Microsoft Word 张军-二校.doc

Size: px

Start display at page:

Download "Microsoft Word 张军-二校.doc"

措品窦
7 years ago
Views:

1 5 11 Vol. 5 No Journal of Food Safety and Quality Nov., 2014 HPLC-MS/MS 张军 1*, 杜平 2 (1., ; 2., ) 摘要 : 目的 - 方法 40% (v:v), 0.22 μm, Agilent ZORBAX RX-SIL (100 mm 3.0 mm,1.8 μm) ; 0.2% +10 mmol/l A, B ; 0.4 ml/min (ESI + ), (MRM) 结果 0.2~0.5 μg/l mg/kg 92.2%~98.7%, 1.9%~6.7% 结论, 关键词 : ; ; ; Optimized detection method for chlormequat and mepiquat in cotton seed oil and its by-products using high performance liquid chromatography-mass spectrometry ZHANG Jun 1*, DU Ping 2 (1. Xinjiang Agricultural Vocational Technical College, Changji , China; 2. Xinjiang Chalkis Natural Plant High-Tech Institute, Urumqi , China) ABSTRACT: Objective To establish a detection method of chlormequat and mepiquat from cottonseed oil and by-products by high performance liquid chromatography-mass spectrometry (HPLC-MS/MS). Methods The samples were extracted by water or containing 40% acetonitrile (v:v) buffer solution, and purified by 0.22 μm filter membrane, and separated in Agilent ZORBAX RX-SIL column (100 mm 3.0 mm, 1.8 μm). The mobile phase was divided into A solution with 0.2% formic acid +10 mmol/l ammonium acetate aqueous, B solution with methanol, to elute of a flow rate at 0.4mL/min. Electrospray ionization in the positive ion mode (ESI + ), multiple reaction monitoring mode (MRM) detection. Results It showed there was a good linearity in the range of 0.2~0.5 μg/l for chlormequat and mepiquat, the recovery of standard addition was 92.2%~98.7%, the relative standard deviation was 1.9~6.7% in 1, 5, and 10.0mg/kg levels. Conclusion The method could better meet the test requirement in sensitive, accurate, and the recovery rate. KEY WORDS: cottonseed oil; cottonseed meal; chlormequat; mepiquat 基金项目 : (XJNZYKJ ) Fund: Supported by Xinjiang Agricultural Vocational Technical College Natural Science Key Project (XJNZYKJ ) * 通讯作者 :,, wusuzj@163.com *Corresponding author: ZHANG Jun, Associate Professor, Xinjiang Agricultural Vocational Technical College, No. 29, East Cultural Road, Changji , China. wusuzj@163.com

2 11, : HPLC-MS/MS 引言 (chlormequat),,, : 2-,,,,,,,, [1] (mepiquat), 鎓,, : 1, 1-,,,,,,,,,,,,, [2-5] [6], [7],,, [8], [9], (), (CAC) 50, 136, 130 [10], GB ,,, GB/T , ( ), [11],,, - [12-13] - [14-16],,, (), - (HPLC-MS/MS),,, 2 材料与方法 2.1 仪器与试剂 Agilent RRLC1200,Triple Quad MS/MS6410B - (); BS210S ( ); HR1617(); GT10-1( ); KQ5200DB( ) (, TEDIA ); ( >99%, Dr.Ehrenstorfer ); (, ); ; () 2.2 溶液的配制标准溶液的配制 : 10.0 mg ml,, mg/l :, mg/l : 4,, μg/l 缓冲溶液配制 3.85 g,, 2 g

3 3686 5, 1 L 2.3 样品前处理方法 : 3.0 g 10 ml, -(2:3,v:v) 4 ml, 3 ml,, 3 ml 3,, 5 ml, 0.22 μm : 20, 3 2, 30 min, 3.0 g 50 ml, 40% (v:v) 30 ml, 1 h 1 min, 10 min, 9000 r/min 6 min, 0.22 μm :, 3.0 g 50 ml, 30 ml, 1 min, 10 min, 9000 r/min 6 min, 0.5 ml, 40%(v:v) 25 ml, 30 min, 0.22 μm : 1 4, 2.4 实验条件色谱条件 : Agilent ZORBAX RX-SIL (100 mm 3.0 mm,1.8 μm); : A 0.2% +10 mmol/l, B ; : 0.4 ml/min; : 40 ; : 5 μl 质谱条件 (ESI + ) ; 4000 V; 350 ; 10 L/min; 276 kpa 1 3 结果与讨论 3.1 样品前处理的优化,,,,, 3 : - (2:3, v:v)- (2:3, v:v),, ( 2), -, -,,,,, - (- ),,,,,,,, - - -( 2:3, v:v), :, -;,, Table 1 表 1 矮壮素缩节胺的 MS/MS 采集参数 Chlormequat and Mepiquat chloride MS/MS analysis parameters Fragmentor/V Precursorion(m/z) Production(m/z) Collision energy/v Chlormequat () * 30 Mepiquat chloride () * *quantitative production

4 11, : HPLC-MS/MS 3687 Table 2 表 2 不同提取溶剂的提取效果比较 ( 峰面积 ) Comparison of the extraction effect from different extraction solvent (peak area) μmol/l 4 (1.; 2.) a.10.0 μmol/l ; b.; c. ; d.; e. Fig. 1 Total ion chromatogram of 10.0 μmol/l mixed standard solution and 4 samples in chlormequat and mepiquat (1.chlormequat 2. mepiquat) a.10.0 ppb mixed standard solution of chlormequat and mepiquat; b.cotton seed hulls; c.cottonseed meal; d.cottonseed oil; e.mushroom Table 3 表 3 矮壮素缩节胺在 4 种基质中的线性方程相关系数检出限和定量限 Linear equations, correlation coefficient, LOD and LOQ of chlormequat and mepiquat chloride in 4 matrixes. r LOD/(μg/L) LOQ/(μg/L) Y=1038.6X Y=1135.4X Y=836.2X Y=967.5X Y=1102.9X Y=1010.6X Y=1219.7X Y=1196.2X

