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1 4 3 Vol. 4 No Journal of Food Safety and Quality Jun., 2013 * 廖鹏, 侯玉兰, 吴婷婷, 刘波, 王华, 陈波 (,, ) 摘要 : 目的 (DCBI-MS) 方法 DCBI-MS,, 6 结果 1 min, 6, , mg/l 结论,, 关键词 : ; ; Rapid determination of trace estrogens with DCBI-MS method LIAO Peng, HOU Yu-Lan, WU Ting-Ting, LIU Bo, WANG Hua, CHEN Bo * (Key Laboratory for Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha , China) ABSTRACT: Obiective A rapid method for detection of the trace estrogens was developed with the desorption corona beam ionization mass spectrometry(dcbi-ms) technique. Methods The rapid qualitative and semi-quantitative identification of 6 kinds of estrogens, including norethindrone, progesterone, medroxyprogesterone acetate, levonorgestrel, megestrol acetate and clomiphene citrate in samples was performed by comparing MS and MS 2 spectra of samples with standard substances by DCBI-MS. Results All of the 6 target molecules were detected within 1 min. Quantification was achieved based on the molecular ion in MS spectra of each analyte. The semi-quantitative analysis for 6 estrogens was reliable. The linear coefficient of megestrol acetate was while progesterone was The LOD of 6 kinds of estrogens were , 0.045, , 0.05, 0.15, 0.1 mg/l, respectively. Conclusion Without tedious sample pretreatments, the developed DCBI-MS is simple, rapid, sensitive for screening and semi-quantitative analysis of the estrogens additives in health foods and traditional Chinese patent medicines. KEY WORDS: desorption corona beam ionization mass spectrometry (DCBI-MS); estrogen; rapid detection 基金项目 : ( ) Fund: Supported by the National Natural Science Foundation of China( ) * 通讯作者 :,,, dr-chenpo@vip.sina.com *Corresponding author: CHEN Bo, Professor, Key Laboratory for Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, No.36, Lushan Road, Changsha , China. dr-chenpo@vip.sina.com

1 mg/l 结论,, 关键词 : ; ; Rapid determination of trace estrogens with DCBI-MS method LIAO Peng, HOU Yu-Lan, WU Ting-Ting, LIU Bo, WANG Hua, CHEN Bo * (Key Laboratory for Chemical Biology & Traditional

2 3, : 引言,,,, ; ;,,,,, ;, [1-2],,,, [3], [4] [5] [6] [7] / (GC-MS) / (LC-MS), [8] [9] [10], GC-MS,, DESI DART [11-12], (desorption corona beam ionization, DCBI) [13-14] DCBI, DCBI, DCBI,, DCBI, 6, ESI, 2 材料与方法 2.1 试剂与仪器 ( >99%,, 1 ); 1 6 Fig. 1 Structure of six kinds of estrogens

3 732 4 (HPLC, ); ( Millipore ) : g, 9 10 ml, 5 ml, 5 min,,, 1000 mg/l, mg/l Thermo Finnigan-LCQ, LCQ-tune ( ); DCBI ( ), ( ); KQ3200E ( ); (25 µl) 2.2 样品制备 : (, ) 1.0 g, 100 ml, 50 ml, 20 min,,, : μl 10 ml,, 20 mg/l :, 10 μl, DCBI 3 结果与分析 3.1 DCBI 源及质量分析器条件优化 6, DCBI DCBI, 3.5 kv, 10 µa, (He) 0.6 ml/min, V, 260, 5 V (CID), 0.5 Da,, DCBI-MS 6, 1 min, 3.2 DCBI-MS 快速检测 6 10 mg/l DCBI-MS ( ) ( ), 2 2, DCBI m/z m/z [M+H] + ( ) DCBI Fig. 2 2 DCBI(+) Mass spectra of medroxyprogesterone acetate and megestrol acetate by DCBI-MS

0 g, 100 ml, 50 ml, 20 min,,, : 6 200 μl 10 ml,, 20 mg/l :, 10 μl, DCBI 3 结果与分析 3.1 DCBI 源及质量分析器条件优化 6, DCBI DCBI, 3.5 kv, 10 µa, (He) 0.

4 3, : 733 m/z [M+H] +, 3, m/z , 4, CID 30%, m/z m/z m/z m/z m/z , m/z ( ) m/z M +, m/z m/z m/z m/z m/z , m/z ( ) DCBI m/z , m/z , 5, CID 35%, m/z m/z m/z m/z m/z 97.03, m/z ( ) m/z , m/z , 6, CID 33%, m/z m/z m/z m/z , m/z DCBI(+) Fig. 3 Mass spectra of levonorgestrel and clomiphene citrate by DCBI-MS Fig. 4 4 DCBI(+) Secondary mass spectrometry of levonorgestrel and clomiphene citrate by DCBI-MS

24 m/z 239.15 m/z 215.16 m/z 97.03, m/z 297.23 ( 298.42) m/z 299.41, m/z 299.41, 6, CID 33%, m/z 281.17 m/z 263.19 m/z 223.20 m/z 171.09, m/z 281.

