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1 7 4 Vol. 7 No Journal of Food Safety and Quality Apr., 2016 林芳, 王一欣, 李涛 *, 刘海静, 袁磊 (, ) 摘要 : 目的 (UPLC) - (GC-MS), 方法 -, UPLC UPLC ZORBAX SB-C 18 ( mm, 1.8 μm), 0.1%, 0.4 ml/min, 210 nm GC-MS DB-5MS (30 m 0.25 mm 0.25 μm), : 150 (1 min), 8 /min 250 (5 min), 12 /min 280 (15 min), EI, 2 min, 50~600 amu 结果 23 min, UPLC, 结论, 关键词 : ; ; ; - ; Study on determination of new illegal additives in sleep-improving health-care foods LIN Fang, WANG Yi-Xin, LI Tao *, LIU Hai-Jing, YUAN Lei (Shaanxi Institute for Food and Drug Control, Xi an , China) ABSTRACT: Objective To establish a method of ultra performance liquid chromatography and gas chromatography-mass spectrometry for determination and confirmation of new illegal drug added in sleep-improving health-care foods. Method The samples were extracted through solvent ultrasonic extraction or the liquid-liquid extraction and tested by UPLC. In the UPLC method, ZORBAX SB-C 18 column ( mm, 1.8 μm)was used with the mobile phase of acetonitrile and 0.1% phosphoric acid for linear gradient elution. The flow rate was 0.4 ml/min. The detection wave lengths were 210 nm for preliminary screening. The analytical capillary column of GC-MS was DB-5MS (30 m 0.25 mm 0.25 μm). The temperature programming was as follows: the initial temperature was set at 150 (1 min); then raised to 250 (5 min) with heating speed of 8 /min, and to 280 (15 min) with heating speed of 12 /min. The EI ion source was selected and the solvent delayed by 2 min. The MS scanning was set at the range of 50~600 amu. Results New illegal additives in sleep-improving health-care foods could be effectively detected within 23 min. Through analyzing by UPLC, a suspicious chromatographic peak was detected and then was confirmed to be a new kind of illegal additive flunarizine hydrochloride by GC-MS method. Conclusion The 基金项目 : (2014FWPT-01) Fund: Supported by the Shaanxi Science and Technology Co-ordination Innovation Project (2014FWPT-01) * 通讯作者 :,, westyx@126.com. *Corresponding author: LI Tao, Vice Director Pharmacist, Shaanxi Institute for Food and Drug Control, No.21, Kejiwu Road, Gaoxin District, Xi an , China. westyx@126.com.

2 method is rapid, simple and accurate, which provides research mentality and reference for the determination of new illegal additive in health foods. KEY WORDS: health foods; new illegally additives; flunarizine hydrochloride; gas chromatography-mass spectrometer; ultra performance liquid chromatography 1 引言,, [1] [2],, 38,, [3-8] , (State food and drug administration, SFDA) ( ) [9], 6,,,,,, (TLC) [10] (HPLC) [11] - (LC-MS) [12] (GC) [13] - (GC-MS) [14,15] (UPLC) - (GC-MS), SFDA [16-18], (ultra performance liquid chromatography, UPLC) - (gas chromatography-mass spectrometry,gc-ms), GC-MS, 2 材料与方法 2.1 仪器与设备 Agilent1290 Infinity ( 1290, ); GCMS-QP2010 Ultra - ( ); NIST05 NIST05s WILEY7 Autotune ; TACHI CF16RN ( ); TTL-DCLL ( ); HH-S6 ( ); IKA MS3 basic ( ); KQ-500DE ( ); BS223S ( ); Synergy ( ) 2.2 材料与试剂, , 18 (, TEDIA ); (, ) (, ); : ( 99.9%) ( 99.9%) ( 99.8%) ( 99.7%) ( 99.4%), ;, 2.3 实验方法 标准溶液的配制 (1) UPLC 0.8 mg/ml : mg, 25 ml, :, 1~2.5 ml 25 ml,,

3 4, : 1633 (2) GC-MS, 20 mg, 20 ml, 1 ml, 20 ml, 色谱条件 (1) UPLC : ZORBAX SB-C 18 (2.1 mm 150 mm, 1.8 μm), : 30 ; : 210 nm; : 1 μl; : 0.4 ml/min; A:, B: 0.1%, : 15 min, : : 190~400 nm, : 1.0 nm, : (2) GC-MS : DB-5MS (30 m 0.25 mm 0.25 μm), Restek ; ( 150, 1 min, 8 /min 250, 5 min, 12 /min 280, 15 min); 2:1; (He), 7.5 ml/min, 1.5 ml/min; 280 ; 150 ; kpa; 1 μl : EI, 250 ; 70 ev;, Scan, 50~600 amu; 2 min 样品前处理 [18],,, [16,17] UPLC : ( 10 ml, 5 ml, 10 ml), 10 ml, 3, 10 ml,, 5 min,, 1 ml, 0.45 μm GC-MS : ( 2, 4, 1 ; ), 10 ml 20 min, 3000 r/min 5 min, 5 ml,,, 1 ml, 0.45 μm 3 结果与分析 3.1 色谱条件的优化 ZORBAX SB-C 18 (2.1 mm 150 mm, 1.8 μm), -0.1%, 1, 12 min 18, 1, 18 [16] 表 1 梯度洗脱条件 Table 1 Gradient elution conditions /min ( )% (0.1% )% UPLC 初筛鉴别 UPLC,, ( 2) 8 min, 18 ( 1), 14,,, 3,, 1-0.1% Fig. 1 Chromatogram of mixed standard solution separated by gradient elution using acetonitrile-0.1% phosphate buffer as the mobile phase. 1. ; 2. ; 3. ; 4. ; 5. ; 6. ; 7. ; 8. ; 9. ; 10. ; 11. ; 12. ; 13. ; 14. ; 15. ; 16. ; 17. ; 18.

4 GC-MS 法测定, 2.3.3, GC-MS Scan,,,, A, 98%, 4~5,, ( B),, 6~7,, 2 UPLC Fig. 2 Chromagtogram of suspected sample Fig. 3 3 (a) (b) Comparison of spectrogram of suspected sample(a) and lorazepam standard(b) Fig. 4 4 Mass spectrum of the sample

5 4, : 1635 Fig. 5 5 Spectral library search results of the sample Fig. 6 6 Mass spectrum of flunarizine hydrochloride Fig. 7 7 Comparison of flunarizine hydrochloride standard and standard mass spectral library 4 结论, Ca 2+,,,,, UPLC GC-MS,, 参考文献 [1],,,. [J]., 2014, 11(7): Zhang Y, Min CY, Hao G, et al. Screening method for illegally added chemicals in health foods [J]. Chin Licd Pharrm, 2014, 11(7): [2],,,. [J]., 2013, 27(11): Guo ZX, Dong PZ, Shen GH, et al. Characteristics of illegal addition of chemicals to health food and recommendations for supervision [J]. Chin Pharm, 2013, 27(11): [3],,. [J]., 2014, 18(1): 4 7. Luo L, Wang CJ, Deng DT. The present research development of losing

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