1.6	1.4
29	y=1.01×10⁴x+3.20×10⁴	0.999	0.4	0.4	0.4	1.2	1.3	1.1
30	y=4.36×10⁴x+1.91×10⁴	0.993	0.6	0.6	0.6	1.8	1.9	1.7
31	y=1.99×10⁴x+2.80×10⁴	0.998	0.7	0.5	0.4	2.1	1.5	1.2
32	y=1.65×10⁴x+2.71×10⁴	0.996	0.5	0.5	0.5	1.5	1.6	1.4
33	y=7.89×10⁴x+1.32×10⁵	0.996	0.4	0.4	0.4	1.2	1.3	1.1
34	y=7.87×10⁴x+1.40×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
35	y=2.00×10⁴x+7.61×10⁴	0.999	0.6	0.6	0.6	1.8	1.9	1.7
36	y=1.07×10⁴x+7.99×10⁴	0.994	0.7	0.5	0.4	2.1	1.5	1.3
37	y=2.36×10⁴x+1.19×10⁴	0.999	0.3	0.3	0.3	0.9	1.0	0.8
38	y=2.38×10⁴x+1.90×10⁴	0.997	0.7	0.6	0.5	2.1	1.8	1.5
39	y=1.01×10⁵x+6.94×10⁴	0.995	0.5	0.5	0.5	1.5	1.6	1.4
40	y=7.42×10⁴x+6.78×10⁴	0.998	0.6	0.6	0.4	1.8	1.9	1.2
41	y=2.06×10⁵x+7.55×10⁴	0.999	0.6	0.6	0.6	1.8	1.9	1.7
42	y=1.01×10⁵x+1.89×10⁴	0.997	0.7	0.5	0.5	2.1	1.5	1.5
43	y=1.51×10⁴x+1.39×10⁵	0.993	0.4	0.4	0.4	1.2	1.3	1.1
44	y=1.59×10⁵x+3.72×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
45	y=5.17×10⁴x+7.31×10⁴	0.992	0.6	0.6	0.6	1.8	1.9	1.7
46	y=4.25×10⁴x+1.51×10⁴	0.998	0.6	0.6	0.6	1.8	1.9	1.7
47	y=4.80×10⁵x+2.48×10⁴	0.999	0.4	0.4	0.4	1.2	1.3	1.1
48	y=8.54×10⁴x+4.71×10⁴	0.999	0.6	0.4	0.3	1.8	1.2	1.0
49	y=5.93×10⁴x-1.17×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
50	y=5.96×10⁵x-2.68×10⁴	0.999	0.7	0.6	0.5	2.1	1.8	1.5
51	y=7.87×10⁴x-4.95×10⁴	0.992	0.4	0.4	0.4	1.2	1.3	1.1
52	y=2.78×10⁴x-1.59×10⁴	0.996	0.6	0.6	0.6	1.8	1.9	1.7
53	y=2.74×10⁴x+2.26×10⁴	0.998	0.5	0.5	0.5	1.5	1.6	1.4
54	y=3.74×10⁴x+6.34×10⁴	0.996	0.6	0.6	0.4	1.8	1.9	1.2
55	y=7.24×10⁴x+1.00×10⁵	0.991	0.6	0.6	0.6	1.8	1.9	1.7
56	y=3.40×10⁴x+1.32×10⁵	0.996	0.8	0.6	0.3	2.4	1.8	0.9
57	y=3.38×10⁵x-3.30×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
58	y=1.56×10⁴x+1.93×10⁴	0.998	0.5	0.5	0.5	1.5	1.6	1.4
59	y=3.27×10⁵x-2.51×10⁴	0.999	0.7	0.5	0.4	2.1	1.5	1.3
60	y=2.24×10⁴x+6.98×10⁴	0.999	0.7	0.6	0.5	2.1	1.8	1.5

No.	Linear equation	r	LODs/(μg/kg)			LOQs/(μg/kg)
No.	Linear equation	r	Whey protein powder	Pectin protein peptide	Energy drink	Whey protein powder	Pectin protein peptide	Energy drink
1	y=2.69×10⁴x+3.40×10⁴	0.997	0.6	0.6	0.3	1.8	1.9	0.9
2	y=1.10×10⁵x+8.86×10⁴	0.993	0.8	0.6	0.4	2.4	1.8	1.2
3	y=2.81×10⁴x+5.80×10⁴	0.990	0.5	0.5	0.5	1.5	1.6	1.4
4	y=1.07×10⁴x+9.31×10⁴	0.997	0.6	0.6	0.5	1.8	1.9	1.5
5	y=8.98×10³x+1.39×10⁴	0.988	0.4	0.4	0.4	1.2	1.3	1.1
6	y=1.87×10⁴x+3.70×10⁵	0.993	0.6	0.6	0.6	1.8	1.9	1.7
7	y=1.17×10⁴x+1.08×10⁴	0.998	0.3	0.3	0.3	0.9	1.0	0.8
8	y=1.09×10⁴x+9.74×10⁴	0.995	0.4	0.4	0.4	1.2	1.3	1.1
9	y=1.66×10⁴x+6.96×10⁴	0.997	0.8	0.6	0.5	2.4	1.8	1.5
10	y=7.17×10⁴x+6.17×10⁴	0.994	0.2	0.2	0.2	0.6	0.6	0.6
11	y=7.61×10⁴x+4.71×10⁴	0.991	0.4	0.4	0.4	1.2	1.3	1.1