5 3688 5, -, ; -,, 3.2 色谱条件的优化 C 18, 20%,,, (40%),, A HCOOH NH 4 AC, ph, HCOOH 0.1% 0.2%,,,,, 0.2% HCOOH, 线性范围和检出限 μm, (Y), (X),,, (LOD) (LOQ) 精密度和加标回收率 4, 5, 1.3, ( 4) 3.5 实际样品检测 5 2, 5, 5,,,, 0.2 μg/kg, 0.4 μg/kg, 6#,,,, Table 4 表 4 矮壮素缩节胺在 4 种样品中的加标回收率和精密度 (n=5) Recoveries and precision of chlormequat and mepiquat in 4 samples (n=5) /(mg/kg) /% RSD/% /(mg/kg) /% RSD/%

6 11, : HPLC-MS/MS 3689 Table 5 表 5 3 种样品中矮壮素缩节胺的含量 (n=4) Content of chlormequat and mepiquat in 3 samples (n=4) /(mg/kg) /(mg/kg) 结论 HPLC-MS/MS, mg/kg %~98.7%, 1.9%~6.7%,, : 1.37 mg/kg~8.60 mg/kg, 1.90 mg/kg~4.32 mg/kg; 0.11 mg/kg~0.58 mg/kg, 0.16 mg/kg~0.41 mg/kg; mg/kg~0.068 mg/kg, 0.29 mg/kg~0.47 mg/kg 参考文献 [1],,,. [J]., 2008, 10(34): Zhang X, Jin F, Qian YZ, et al. Research progress in determination of chlormequat chloride and mepiquatchloride in food [J]. Food Fer Ind, 2008, 10(34): [2] Tomer H, Blottner S, Kuhla S, et al. Influence of chlorochloline chloride treated wheat on selcted in vitro fertility parameters in mice [J]. Reprod Toxicol, 1999, 13: [3] Sorensen MT, Danielsen V. Effect of the plant growth regulator, chlormequat, on mammalian fertility [J]. Int J Androl, 2006, 29: [4] Hagemeister H, Kuhla S, Langhammer M, et a1. Study of the influence of chlorochorine chloride (CCC. chlormequat) on selected fertility parameters in lab mice [J]. Schrift Bundes Ernaehrung Landwirtsch Forsten Reihe A Angewandle Wissenschaft, 1999, 483: [5] Andersen HR, Anderson A. Environ. Comparison of short-term estrogenicity tests for identification of hormone-disrupting chemicals [J]. Environ Health Prospect, 1999, 107(Supply 1): [6]. [M]. :, 1997: 473. Zhang YB. Pesticide [M]. Beijing: Chinese Material Press, 1997: 473. [7],,. [J]., 2010, 47(10): Feng S, Zhang XL, Wang JD. Progress of analytical method of determination of chlormequat chloride and mepiquant chloride [J]. Xinjiang Agric Sci, 2010, 47(10): [8]. [J]., 2005, 30(1): Du W. Characteristic and refining technology comparison of cottonseed oil [J]. Chin Oil fat, 2005, 30 (1): [9],,. [J]., 2010, 35(7): Lan HB, Zhang L, Yun Z. Comprehensive utilization and deep

7 processing of cottonseed [J]. Chin Oil fat, 2010, 35(7): [10],,,. CCPR 46 [J]., 2014, 16: 336. Wu LH, Duan LF, Song WC, et al. The new progress of formulating standards for pesticides residue limits in The forty-sixth annual meeting of CCPR Chinese [J]. J Pes Sci, 2014, 16: 336. [11],,,. [J]., 2011, 29(3): Zhou X, Xu JG, Chen ZD, et al. Simultaneous determination of chlormequat chloride and mepiquat chloride inplants by mobile phase ion chromatography [J]. Chin J Chrom, 2011, 29(3): [12] GB/T [S]. :, GB/T Determination of the residues of chlorcholine chloride in cereals[s]. Beijing: China Standards Press, [13],,,. - [J]., 2008, 18(6): Zhao YX, Song GL, Zhang J, et al. Determination of chlormequcat chloride residue in grains by gas chromatography-mass spectrometry [J]. Chin J Heal Lab, 2008, 18(6): [14],,,. - [J]., 2007, 35(10): Wang JH, Lu XY, Huang M, et al. Rapid screening and confirmation of Chlormequat and Mepiquat residues in tomato and its products using liquid chromatography with electrospray tandem mass spectrometry[j]. Chin J An chem, 2007, 35(10): [15] Zhao Y, Lazou K, Schelfautm, et al. Determination of chlormequat residues in pears and pear concentrates by benchtop LC-ESI-MS[J]. Chromatogr, 2000, 51(9): [16] Evans C S, Starin J R, Goodall D M, et al. Improved sensitivity in detection of chlormequat by liquid chromatography-mass spectrometry[j]. J Chromatogr: A, 2000, 897(1/2): 作者简介 ( 责任编辑 : 白洪健 ) 张军, 副教授, 主要研究方向为食品科学及安全管理 wusuzj@163.com

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.