Microsoft Word 肖家勇-二校 93

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1 7 1 Vol. 7 No Journal of Food Safety and Quality Jan., 2016 肖家勇 1, 李莉 2, 丁利 1, 朱绍华 1, 龚强 1, 付善良 1, 王利兵 (1.,,, ; 2., ) 1* 摘要 : 目的 6 - (HPLC-MS/MS) 方法 Agilent ZORBAX SB-C 18, -0.1%,, 0.35 ml/min; (ESI+), (MRM);, 结果 6 (r ), 0.04~0.2 μg/kg, 0.01~0.04 μg/kg 81.9%~103.9%, 7.2% 结论,, 6 关键词 : ; - ; Determination of phthalates in food by gel permeation chromatography-high performance liquid chromatography-tandem mass spectrometry XIAO Jia-Yong 1, LI Li 2, DING Li 1, ZHU Shao-Hua 1, GONG Qiang 1, FU Shan-Liang 1, WANG Li-Bing 1* (1. Technology Center of Hunan Entry-Exit Inspection and Quarantine Bureau, State Key Laboratory of Food Safety Testing, Hunan Key Laboratory of Food Safety Science & Technology, Changsha , China; 2. Chinese Academy of Inspection and Quarantine, Beijing China) ABSTRACT: Objective To establish a method for the simultaneous determination of 6 kinds of phthalates in food by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Methods The samples were separated by an Agilent ZORBAX SB-C 18 column with a mobile phase of methanol-0.1% formic acid/water in gradient elution mode at the flow rate of 0.35 ml/min. The mass spectrometry worked in the positive ion mode, and multiple reaction monitoring (MRM) was adopted for the quantification of the analytes. Samples were purified by gel permeation chromatography (GPC) after extraction with organic solvents. Results A good linearity for 6 kinds of phthalates was achieved, with all correlation coefficients more than Average recoveries of 6 analytes at three spiked level were ranged from 81.9% to 103.9%, with RSDs less than 7.2%. The limits of quantification and detection of the method was 0.04~0.2 μg/kg and 0.01~0.04 μg/kg, respectively. Conclusion The established method is sensitive and simple, and suitable for 基金项目 : (2012BAD29B05) Fund: Supported by the National Key Technology Research and Development Program of the Ministry of Science and Technology of China (2012BAD29B05) * 通讯作者 :,, wanglb0419@126.com *Corresponding author: WANG Li-Bing, Researcher, Hunan Key Laboratory of Food Safety Science Technology, Technology Center of Hunan Entry-Exit Inspection and Quarantine Bureau, Changsha , China. wanglb0419@126.com

2 92 7 the determination of 6 kinds of phthalates in food. KEY WORDS: phthalates; high performance liquid chromatography-tandem mass spectrometry; gel permeation chromatography 1 引言 (phthalic acid esters, PAEs),,, [1-3], PVC,,, 60%,,, [4,5] [6],, - [7-10],,, -, - [11] (DHXP)(BBP) (DCHP)(DHP) (DPRP) (DBEP) 6, - 6,, 2 材料与方法 2.1 材料试验材料, 仪器与试剂 API 4000 ( ); 20A (); ( Sigma ); (Turbo Vap II, Caliper ); GPC (GPC Vario, Lctech ); (KQ-250E, ) HPLC ( Merck ), ( ); (DHXP) (BBP) (DCHP) (DHP) (DPRP) (DBEP) ( 99%, Sigma ); ( Millipore ) 2.2 方法标准溶液的配制 (DHXP) (BBP) (DCHP) (DHP) (DPRP) (DBEP) 10.0 mg, 10 ml, 1.0 mg/ml, 4 1 ml 10 ml,, 100 μg/ml, 4, 1.0 μg/ml 仪器条件 : Agilent ZORBAX SB-C 18 (100 mm 2.1 mm, 3.5 μm); : A, B 0.1%, : 0~10.0 min, 50%~2%B, 10.0~15.0 min, 2%B, 15.1 min, 50%B, 15.0~20.0 min, 50%B; : 10 μl; : 0.35 ml/min; : 35 (ESI); : ; (Gas1): 413 kpa(60.00 psi); (Gas2): 448 kpa(65.00 psi); (IS):

3 1, : V; (Cur): 172 kpa(25.00 psi); (TEM): 500 ; : (MRM) 样品前处理 5.0 g 20 ml, 10 ml 2,, 40, 7.0 ml - (1:1, V:V), GPC GPC - (1:1, V:V), 5.0 ml/min; s; 6400 μl GPC 40, 1.0 ml, 0.45 µm HPLC-MS/MS 3.2 质谱条件的优化 (ESI+), (FIA), 6 (MRM), 6, 1 6 MRM 2 表 1 多反应检测扫描模式检测 6 种邻苯二甲酸酯类物质的质谱参数 Table 1 MS parameters for the analysis of 6 kinds of PAEs m/z m/z DP/V CE/V EP/V CXP/V 3 结果与讨论 3.1 色谱条件的优化, 6, ESI+,,,, 6,, ( 1), -0.1% C 18,,,, 98%, DPRP BBP DCHP DHXP DHP DBEP * 149* * * * * * Fig. 1 Effect of mobile phase modifier

