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1 4 3 Vol. 4 No Journal of Food Safety and Quality Jun., 2013 * 刘波, 吴婷婷, 侯玉兰, 廖鹏, 王华, 陈波 (,, ) 摘要 : 目的 6 (,,,,, ) 方法 DCBI-MS,, 6 结果, R , 1 mg/l, 8% 40% 结论,,,, 关键词 : ; ; ; ; Rapid determination of sugar-reducing medicine in health food by DCBI-MS method LIU Bo, WU Ting-Ting, HOU Yu-Lan, LIAO Peng, WANG Hua, CHEN Bo * (Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha , China) ABSTRACT: Obiective To develop a rapid method for detection of 6 kinds of sugar-reducing medicines (nateglinide, dimethyldiguanide, voglibose, glipizide, pioglitazone, repaglinide) with the desorption corona beam ionization mass spectrometry (DCBI-MS) technique. Methods The rapid qualitative and semi-quantitative identification of 6 kinds of sugar-reducing medicines including nateglinide, dimethyldiguanide, voglibose, glipizide, pioglitazone and repaglinide in samples were performed by comparing MS and MS 2 spectra of samples with standard substances by DCBI-MS. Results The method showed a good linearity in a given range for all of analytes. The linear coefficients of analytes were higher than The LODs of 6 sugar-reducing medicines were lower than 1 mg/l. The RSDs of the method ranges from 8% to 40%. Conclusion The developed DCBI-MS is simple, rapid, sensitive for screening and semi-quantification of the sugar-reducing medicines in health foods and traditional Chinese patent medicines and it provides the basis for further accurate regulation test. KEY WORDS: desorption corona beam ionization mass spectrometry; rapid detection; health food; illegal additives; sugar-reducing medicines 基金项目 : ( ) (CX2012B205) Fund: Supported by the National Natural Science Foundation of China ( ) and Graduate Student Research Innovation Project in Hunan Province (CX2012B205) * 通讯作者 :,,, [email protected] *Corresponding author: CHEN Bo, Professor, Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha , China. [email protected]

2 3, : 引言,, [1-3] 2006, 3, ;, [4], - [5,6],,,, DESI DART [7-9],, (desorption corona beam ionization, DCBI) [10-11] DCBI, DCBI,, DCBI DCBI, 6 (,,,,, ) DCBI,, 2 材料与方法 2.1 样品与试剂 6 : (nateglinide) (epalrestat) (voglibose) (glipizide) (pioglitazone) (repaglinide), >98%, 1 ; (HPLC ),, 1, 标准溶液的制备 g, 10 ml,, ( 150 W, 50 Hz) 20 min,, 1000 mg/l mg/l 2.3 样品溶液的制备 : 0.6 g,, 25 ml ( 150 W, 50 Hz) 20 min,, 50 ml, 10 μl, DCBI : 1.0 g, 100 ml, 50 ml, ( 150 W, 50 Hz) 20 min,,, 2.4 仪器与参数 DCBI, ; ( ( ) ); Thermo Finnigan-LCQ, LCQ-tune ( );

3 724 4 KQ3200E ( ) DCBI : 0.6 L/min, +3.5 kv, 220, 10 µl; LCQ :, (Scan), +5 V, 260, +15 V (CID), 0.5 Da, Fig. 1 1 Structure of six kinds of sugar-reducing medicines Table 1 表 1 供试样品的标示成分 Marked herbal ingredients of local marketed samples Table 2 表 2 阳性样品的标示成分 Marked herbal ingredients of provided positive samples 1 J G G G Z

4 3, : 结果与分析 3.1 仪器条件优化, DCBI,, 3 (120, 180, 220 ) 6 ( 12.5 mg/l, 20 mg/l) 2 120,, DCBI,, 6,,,, 180, 220,, Fig. 2 Source temperature effect on the desorption efficiency 3.2 DCBI-MS 一级质谱定性分析 DCBI-MS, 6 1 min, 3 (M W : 317) (M W : 129) (M W : 267) (M W : 445) (M W : 356) (M W : 452) m/z 318 m/z 130 m/z 268 m/z 446 m/z 357 m/z 453,, 10% 50% CID, 10% 6 3, ESI, (M W : ) DCBI m/z [M+H] +, m/z , CID 40%, m/z m/z m/z m/z m/z , m/z ,, 3.3 DCBI-MS 半定量分析, DCBI, 6, 3, 2-3, 1 mg/l, mg/l,,, DCBI-MS, 5,, 6 DCBI-MS 8% 40% 20.8 mg/l RSD 22% 60% 80% DCBI-MS,, 3.4 实际样品检测, DCBI-MS,,, DCBI-MS, 6 (,,,,, ) 10 mg/l, 10 μl, DCBI, 4

