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1 5 5 Vol. 5 No Journal of Food Safety and Quality May., * 潘小红 (, 411) 摘要 : 目的 (ultra performance liquid chromatography/time-of-flight mass spectrometry, UPLC-Q-TOF-MS-MS) 22 方法, /, ACQUITY TM UPLC HSS T3(5 mm 1.8 mm 1.7 μm),.1-, (ESI),, 22 结果 22, 22, 1 ng, 结论,, 关键词 : ; ; Rapid identification of 22 drugs illegally added into improving sleep health foods by ultra performance liquid chromatography/time-of-flight mass spectrometry method PAN Xiao-Hong* (Hunan Institute for Food and Drug Control, Changsha 411, China) ABSTRACT: Objective To establish a rapid ultra performance liquid chromatography/time-of-flight mass spectrometry method to identify 22 kinds of drugs illegally added into improving sleep health foods. Methods A method of the ultra performance liquid chromatography-mass spectrometry (UPLC-MS/MS) was used to detect the 22 kinds of drugs illegally, samples were extracted with methanol. By the separation column of ACQUITY TM UPLC HSS T3 (5 mm 1.8 mm 1.7 μm), the gradient elution of the mobile phase consisted of.1 formic acid acetate solution and the mass spectrometer conditions (ESI) as operated in positive or negative ion mode and in two scan modes including full scan MS. Results A good resolution of 22 drugs illegally added into the food for improving sleep health was obtained by UPLC-MS/MS, of which the determination limits were all below 1. ng. Conclusion The method which showed sufficiently selective and sensitive could be used to detect illegal drugs in the food for improving sleep health KEY WORDS: ultra performance liquid chromatography/time-of-flight mass spectrometry; improving sleep health foods, illegal adding 基金项目 :,,, panxiaohong56781@ 163.com *Corresponding author: PAN Xiao-Hong, Senior Nutritionist, Research Assistant, Major research in the inspection, research and development of food, medicine, health food and cosmetics. Hunan Institute for Food and Drug Control, No.6, Baxi Road, Furong District, Changsha 411, China. [email protected].

2 5 : ,,,, ( ), ,, [1],,,, 3, , [2-4], -,,, (UPLC-Q- TOF-MS-MS), (UPLC), (Q-TOF- MS-MS), [5-7], 22, 1 仪器与试剂 Waters Q-TOF Premier TOF, ESI ; Waters Acquity TM ; R-215 Buchi 22 1, Merck : ( ) 表 1 22 种标准品的详细信息 Table 1 The detailed information of 22 standard substance () / Dr / / () / / / / / / UV / / / / 15 3 h / / / / / / / / / / / / / / / h / / /

3 实验方法 2.1 色谱条件 : ACQUITY TM UPLC HSS T3(5 mm 1.8 mm 1.7 μm), Agilent EC-C 18 (15 mm 2.1 mm, 2.7 μm), Halo TM C 18 (1 mm 2.1 mm 2.7 μm), ACQUITY TM UPLC BEH C 18 (1 mm 2.1 mm 1.7 μm); 3 ; 5 μl;.3 ml/min,.1 (A)- (B), 2.2 质谱条件 ESI ; 3 kv; 3 V; 3 V;.1 V; 35 ; 7 L/h; 13~35 V, () 5~5 (ESI+): 17 (ESI-): 标准品的配制 标准品储备溶液的配制 mg, 5 ml,, 混合标准品溶液的配制,.1~2. μg/ml 22, (ESI+ ESI-) 2.4 供试品的制备 固体试样 1,, (,, )(, ), 5. ml,, 3 min( 25 W, 33 khz),,,,, 1. ml 1 ml,, 液体试样 5~1,,,,, ml 2.5 样品测定 5 μl, 3 结果与分析 3.1 液相色谱条件的优化 4, 4,, ACQUITY TM UPLC HSS T3(5 mm 1.8 mm 1.7 μm), (ESI+) - (ESI-), mol/l,,, -.1, 2,, 1 1, ESI+ ESI-, 表 2 不同电离模式中流动相梯度洗脱时间表 Table 2 The schedule the gradient elution in different ionization modes /min /(ml min 1 ) A B Curve /min) /(ml min 1 ) A B Curve / :.1 (A)- (B)

4 5 : 质谱条件的优化.4 μg/ml, ESI,,, 3 V, MS/MS, 2, 种化学物质的谱图特性, 22, 3, 4 Fig. 1 1 ( : 1-ESI+, 2-ESI-) Total ion-current grams of standard substance (Note: 1-ESI+, 2-ESI-) Table 3 表 3 22 种改善睡眠类的质谱条件优化结果 Results of best choices of MS conditions of 22 kinds of drugs illegally added improving sleep health foods (component) (Min) (ps eudomolecular ions)/() (collision energy)/ev (fragment ions from full scan MS/MS)/() (ng) , , , , , , , , , , 29.17, , , , , 27.2, , 25.18, , , , 25.18, , , , , , , , , , , , , , 15.37,