12	y=5.01×10⁴x+2.24×10⁴	0.991	0.4	0.4	0.4	1.2	1.3	1.1
13	y=1.77×10⁴x+2.27×10⁴	0.997	0.7	0.5	0.4	2.1	1.5	1.3
14	y=7.82×10⁴x+5.42×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
15	y=2.86×10⁴x+3.18×10⁴	0.996	0.3	0.3	0.3	0.9	1.0	0.8
16	y=7.67×10⁵x+3.41×10⁵	0.999	0.4	0.4	0.4	1.2	1.3	1.1
17	y=6.26×10⁵x+8.36×10⁴	0.995	0.5	0.5	0.5	1.5	1.6	1.4
18	y=3.81×10⁴x+6.41×10⁴	0.996	0.4	0.4	0.4	1.2	1.3	1.1
19	y=9.29×10⁴x+1.09×10⁵	0.993	0.5	0.5	0.5	1.5	1.6	1.4
20	y=1.72×10⁵x+3.52×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
21	y=2.34×10⁴x+1.33×10⁴	0.998	0.7	0.6	0.5	2.1	1.8	1.5
22	y=1.34×10⁵x+1.38×10⁴	0.995	0.6	0.6	0.6	1.8	1.9	1.7
23	y=6.42×10⁴x+6.68×10⁴	0.998	0.4	0.4	0.4	1.2	1.3	1.1
24	y=1.98×10⁴x+1.74×10⁴	0.996	0.6	0.5	0.4	1.8	1.5	1.3
25	y=8.79×10⁴x+1.52×10⁴	0.997	0.6	0.6	0.5	1.8	1.9	1.5
26	y=8.46×10⁴x+4.06×10⁴	0.999	0.6	0.4	0.3	1.8	1.2	1.0
27	y=3.22×10⁴x+1.09×10⁴	0.998	0.6	0.6	0.4	1.8	1.9	1.2
28	y=4.51×10⁴x+4.85×10⁴	0.993	0.5	0.5	0.5	1.5	1.6	1.4
29	y=1.01×10⁴x+3.20×10⁴	0.999	0.4	0.4	0.4	1.2	1.3	1.1
30	y=4.36×10⁴x+1.91×10⁴	0.993	0.6	0.6	0.6	1.8	1.9	1.7
31	y=1.99×10⁴x+2.80×10⁴	0.998	0.7	0.5	0.4	2.1	1.5	1.2
32	y=1.65×10⁴x+2.71×10⁴	0.996	0.5	0.5	0.5	1.5	1.6	1.4
33	y=7.89×10⁴x+1.32×10⁵	0.996	0.4	0.4	0.4	1.2	1.3	1.1
34	y=7.87×10⁴x+1.40×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
35	y=2.00×10⁴x+7.61×10⁴	0.999	0.6	0.6	0.6	1.8	1.9	1.7
36	y=1.07×10⁴x+7.99×10⁴	0.994	0.7	0.5	0.4	2.1	1.5	1.3
37	y=2.36×10⁴x+1.19×10⁴	0.999	0.3	0.3	0.3	0.9	1.0	0.8
38	y=2.38×10⁴x+1.90×10⁴	0.997	0.7	0.6	0.5	2.1	1.8	1.5
39	y=1.01×10⁵x+6.94×10⁴	0.995	0.5	0.5	0.5	1.5	1.6	1.4
40	y=7.42×10⁴x+6.78×10⁴	0.998	0.6	0.6	0.4	1.8	1.9	1.2
41	y=2.06×10⁵x+7.55×10⁴	0.999	0.6	0.6	0.6	1.8	1.9	1.7
42	y=1.01×10⁵x+1.89×10⁴	0.997	0.7	0.5	0.5	2.1	1.5	1.5
43	y=1.51×10⁴x+1.39×10⁵	0.993	0.4	0.4	0.4	1.2	1.3	1.1
44	y=1.59×10⁵x+3.72×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
45	y=5.17×10⁴x+7.31×10⁴	0.992	0.6	0.6	0.6	1.8	1.9	1.7
46	y=4.25×10⁴x+1.51×10⁴	0.998	0.6	0.6	0.6	1.8	1.9	1.7
47	y=4.80×10⁵x+2.48×10⁴	0.999	0.4	0.4	0.4	1.2	1.3	1.1
48	y=8.54×10⁴x+4.71×10⁴	0.999	0.6	0.4	0.3	1.8	1.2	1.0
49	y=5.93×10⁴x-1.17×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
50	y=5.96×10⁵x-2.68×10⁴	0.999	0.7	0.6	0.5	2.1	1.8	1.5
51	y=7.87×10⁴x-4.95×10⁴	0.992	0.4	0.4	0.4	1.2	1.3	1.1
52	y=2.78×10⁴x-1.59×10⁴	0.996	0.6	0.6	0.6	1.8	1.9	1.7
53	y=2.74×10⁴x+2.26×10⁴	0.998	0.5	0.5	0.5	1.5	1.6	1.4
54	y=3.74×10⁴x+6.34×10⁴	0.996	0.6	0.6	0.4	1.8	1.9	1.2
55	y=7.24×10⁴x+1.00×10⁵	0.991	0.6	0.6	0.6	1.8	1.9	1.7
56	y=3.40×10⁴x+1.32×10⁵	0.996	0.8	0.6	0.3	2.4	1.8	0.9
