4 3 Vol. 4 No. 3 2013 6 Journal of Food Safety and Quality Jun., 2013 * 刘波, 吴婷婷, 侯玉兰, 廖鹏, 王华, 陈波 (,, 410081) 摘要 : 目的 6 (,,,,, ) 方法 DCBI-MS,, 6 结果, R 2 0.98, 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 410081, 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 0.98. 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 : (21275049) (CX2012B205) Fund: Supported by the National Natural Science Foundation of China (21275049) and Graduate Student Research Innovation Project in Hunan Province (CX2012B205) * 通讯作者 :,,, E-mail: dr-chenpo@vip.sina.com *Corresponding author: CHEN Bo, Professor, Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha 410081, China. E-mail: dr-chenpo@vip.sina.com
3, : 723 1 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, 2 2.2 标准溶液的制备 0.0100 g, 10 ml,, ( 150 W, 50 Hz) 20 min,, 1000 mg/l 0.5 5 25 50 100 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 ( );
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 1 2 3 Table 2 表 2 阳性样品的标示成分 Marked herbal ingredients of provided positive samples 1 J20060011 2 G20050088 3 G20070225 4 G20050141 5 Z20050771
3, : 725 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,, 220 2 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 : 317.43) DCBI m/z 318.41 [M+H] +, m/z 318.41, CID 40%, m/z 120.12 m/z 166.01 m/z 256.29 m/z 271.99 m/z 300.12, m/z 166.01,, 3.3 DCBI-MS 半定量分析, DCBI, 6, 3, 2-3, 1 mg/l, 0.0385 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
726 4 ( )
3, : 727 3 Fig. 3 MS and MS 2 spectra of 6 kinds of sugar-reducing medicines by DCBI-MS
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) 0.075 15.000 Y=3.361X+1.923 0.999 0.0385 1.250 62.500 Y=0.230X+0.304 0.994 0.6250 1.625 81.250 Y=3.264X 18.510 0.983 0.8125 1.775 88.750 Y=0.723X 2.394 0.996 0.8875 1.875 187.500 Y=0.588X 3.568 0.996 0.1875 0.104 20.800 Y=2.244X 0.109 0.999 0.1040 Fig. 4 4 Mass spectra of a negative samples spiked with drugs by DCBI-MS,, DCBI-MS 3,, 3 6 ; 5, 1 2 3 m/z 130, 4 m/z 453, 5 m/z 357 4 结论 6 DCBI-MS DCBI,,, 6, DCBI-MS, 1 min,,
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