5 Table 4 表 4 22 种标准品特征离子及碎片离子图 Characteristic ion and fragment ions gram of 22 kinds of standard substance (component) (characteristic ion gram) (daughter ion scan gram) Da 1.5e Da 1.14e Da 1.18e S Da 9.91e Da 6.1e Da 1.84e Da 8.66e Da 1.39e Da 5.4e Da 5.48e HBSHUI5 26 (2.4) Cm (1:4) 1: TOF MSMS 33.32ES e HBSHUI5 18 (2.66) Cm (8:24) 2: TOF MSMS HBSHUI5 9 (2.863) Cm (8:1) 4: TOF MSMS 3.23ES e HBSHUI5 12 (2.751) Cm (1:14) 3: TOF MSMS ES e HBSHUI5 9 (2.991) Cm (7:11) 5: TOF MSMS ES e (2 869) C (13 135) 1TOFMSES HBSHUI5 8 (3.128) Cm (5:11) : TOF MSMS ES+ 1.56e HBSHUI5 7 (3.163) Cm (5:9) : TOF MSMS ES+ 2.83e HBSHUI5 17 (4.946) Cm (1:28) : TOF MSMS ES e6 HBSHUI5 37 (5.52) Cm (24:44) 9: TOF MSMS ES e HBSHUI5 34 (6.291) Cm (22:47) 1: TOF MSMS 36.28ES e HBSHUI5 1 (6.634) Cm (4:16) : TOF MSMS ES e5

6 5 : 续表 4 (component) (characteristic ion gram) (daughter ion scan gram) Da 6.14e Da 5.64e Da 3.8e Da 1.24e Da 1.8e Da 3.3e Da 2.9e Da 3.8e Da 4.36e HBSHUI5 13 (6.771) Cm (8:18) 12: TOF MSMS 2.22ES e HBSHUI5 12 (6.98) Cm (6:19) : TOF MSMS 287.2ES e5 HBSHUI5 24 (7.46) Cm (16:29) 14: TOF MSMS 39.23ES e HBSHUI5 14 (7.644) Cm (9:17) : TOF MSMS ES+ 5.22e HBSHUI5 14 (7.78) Cm (11:17) 16: TOF MSMS ES e HBSHUI5 2 (8.123) Cm (12:29) 17: TOF MSMS 285.2ES e HB (3.28) Cm (83:161) 1: TOF MSMS 183.3ES e HB (5.488) Cm (16:184) HB32 7 (6.973) Cm (4:98) : TOF MSMS 231.3ES e : TOF MSMS ES- 2.1e HB32 75 (7.41) Cm (7:81) 4: TOF MSMS ES e

7 Da 3.42e HB32 6 (7.738) Cm (55:63) 5: TOF MSMS ES e , 22, 4, 3.4 检出限,, [8], 22,,, S/N = 3,, 3 3, 22, 1 ng, 3.5 方法的优化及专属性 ,, 3,,,,,, 3 22, 2924,,,, 5, 3, 22,, 5,,, S/N 3,, 22,, Table 5 表 5 样品及样品加标的离子图 (ESI-) Ion-current grams of sample and sample with recoveries (ESI-) (component) 22:39:18-Jul-213-1BP TIC e :36:4418-Jul-213-1BP Da e BP Da e BP TIC e :39:18-Jul-213-1BP BP Da 9.96e Da 1.7e5-1BP Da e BP Da 6.e4

8 5 : BP Da e BP Da 5.67e5-1BP Da e BP Da 8.27e5 2 Fig. 2 Ion-current grams of sample 3.6 样品的测定结果, [8 9],,,,,, 2 2,,, 4 讨论 - (UPLC-MS-MS-MS), 1.7 μm, UPLC-Q-TOF/MS : UPLC, 1 min 22, ;,, TOF/MS,,, 22 1 ng, , 15, 4 3,,,, 5 ml, 1,.22 μm,,,, 22,,,, 1 ng,,,,, 1,,,,, 22,,,

9 1532 5,,,,, 参考文献 [1] [EB/OL] The special action of "four not" against health food was comprehensively deployed by Administration[EB/OL]. gov.cn/ws1/cl1523 /8196.html [2] [Z] The approved compensation process and inspecting item of China food and Drug Administration. Serial number Sedative Chinese patent medicines [Z] [3] [Z] The approved compensation process and inspecting item of China food and Drug Administration. Serial number 2124.Sedative Chinese patent medicines and Health food [Z] [4] [Z] The approved compensation process and inspecting item of China food and Drug Administration. Serial number 2132.Improving sleep Chinese patent medicines and Health food [Z] [5] Li SL, Lai SF, Song JZ, et al. Decocting-induced chemical transformations and global quality of Du-Shen-Tang, the decoction of ginseng evaluated by UPLC-Q-TOF-MS/MS based chemical profiling approach [J]. J Pharm Biomed Anal, 21, 53: [6] Li SL, Song JZ, Qiao CF, et al. UPLC-PDA-TOF MS based chemical profiling approach to rapidly evaluate chemical consistency between traditional and dispensing granule decoctions of traditional medicine combinatorial formulae [J]. J Pharm. Biomed Anal, 21, 52: [7] Li L, Luo GA, Liang QL, et al. Rapid qualitative and quantitative analyses of Asian ginseng in adulterated American ginseng preparations by UPLC/Q-TOF-MS [J]. J Pharm. Biomed Anal, 21, 52: [8],,,. LC-MS/MS 18 [J]., 212, 3 (1): Wang ZY, Li D, Wen HM, et al. Screening for 18 mixed illegally cough-relieving chemical composition in health food by LC-MS/MS [J]. Chin Arch Trad Chin Med, 212, 3 (1): [9],,,. UPLC-MS/MS 7 [J]., 212, 1 (1): Li YB, Meng QY, Zhong QY, et al. Rapid identification of 7 drugs illegally added into weight reducing health foods by UPLC-MS/MS [J]. Cent South Pharm. 212, 1 (1): 作者简介 ( 责任编辑 : 张宏梁 ) 潘小红, 高级营养师, 助理研究员, 主要研究方向为食品 药品 保健食品及化妆品的检验及研发 [email protected]