57	y=3.38×10⁵x-3.30×10⁴	0.999	0.5	0.5	0.5	1.5	1.6	1.4
58	y=1.56×10⁴x+1.93×10⁴	0.998	0.5	0.5	0.5	1.5	1.6	1.4
59	y=3.27×10⁵x-2.51×10⁴	0.999	0.7	0.5	0.4	2.1	1.5	1.3
60	y=2.24×10⁴x+6.98×10⁴	0.999	0.7	0.6	0.5	2.1	1.8	1.5

No.	Added/(μg/kg)			Whey protein powder				Pectin protein peptide			Energy drink
No.	Added/(μg/kg)			Recovery/%		RSD/%		Recovery/%		RSD/%	Recovery/%	RSD/%
1		2.50	76.5		6.0		76.8		4.6		78.9		5.8
		5.00	81.3		4.1		86.0		6.6		87.9		4.5
		20.0	84.8		4.8		81.2		6.5		88.7		6.4
2		2.50	91.6		4.5		90.3		5.2		85.1		4.4
		5.00	89.5		4.5		85.6		7.8		93.1		5.1
		20.0	90.4		4.8		90.6		4.8		90.9		4.8
3		2.50	81.5		6.0		82.5		5.2		86.9		4.8
		5.00	85.1		6.2		85.8		6.6		93.5		5.1
		20.0	89.3		4.6		87.9		6.9		86.4		6.4
4		2.50	103.6		7.1		108.2		6.0		102.3		6.8
		5.00	107.8		6.8		97.5		7.7		93.5		4.9
		20.0	101.3		5.6		110.3		7.4		107.8		7.6
5		2.50	84.7		4.2		83.5		6.1		86.0		7.3
		5.00	88.4		5.4		87.1		4.6		86.0		6.0
		20.0	91.4		6.8		90.1		5.8		89.8		4.5
6		2.50	84.1		6.6		84.8		7.4		93.0		5.7
		5.00	87.9		5.5		86.6		7.1		85.4		7.3
		20.0	83.1		6.8		81.9		5.9		89.4		7.0
7		2.50	86.2		7.1		87.5		7.4		84.4		5.8
		5.00	91.1		5.0		89.7		7.7		87.7		7.3
		20.0	87.5		3.2		86.1		5.4		92.5		7.6
8		2.50	83.8		4.2		82.8		3.5		88.9		5.4
		5.00	90.1		5.6		88.8		4.6		85.1		3.5
		20.0	92.5		5.7		85.0		6.1		91.6		4.5
9		2.50	87.6		4.8		86.2		6.2		93.9		6.0
		5.00	92.3		3.2		88.5		5.2		89.0		6.1
		20.0	88.5		7.8		87.2		3.5		93.8		5.1
10		2.50	109.3		6.2		91.4		8.5		103.3		3.5
		5.00	103.5		6.9		107.4		6.9		94.5		8.4
		20.0	106.3		5.4		102.8		7.5		105.7		6.8
11		2.50	86.0		4.8		84.7		5.8		94.4		7.4
		5.00	84.1		6.0		92.4		5.2		87.4		5.7
		20.0	89.5		7.5		88.2		6.6		85.4		5.1
12		2.50	84.1		6.9		82.8		8.1		91.0		6.4
		5.00	86.2		7.1		93.1		7.5		85.4		8.0
		20.0	88.5		6.8		87.2		7.7		87.7		7.4
13		2.50	93.3		5.7		83.1		7.4		89.9		7.6
		5.00	90.3		6.4		89.0		6.2		94.8		7.3
		20.0	86.1		5.1		84.9		7.0		91.7		6.1
14		2.50	92.4		7.1		91.1		5.6		87.6		6.9
		5.00	88.2		4.5		91.3		7.7		93.9		5.5
		20.0	87.4		5.4		86.0		4.8		89.6		7.6
15		2.50	101.2		5.9		99.5		5.8		103.5		4.8
		5.00	93.5		7.9		105.6		6.4		95.3		5.7
		20.0	106.8		6.1		92.1		8.6		104.8		6.3
16		2.50	90.4		6.8		93.5		6.7		88.7		8.5
		5.00	89.5		5.0		88.2		7.4		91.9		6.6
		20.0	93.0		6.2		91.5		5.4		91.0		7.3
17		2.50	84.0		4.5		82.6		6.9		94.4		5.4
		5.00	85.7		7.6		90.4		4.8		85.3		6.8
		20.0	86.3		8.3		85.0		8.2		87.0		4.8
18		2.50	93.4		6.8		89.5		9.0		87.7		8.1
		5.00	88.8		7.5		87.5		7.4		94.9		8.8
		20.0	89.3		3.2		87.9		8.1		90.2		7.3
19		2.50	73.7		7.3		84.3		5.0		79.2		6.4