5 734 4 Fig. 5 5 DCBI(+) MS and secondary mass spectrometry of progesterone by DCBI-MS Fig. 6 6 DCBI(+) MS and secondary mass spectrometry of norethindrone by DCBI-MS DCBI-MS, 10 μl, DCBI 7, 6, m/z m/z m/z m/z m/z m/z ,,

6 3, : 黄体酮和炔诺酮在 DCBI 源和 ESI 源中的响应差异,,, ESI, ESI, DCBI, (5 mg/l) ( ) ESI, DCBI, m/z , (5 mg/l) ( ) ESI, DCBI, m/z , [M+H] +, [2M+H] + m/z ESI, DCBI, APCI,, DCBI, ESI DCBI, DCBI 3.4 DCBI-MS 二级质谱扫描确证与半定量分析 mg/l, mg/l m/z ( ) m/z ( ) m/z ( ) m/z ( ) m/z ( ) m/z ( ),, 1, R 2 = , , RSD 9.25% 62.51%, 0.09 mg/l RSD 21.13%, 45 mg/l RSD 16.79%, Fig. 7 7 DCBI(+) Mass spectrometry of a negative samples and a negative samples spiked with drugs by DCBI-MS 表 1 DCBI-MS 方法中 6 种目标物的线性范围和检出限 Table 1 Calibration curves and detection limits of six targets detected by DCBI-MS (mg/l) (mg/l) Y=3.4434X Y=4.6194X Y=1.6643X Y=14.23X Y=0.5891X Y=0.6767X

35( ),, 1, R 2 = 0.9471, 0.9998, RSD 9.25% 62.51%, 0.09 mg/l RSD 21.13%, 45 mg/l RSD 16.79%, Fig.

7 736 4 DCBI,,, DCBI-MS, 4 结论 6 DCBI-MS, 1 min 6, 6, mg/l,,,,, 参考文献 [1] Sun CH, Peng SG. The effect of environment hormone in meat on human health [J]. Meat Hyg, 1999, 1: [2] Chen XH, Sheng XF, Jin MC. Simultaneus determination of eight progesterone derivatives residues in milk by ultra-fast liquid chromatography coupled with tandem mass spectrometry [J]. Chin J Health Lab Technol, 2010, 20(11): [3] Gu ZW, Hong Q, Liu ZB. Medroxyprogesterone acetate once again get European into the food safety crises [J]. Chin J Environ Occup Med, 2002, 19(5): 280. [4] Mu H, Li L, Zhou L. Determination for estradiol contents in the powder of blastoderm of mutton by radioimmunoassay method [J]. Chin Publ Health, 2002, 18(3): [5] Yan XF, Guo ZH, Zuo WX, et al. Detection of clenbuterol in animal feed by ELISA [J]. Chin J Vet Drug, 2003, 37(12): [6] Wang J, Hu JG, Li JH. Assay for conjugated estrogens in premarin for injection and in premarin cream using GC-FID by Trimethylsilylating [J]. Chin J Pharm Anal, 2001, 21(1): [7] Lin YZ, Zhang SY, Liang W, et al. Determination on residue of salbutamol and 8 kinds estrogen in meat and meat products by HPLC [J]. Chin Publ Health, 2002, 18(12): [8] Fuh MR, Huang SY, Lin TY, Determination of residual anabolic steroid in meat by gas chromatography-ion trap-mass spectrometer [J]. Talanta, 2004, 64(2): [9] Qin Y, Chen J, Zhang MJ. Determination of anabolic hormones multi-residues in animal muscle tissues using liquid chromatography-tandem mass spectrometry [J]. Chin J Anal Chem, 2006, 34(1): [10] Nielen MWF, van Engelen MC, Zuiderent R, et al. Screening and confirmation criteria forhormone residue analysisusing liquid chromatography accuratemass time-of-flight, Fourier transform ion cyclotron resonance and orbitrapmass spectrometry techniques [J]. Anal Chim Acta, 2007, 586(1-2): [11] Chen HW, Hu B, Zhang X. Fundamental principles and practical applications of ambient ionization mass spectrometry for direct analysis of complex samples [J]. Chin J Anal Chem, 2010, 38(8): [12] Chen HW, Lai JH, Zhou YF, et al. Instrumentation and characterization of surface desorption atmospheric pressure chemical ionization mass spectrometry [J]. Chin J Anal Chem, 2007, 35(8): [13] Wang H, Sun WJ, Zhang JS, et al. Desorption corona beam ionization source for mass spectrometry [J]. Analyst, 2010, 135: [14] 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: 作者简介 ( 责任编辑 : 赵静 ) 廖鹏, 硕士研究生, 主要研究方向为分离分析化学 lplmyxty@163.com 陈波, 博士, 教授, 主要研究方向为分离分析化学, 针对的具体分析对象为食品和中草药 dr-chenpo@vip.sina.com

Chin J Health Lab Technol, 2010, 20(11): 2671 2675. [3] Gu ZW, Hong Q, Liu ZB. Medroxyprogesterone acetate once again get European into the food safety crises [J].

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<4D F736F F D D C1F5B2A82DD7F7D5DFBCF2BDE9D3C3CFEACFB8B5C4A3A1> 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