5 726 4 ( )

6 3, : Fig. 3 MS and MS 2 spectra of 6 kinds of sugar-reducing medicines by DCBI-MS

7 728 4 Table 3 表 3 降糖类药物的线性范围及检出限 Linear range and LOD of sugar-reducing medicines (mg/l) R 2 (mg/l) Y=3.361X Y=0.230X Y=3.264X Y=0.723X Y=0.588X Y=2.244X Fig. 4 4 Mass spectra of a negative samples spiked with drugs by DCBI-MS,, DCBI-MS 3,, 3 6 ; 5, m/z 130, 4 m/z 453, 5 m/z 结论 6 DCBI-MS DCBI,,, 6, DCBI-MS, 1 min,,

8 3, : 729 DCBI-MS,,,, 参考文献 [1],. [J]., 2010, 7(2): Wu YS, Wu Y. Determination of gliclazide and glibenclamide illegally added into poria cocos dioscorea rhizoma tablets by HPLC [J]. Anti Infect Pharm, 2010, 7(2): [2],. [J]., 2011, 31(2): Xiao SX, Li YJ. Exploration of a systematic rapid screening strategy by analysis of chemical components illegally added in anti-diabetes traditional Chinese medicines and healyh foods [J]. Chin J Pharm Anal, 2011, 31(2): [3],,. [J]., 2008, 12(10): Wan Q, Guan YY, Cheng Z. Qualitative identification of illegal adding of sulphonylurea to antidiabetic food for health care [J]. Anhui Med Pharm, 2008, 12(10): [4],,. LC-MS/MS 3 [J]., 2012, 21(6): Wang ZQ, Hu LF, Cao GZ, et al. Determination of three kinds of metformin hydrochloride preparations in Beagle dog plasma by LC-MS/MS and study on its pharmacokinetic [J]. Chin J Clin Pharm, 2012, 21(6): [5],,. HPLC-MS [J]., 2006, 14(6): Xia SN, Wang ZY, Li D. Studies on Identification for Glibenclamide Gliclazide Glimepiride Mixed in TangLeShu Capsules by HPLC-MS Method [J]. Pharm Clin Res, 2006, 14(6): [6],,. HPLC [J]., 2010, 22(1): Chen AP, Shen CY, Zhang ZH. Determination of Gliclazide in Gliclazide capsules by HPLC [J]. Strait Pharm, 2010, 22(1): [7] Chen HW, Zheng J, Wang WP, et al. Desorption electrospray ionization mass spectrometry for fast detection of alkaloids in fructus evodiae [J]. Anal Chem, 2009, 37(2): [8] Chen HW, Lai JH, Zhou YF, et al. Instrumentation and Characterization of Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry [J]. Anal Chem, 2007, 35(8): [9] Chen HW, Talaty NN, Takáts Z, et al. Desorption electrospray ionization mass spectrometry for high-throughput analysis of pharmaceutical samples in the ambient environment [J]. Anal Chem, 2005, 77(21): [10] Wang H, Sun WJ, Zhang JS, et al.. Desorption corona beam ionization source for mass spectrometry [J]. Analyst, 2010, 135: [11] Li X, Wang H, Sun WJ, et al. Desorption corona beam ionization coupled with a Poly(dimethylsiloxane) Substrate: Broadening the Application of Ambient Ionization for Water Samples [J]. Anal Chem, 2010, 82(22): 作者简介 ( 责任编辑 : 张宏梁 ) 刘波, 硕士研究生, 主要研究方向为主要研究方向为分离分析化学 [email protected] 陈波,,, - Wageningen,,,, 7, 80, , 2005, 1 3