		5.00	90.2		4.9		86.4		7.1		88.4		4.9
		20.0	86.4		5.8		86.6		4.9		89.1		7.1
20		2.50	104.6		5.4		108.7		5.7		95.3		4.8
		5.00	95.5		5.4		100.3		5.2		92.4		5.6
		20.0	104.5		5.8		105.3		5.2		91.3		5.2
21		2.50	89.1		7.3		90.8		5.7		87.3		5.2
		5.00	92.3		7.5		84.2		7.1		90.4		5.6
		20.0	88.7		5.5		88.4		7.5		86.8		7.1
22		2.50	112.7		8.5		105.2		5.4		91.1		7.4
		5.00	106.4		8.2		100.4		8.4		89.4		5.4
		20.0	104.3		6.8		97.8		8.0		82.7		8.3
23		2.50	88.2		5.0		83.9		6.7		86.4		8.0
		5.00	88.3		6.5		87.5		5.0		86.5		6.6
		20.0	105.7		8.2		90.5		6.3		90.3		4.9
24		2.50	95.4		7.9		85.2		8.0		93.4		6.3
		5.00	87.6		6.7		87.0		7.7		85.8		8.0
		20.0	83.2		8.2		82.3		6.4		89.8		7.6
25		2.50	86.6		8.5		87.9		8.0		84.8		6.4
		5.00	103.6		6.0		90.2		8.4		88.1		8.0
		20.0	94.9		3.9		86.5		5.9		92.9		8.3
26		2.50	91.2		5.0		83.2		3.8		89.3		5.9
		5.00	87.3		6.8		89.2		5.0		104.5		3.9
		20.0	84.4		6.9		85.4		6.7		92.1		4.9
27		2.50	96.3		5.8		86.6		6.8		94.3		6.6
		5.00	88.2		3.9		88.9		5.7		89.4		6.7
		20.0	96.2		9.4		87.6		3.8		94.2		5.6
28		2.50	92.2		7.5		81.1		9.3		90.3		3.9
		5.00	94.2		8.3		88.6		7.5		105.4		6.2
		20.0	89.6		6.5		91.0		8.1		91.4		7.4
29		2.50	86.0		5.8		85.1		6.3		94.8		5.1
		5.00	86.8		7.3		92.8		5.7		87.8		6.3
		20.0	83.3		9.0		88.6		7.1		103.2		5.6
30		2.50	91.1		8.3		83.2		8.8		91.4		7.1
		5.00	88.9		8.5		93.6		8.1		85.8		8.8
		20.0	85.1		8.2		87.6		8.4		88.1		8.1
31		2.50	88.1		6.9		83.5		8.0		90.3		8.3
		5.00	84.6		7.8		89.4		6.8		95.3		8.0
		20.0	88.7		6.2		85.3		7.6		92.2		6.7
32		2.50	87.0		8.5		91.5		6.1		88.0		7.5
		5.00	80.5		5.4		91.8		8.4		94.3		6.0
		20.0	84.1		6.5		86.5		5.2		90.1		5.3
33		2.50	84.2		7.2		85.4		6.3		89.2		5.2
		5.00	87.9		9.5		86.9		7.0		83.6		6.3
		20.0	90.9		7.4		86.4		9.4		85.8		7.0
34		2.50	103.5		8.2		104.6		7.2		108.3		9.3
		5.00	94.5		6.0		93.9		8.0		93.4		7.2
		20.0	107.1		7.5		108.3		5.9		98.2		8.0
35		2.50	85.7		5.4		83.0		7.5		94.8		5.9
		5.00	90.5		9.2		90.8		5.2		85.7		7.4
		20.0	87.0		10.1		85.4		8.9		87.4		5.2
36		2.50	83.3		8.2		89.9		9.8		88.1		8.9
		5.00	89.6		9.0		87.9		8.0		95.4		4.7
		20.0	91.9		3.9		88.4		8.8		90.6		8.0
37		2.50	87.0		6.9		80.1		4.7		75.3		6.1
		5.00	91.7		4.7		82.0		6.8		83.9		4.7
		20.0	88.0		5.5		82.3		4.6		84.7		6.7
38		2.50	89.8		5.1		86.2		5.4		81.2		4.5
		5.00	89.0		5.1		81.7		4.9		88.9		5.3
		20.0	92.4		5.5		80.5		4.9		86.7		5.0
39		2.50	106.5		6.9		96.3		5.4		92.9		5.0
		5.00	98.4		7.2		100.0		6.8		95.9		5.3
		20.0	108.5		5.3		94.9		7.1		92.5		6.7
40		2.50	83.6		8.1		82.3		5.2		86.5		7.0
		5.00	85.7		7.8		81.0		7.9		84.9		5.1