4 干扰的排除,, ;, ; 24 h 2, 2 6 (a 5 ng/ml, b ) Fig. 2 MRM chromatograms of 6 kinds of PAEs (a: 5 ng/ml standard solution, b: blank solution) 3.5 线性范围与检测限 6, 2.2.2,,, 6, (LOD) (LOQ) 3 10 (S/N), 2 2,, GB/T , 0.01~0.04 μg/kg 3.3 GPC 条件的优化 6 ( 0.1 µg/ml), GPC, 12 min, 12 min 2 min, HPLC-MS/MS, 6 ( 3) 3, 6 14~30 min 表 2 6 中邻苯二甲酸酯的线性范围检测限及定量限结果 Table 2 Linear ranges, limit of detection and limit of quantification of 6 kinds of PAEs (ng/ml) LOD(μg/kg) LOQ(μg/kg) DPRP 0.2~ BBP 0.2~ DCHP 0.2~ DHXP 0.2~ DHP 0.2~ DBEP 1.0~ Fig. 3 Elution curve of 6 kinds of PAEs

5 1, : 准确度与精密度 6,, 4 24 h, 3,, 6, (RSD%) 实际样品的检测 ( ) 6, 6 DPRP DHXP DBEP 19, BBP DCHP ( 42.1% 31.6%), 0.04~0.77 µg/kg, DHP ( 2 ), 0.04 µg/kg 4 4 结论 - (HPLC-MS/MS) 6,,, 表 3 3 个添加水平的回收率和精密度 (n=6) Table 3 Recoveries and precisions for blank sample spiked at 3 different levels (n=6) DPRP BBP DCHP DHXP DHP DBEP (µg/kg) (%) RSD(%) MRM Fig. 4 MRM chromatogram of sample

6 96 7 参考文献 [1] Janjua NR, Mortensen GK, Andersson AM, et al. Systemic uptake of diethyl phthalate, dibutyl phthalate, and butyl paraben following whole-body topical application and reproductive and thyroid hormone levels in humans [J]. Environ Sci Technol, 2007, 41(15): [2],. [J]., 2006,16(3): Dong FY, Yan J. Regulations of EU and American on disabled PAEs, and the beginning and end of their introduction [J]. Inspect Quarant Sci, 2006, 16(3): [3],,,. [J]., 2007, 24 (10): Wang XY, Lin XT, Ke HM, et al. Investigation of environmental pollutants of PAEs in Beijing families [J]. J Environ Heal, 2007, 24 (10): [4],. PVC [J]., 2007, 28(8): Li BP, Lin QB. Review on the migration of chemicals from PVC plastic packaging materials to foodstuffs [J]. Sci Technol Food Ind, 2007, 28(8): [5]. SPE-GC-MS 18 [J]., 2010, 31(11): Huang YH. Simultaneous determination of 18 phthalate acid esters migration in milk powder by solid phase extraction coupled with gas chromatography-mass spectrometry [J]. Food Res Dev, 2010, 31(11): [6],,,. [J]., 2007, 24(9): Wang XY, Lin XT, Ke HM, et al. Researches of effects of phthalate esters on rodents and human [J]. J Environ Heal, 2007, 24(9): [7] Guo BY, Wen B, Shan XQ, et al. Separation and determination of phthalates by micellar electrokinetic chromatography [J]. J Chromatogr A, 2005, 1095: [8] Carrillo JD, Martinez MP, Tena MT. Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry use of deuterated phthalates as internal standards [J]. J Chromatogr A, 2008, 1181: [9] Caroline S, Mireille MV, David B, et al. Development and validation of methods for the trace determination of phthalates in sludge and vegetables [J]. J Chromatogr A, 2005, 1072: [10],,,. [J]., 2008, 6: Xu XH, Fang XM, Ding ZP, et al. Determination of phthalic acid esters in milk by high performance liquid chromatography[j]. Chem Bull, 2008, 6: [11],,,. -., 2007, 25(5): Liu C, Li LS, Wang SW, et al. Determination of phthalates in drinks by HPLC-ESI/MS [J]. Chin J Chromatogr, 2007, 25(5): 作者简介 ( 责任编辑 : 白洪健 ) 肖家勇, 高级工程师, 主要研究方向为食品安全检测 xiaojy@hn.ciq 王利兵, 研究员, 主要研究方向为食品安全检测 Wanglb@hn.ciq

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min 25 4 2013 8 监测技术 5 1 2 1 ( 1. 江苏省疾病预防控制中心, 江苏南京 210009; 2. 南京医科大学第二附属医院, 江苏南京 210029) 5 Phenomenex kinetex C 18 2. 6 μm 4. 6 mm 150 mm 10 mmol /L ph 2. 5 + 60 40 DAD 280 nm 5 20. 0 mg /L ~ 100 mg /L 0.