		20.0	88.0		6.4		79.6		7.6		78.5		7.9
41		2.50	92.8		4.8		79.7		6.3		82.0		7.6
		5.00	89.8		6.2		83.1		4.7		82.1		6.3
		20.0	85.6		7.8		86.0		6.0		85.7		4.7
42		2.50	91.8		7.5		81.0		7.6		88.7		6.0
		5.00	87.7		6.3		82.7		7.3		81.5		7.6
		20.0	86.9		7.8		78.2		6.1		85.3		7.3
43		2.50	81.4		8.1		83.5		7.6		80.6		6.1
		5.00	83.6		5.7		85.6		7.9		83.7		7.6
		20.0	86.8		3.7		82.2		5.6		88.3		7.9
44		2.50	89.9		4.8		79.1		3.7		84.8		5.6
		5.00	89.0		6.4		84.7		4.7		81.2		3.7
		20.0	92.4		6.6		81.1		6.3		87.5		4.7
45		2.50	83.5		5.5		82.3		6.4		89.6		6.3
		5.00	85.2		3.7		84.5		5.4		84.9		6.4
		20.0	85.8		9.0		83.2		3.7		89.5		5.3
46		2.50	92.9		7.2		77.1		8.8		85.8		3.7
		5.00	88.3		7.9		84.2		7.1		87.6		8.8
		20.0	88.7		6.2		86.5		7.7		86.8		7.0
47		2.50	79.3		5.5		80.9		6.0		90.1		7.7
		5.00	84.8		6.9		88.2		5.4		83.4		6.0
		20.0	81.2		8.6		84.2		6.8		81.5		5.3
48		2.50	98.3		7.9		79.1		8.4		86.8		6.7
		5.00	89.8		8.1		88.9		7.7		81.5		8.3
		20.0	87.6		7.8		83.2		7.9		83.7		7.7
49		2.50	83.8		6.6		79.3		7.6		85.8		7.9
		5.00	86.8		7.4		84.9		6.4		90.5		7.6
		20.0	83.3		5.8		81.0		7.2		87.5		6.4
50		2.50	107.8		8.1		86.9		5.8		83.6		7.1
		5.00	85.8		5.1		87.2		7.9		89.6		5.7
		20.0	76.6		6.2		82.1		4.9		85.6		7.9
51		2.50	82.9		6.8		81.1		6.0		84.7		5.0
		5.00	83.0		9.1		82.6		6.7		79.4		6.0
		20.0	99.4		7.0		82.0		8.9		81.5		6.6
52		2.50	89.6		7.8		89.3		6.9		84.7		8.9
		5.00	82.3		5.7		84.2		7.6		87.7		6.8
		20.0	78.2		7.2		87.4		5.6		86.8		7.6
53		2.50	81.4		5.1		78.9		7.1		90.1		5.6
		5.00	97.4		8.7		86.3		4.9		81.4		7.0
		20.0	89.2		9.5		81.1		8.5		83.0		5.0
54		2.50	85.7		7.8		85.4		9.3		83.7		8.4
		5.00	82.1		8.6		83.5		7.6		90.6		9.2
		20.0	79.3		3.7		83.9		8.4		86.1		7.6
55		2.50	90.5		6.6		76.0		4.5		89.6		5.8
		5.00	82.9		4.4		77.9		6.4		93.5		4.4
		20.0	90.5		5.2		78.2		4.4		104.8		6.4
56		2.50	86.7		4.9		81.9		5.1		93.6		4.3
		5.00	88.5		4.9		77.6		4.7		102.5		5.0
		20.0	84.3		5.2		76.5		4.7		82.4		4.7
57		2.50	80.8		6.6		82.0		5.1		94.5		4.7
		5.00	81.6		6.8		76.0		6.4		91.3		5.0
		20.0	78.3		5.0		79.7		6.7		88.6		6.4
58		2.50	85.6		7.7		78.2		4.9		82.2		6.7
		5.00	83.6		7.4		77.0		7.6		80.7		4.8
		20.0	80.0		6.1		75.6		7.2		86.5		7.5
59		2.50	82.8		4.5		75.7		6.0		91.4		7.2
		5.00	79.5		5.9		79.0		4.5		85.9		6.0
		20.0	83.4		7.4		81.7		5.7		81.5		4.4
60		2.50	103.4		7.1		87.3		7.2		95.3		5.7
		5.00	89.7		6.0		96.4		6.9		89.4		7.2
		20.0	93.5		7.4		93.1		5.8		97.5		6.9

No.	Added/(μg/kg)			Whey protein powder				Pectin protein peptide			Energy drink
No.	Added/(μg/kg)			Recovery/%		RSD/%		Recovery/%		RSD/%	Recovery/%	RSD/%
1		2.50	76.5		6.0		76.8		4.6		78.9		5.8
		5.00	81.3		4.1		86.0		6.6		87.9		4.5
		20.0	84.8		4.8		81.2		6.5		88.7		6.4
2		2.50	91.6		4.5		90.3		5.2		85.1		4.4
		5.00	89.5		4.5		85.6		7.8		93.1		5.1
		20.0	90.4		4.8		90.6		4.8		90.9		4.8
3		2.50	81.5		6.0		82.5		5.2		86.9		4.8
		5.00	85.1		6.2		85.8		6.6		93.5		5.1
		20.0	89.3		4.6		87.9		6.9		86.4		6.4
4		2.50	103.6		7.1		108.2		6.0		102.3		6.8
		5.00	107.8		6.8		97.5		7.7		93.5		4.9
		20.0	101.3		5.6		110.3		7.4		107.8		7.6
5		2.50	84.7		4.2		83.5		6.1		86.0		7.3
		5.00	88.4		5.4		87.1		4.6		86.0		6.0
		20.0	91.4		6.8		90.1		5.8		89.8		4.5
6		2.50	84.1		6.6		84.8		7.4		93.0		5.7
		5.00	87.9		5.5		86.6		7.1		85.4		7.3
		20.0	83.1		6.8		81.9		5.9		89.4		7.0
7		2.50	86.2		7.1		87.5		7.4		84.4		5.8
		5.00	91.1		5.0		89.7		7.7		87.7		7.3
		20.0	87.5		3.2		86.1		5.4		92.5		7.6
8		2.50	83.8		4.2		82.8		3.5		88.9		5.4
		5.00	90.1		5.6		88.8		4.6		85.1		3.5
		20.0	92.5		5.7		85.0		6.1		91.6		4.5
9		2.50	87.6		4.8		86.2		6.2		93.9		6.0
		5.00	92.3		3.2		88.5		5.2		89.0		6.1
		20.0	88.5		7.8		87.2		3.5		93.8		5.1
10		2.50	109.3		6.2		91.4		8.5		103.3		3.5
		5.00	103.5		6.9		107.4		6.9		94.5		8.4
		20.0	106.3		5.4		102.8		7.5		105.7		6.8
11		2.50	86.0		4.8		84.7		5.8		94.4		7.4
		5.00	84.1		6.0		92.4		5.2		87.4		5.7
		20.0	89.5		7.5		88.2		6.6		85.4		5.1
12		2.50	84.1		6.9		82.8		8.1		91.0		6.4
		5.00	86.2		7.1		93.1		7.5		85.4		8.0
		20.0	88.5		6.8		87.2		7.7		87.7		7.4
13		2.50	93.3		5.7		83.1		7.4		89.9		7.6
		5.00	90.3		6.4		89.0		6.2		94.8		7.3
		20.0	86.1		5.1		84.9		7.0		91.7		6.1
14		2.50	92.4		7.1		91.1		5.6		87.6		6.9
		5.00	88.2		4.5		91.3		7.7		93.9		5.5
		20.0	87.4		5.4		86.0		4.8		89.6		7.6
15		2.50	101.2		5.9		99.5		5.8		103.5		4.8
		5.00	93.5		7.9		105.6		6.4		95.3		5.7
		20.0	106.8		6.1		92.1		8.6		104.8		6.3
16		2.50	90.4		6.8		93.5		6.7		88.7		8.5
		5.00	89.5		5.0		88.2		7.4		91.9		6.6
		20.0	93.0		6.2		91.5		5.4		91.0		7.3
17		2.50	84.0		4.5		82.6		6.9		94.4		5.4
		5.00	85.7		7.6		90.4		4.8		85.3		6.8
		20.0	86.3		8.3		85.0		8.2		87.0		4.8
18		2.50	93.4		6.8		89.5		9.0		87.7		8.1
		5.00	88.8		7.5		87.5		7.4		94.9		8.8
		20.0	89.3		3.2		87.9		8.1		90.2		7.3
19		2.50	73.7		7.3		84.3		5.0		79.2		6.4
		5.00	90.2		4.9		86.4		7.1		88.4		4.9
		20.0	86.4		5.8		86.6		4.9		89.1		7.1
20		2.50	104.6		5.4		108.7		5.7		95.3		4.8
		5.00	95.5		5.4		100.3		5.2		92.4		5.6
		20.0	104.5		5.8		105.3		5.2		91.3		5.2
21		2.50	89.1		7.3		90.8		5.7		87.3		5.2
		5.00	92.3		7.5		84.2		7.1		90.4		5.6
		20.0	88.7		5.5		88.4		7.5		86.8		7.1
22		2.50	112.7		8.5		105.2		5.4		91.1		7.4
		5.00	106.4		8.2		100.4		8.4		89.4		5.4
		20.0	104.3		6.8		97.8		8.0		82.7		8.3
23		2.50	88.2		5.0		83.9		6.7		86.4		8.0
		5.00	88.3		6.5		87.5		5.0		86.5		6.6
		20.0	105.7		8.2		90.5		6.3		90.3		4.9
24		2.50	95.4		7.9		85.2		8.0		93.4		6.3
		5.00	87.6		6.7		87.0		7.7		85.8		8.0
		20.0	83.2		8.2		82.3		6.4		89.8		7.6
25		2.50	86.6		8.5		87.9		8.0		84.8		6.4
		5.00	103.6		6.0		90.2		8.4		88.1		8.0
		20.0	94.9		3.9		86.5		5.9		92.9		8.3
26		2.50	91.2		5.0		83.2		3.8		89.3		5.9
		5.00	87.3		6.8		89.2		5.0		104.5		3.9
		20.0	84.4		6.9		85.4		6.7		92.1		4.9
27		2.50	96.3		5.8		86.6		6.8		94.3		6.6
		5.00	88.2		3.9		88.9		5.7		89.4		6.7
		20.0	96.2		9.4		87.6		3.8		94.2		5.6
28		2.50	92.2		7.5		81.1		9.3		90.3		3.9
		5.00	94.2		8.3		88.6		7.5		105.4		6.2
		20.0	89.6		6.5		91.0		8.1		91.4		7.4
29		2.50	86.0		5.8		85.1		6.3		94.8		5.1
		5.00	86.8		7.3		92.8		5.7		87.8		6.3
		20.0	83.3		9.0		88.6		7.1		103.2		5.6
30		2.50	91.1		8.3		83.2		8.8		91.4		7.1
		5.00	88.9		8.5		93.6		8.1		85.8		8.8
		20.0	85.1		8.2		87.6		8.4		88.1		8.1
31		2.50	88.1		6.9		83.5		8.0		90.3		8.3
		5.00	84.6		7.8		89.4		6.8		95.3		8.0
		20.0	88.7		6.2		85.3		7.6		92.2		6.7
32		2.50	87.0		8.5		91.5		6.1		88.0		7.5
		5.00	80.5		5.4		91.8		8.4		94.3		6.0
		20.0	84.1		6.5		86.5		5.2		90.1		5.3
33		2.50	84.2		7.2		85.4		6.3		89.2		5.2
		5.00	87.9		9.5		86.9		7.0		83.6		6.3
		20.0	90.9		7.4		86.4		9.4		85.8		7.0
34		2.50	103.5		8.2		104.6		7.2		108.3		9.3
		5.00	94.5		6.0		93.9		8.0		93.4		7.2
		20.0	107.1		7.5		108.3		5.9		98.2		8.0
35		2.50	85.7		5.4		83.0		7.5		94.8		5.9
		5.00	90.5		9.2		90.8		5.2		85.7		7.4
		20.0	87.0		10.1		85.4		8.9		87.4		5.2
36		2.50	83.3		8.2		89.9		9.8		88.1		8.9
		5.00	89.6		9.0		87.9		8.0		95.4		4.7
		20.0	91.9		3.9		88.4		8.8		90.6		8.0
37		2.50	87.0		6.9		80.1		4.7		75.3		6.1
		5.00	91.7		4.7		82.0		6.8		83.9		4.7
		20.0	88.0		5.5		82.3		4.6		84.7		6.7
38		2.50	89.8		5.1		86.2		5.4		81.2		4.5
		5.00	89.0		5.1		81.7		4.9		88.9		5.3
		20.0	92.4		5.5		80.5		4.9		86.7		5.0
39		2.50	106.5		6.9		96.3		5.4		92.9		5.0
		5.00	98.4		7.2		100.0		6.8		95.9		5.3
		20.0	108.5		5.3		94.9		7.1		92.5		6.7
40		2.50	83.6		8.1		82.3		5.2		86.5		7.0
		5.00	85.7		7.8		81.0		7.9		84.9		5.1
		20.0	88.0		6.4		79.6		7.6		78.5		7.9
41		2.50	92.8		4.8		79.7		6.3		82.0		7.6
		5.00	89.8		6.2		83.1		4.7		82.1		6.3
		20.0	85.6		7.8		86.0		6.0		85.7		4.7
42		2.50	91.8		7.5		81.0		7.6		88.7		6.0
		5.00	87.7		6.3		82.7		7.3		81.5		7.6
		20.0	86.9		7.8		78.2		6.1		85.3		7.3
43		2.50	81.4		8.1		83.5		7.6		80.6		6.1
		5.00	83.6		5.7		85.6		7.9		83.7		7.6
		20.0	86.8		3.7		82.2		5.6		88.3		7.9
44		2.50	89.9		4.8		79.1		3.7		84.8		5.6
		5.00	89.0		6.4		84.7		4.7		81.2		3.7
		20.0	92.4		6.6		81.1		6.3		87.5		4.7
45		2.50	83.5		5.5		82.3		6.4		89.6		6.3
		5.00	85.2		3.7		84.5		5.4		84.9		6.4
		20.0	85.8		9.0		83.2		3.7		89.5		5.3
46		2.50	92.9		7.2		77.1		8.8		85.8		3.7
		5.00	88.3		7.9		84.2		7.1		87.6		8.8
		20.0	88.7		6.2		86.5		7.7		86.8		7.0
47		2.50	79.3		5.5		80.9		6.0		90.1		7.7
		5.00	84.8		6.9		88.2		5.4		83.4		6.0
		20.0	81.2		8.6		84.2		6.8		81.5		5.3
48		2.50	98.3		7.9		79.1		8.4		86.8		6.7
		5.00	89.8		8.1		88.9		7.7		81.5		8.3
		20.0	87.6		7.8		83.2		7.9		83.7		7.7
49		2.50	83.8		6.6		79.3		7.6		85.8		7.9
		5.00	86.8		7.4		84.9		6.4		90.5		7.6
		20.0	83.3		5.8		81.0		7.2		87.5		6.4
50		2.50	107.8		8.1		86.9		5.8		83.6		7.1
		5.00	85.8		5.1		87.2		7.9		89.6		5.7
		20.0	76.6		6.2		82.1		4.9		85.6		7.9
51		2.50	82.9		6.8		81.1		6.0		84.7		5.0
		5.00	83.0		9.1		82.6		6.7		79.4		6.0
		20.0	99.4		7.0		82.0		8.9		81.5		6.6
52		2.50	89.6		7.8		89.3		6.9		84.7		8.9
		5.00	82.3		5.7		84.2		7.6		87.7		6.8
		20.0	78.2		7.2		87.4		5.6		86.8		7.6
53		2.50	81.4		5.1		78.9		7.1		90.1		5.6
		5.00	97.4		8.7		86.3		4.9		81.4		7.0
		20.0	89.2		9.5		81.1		8.5		83.0		5.0
54		2.50	85.7		7.8		85.4		9.3		83.7		8.4
		5.00	82.1		8.6		83.5		7.6		90.6		9.2
		20.0	79.3		3.7		83.9		8.4		86.1		7.6
55		2.50	90.5		6.6		76.0		4.5		89.6		5.8
		5.00	82.9		4.4		77.9		6.4		93.5		4.4
		20.0	90.5		5.2		78.2		4.4		104.8		6.4
56		2.50	86.7		4.9		81.9		5.1		93.6		4.3
		5.00	88.5		4.9		77.6		4.7		102.5		5.0
		20.0	84.3		5.2		76.5		4.7		82.4		4.7
57		2.50	80.8		6.6		82.0		5.1		94.5		4.7
		5.00	81.6		6.8		76.0		6.4		91.3		5.0
		20.0	78.3		5.0		79.7		6.7		88.6		6.4
58		2.50	85.6		7.7		78.2		4.9		82.2		6.7
		5.00	83.6		7.4		77.0		7.6		80.7		4.8
		20.0	80.0		6.1		75.6		7.2		86.5		7.5
59		2.50	82.8		4.5		75.7		6.0		91.4		7.2
		5.00	79.5		5.9		79.0		4.5		85.9		6.0
		20.0	83.4		7.4		81.7		5.7		81.5		4.4
60		2.50	103.4		7.1		87.3		7.2		95.3		5.7
		5.00	89.7		6.0		96.4		6.9		89.4		7.2
		20.0	93.5		7.4		93.1		5.8		97.5		6.9

Sample	Number of compounds	Analytical method	Preparation method	Preparation time/min	V(Organic solvent)/mL	LOD/ (μg/kg)	Ref.
Bird’s nest	45	UPLC-MS/MS	SPE	>120	40	0.16-2.0	[11]
Milk powder	42	UPLC-MS/MS	QuEChERS	<60	10	0.06-1.5	[12]
Milk	9	UPLC-MS/MS	QuEChERS	<60	10	0.5-10	[18]
Dairy products	6	UPLC-MS/MS	SPE	>120	327	0.05-0.1	[19]
Bullfrogs	9	UPLC-MS/MS	SPE	>120	10	0.5-1.0	[20]
Cosmetics	22	UPLC-MS/MS	SPE	>120	20	0.1-27.4	[24]
Sports nutrition foods	60	UPLC-MS/MS	QuEChERS	<60	10	0.2-0.8	this work