超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯

引用本文: 杨光勇, 郭苍亭, 薛光, 郭金喜. 超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯[J]. 色谱, 2020, 38(12): 1388-1395. doi: 10.3724/SP.J.1123.2020.03020 shu

Citation: YANG Guangyong, GUO Cangting, XUE Guang, GUO Jinxi. Determination of 15 3-chloro-1,2-propanediol fatty acid esters in vegetable oils and fritters by ultra performance convergence chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(12): 1388-1395. doi: 10.3724/SP.J.1123.2020.03020 shu

超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯

杨光勇 ^{1,
,} ,
郭苍亭 ^2, ,
薛光 ^1, ,
郭金喜 ^1,

1.
新疆维吾尔自治区产品质量监督检验研究院, 新疆乌鲁木齐 830011;
2.
乌鲁木齐市疾病预防控制中心, 新疆乌鲁木齐 830026

通讯作者: 杨光勇, E-mail:314808113@qq.com

基金项目:
新疆生产建设兵团食品安全风险监测计划项目（兵市监发[2019]25号）.

摘要: 建立了超高效合相色谱-三重四极杆质谱（UPC²-MS/MS）测定食用植物油和油条中15种3-氯-1，2-丙二醇脂肪酸酯（3-MCPDE）含量的方法。3-MCPDE的结构与甘油酯极为相似，因此很难将其从植物油中分离出来。为降低基质干扰，实验以不同极性的溶剂依次洗脱载有样品的氨基填料层析柱，用UPC²和ACQUITY QDa质谱检测器分析每单元洗脱液以绘制洗脱曲线。分段收集的洗脱液经混合、浓缩和过滤后，以Viridis HSS C18 SB色谱柱（150 mm×2.1 mm，1.8 μm）为分析柱，超临界CO₂和40%乙腈甲醇溶液（含0.1%甲酸）为流动相梯度洗脱，以97%异丙醇水溶液（含0.2%氨水）为补偿液，用配备电喷雾电离源的三重四极杆质谱在正离子、多级反应监测模式下测定，外标法定量。结果表明：15种3-MCPDE在各自范围内线性关系良好（相关系数（r²）≥0.9973），检出限为0.01~0.68 μg/L（S/N=3），定量限为0.04~1.74 μg/L（S/N=10）；在3个加标水平下的平均回收率为81.6%~98.5%（n=9），相对标准偏差为1.8%~6.4%。利用该法对实际样品进行检测，并对考察范围以外的疑似3-MCPDE化合物进行了分析。该法基质兼容性强，操作简便，灵敏度高，专属性好，绿色环保，较传统方法极具优势，用于测定植物油和油条中3-MCPDE单体的种类和含量，结果满意；但该法也存在定性能力较弱、定量过度依赖单体标准品、单酯较二酯离子化效率低等问题，可作为后期研究关注的方向。

关键词:

English

Determination of 15 3-chloro-1,2-propanediol fatty acid esters in vegetable oils and fritters by ultra performance convergence chromatography-tandem mass spectrometry

1.
Xinjiang Uygur Autonomous Region Product Quality Supervision and Inspection Institute, Urumqi 830011, China;
2.
Urumqi Center for Disease Control and Prevention, Urumqi 830026, China

Corresponding author: YANG Guangyong, 314808113@qq.com

Received Date: 19 March 2020
Fund Project:
Food Safety Risk Monitoring Program Project of Xinjiang Production and Construction Corps (Market Supervision and Administration Bureau of Corps, [2019] Reference No. 25).

Abstract: The presence of 3-chloro-1,2-propanediol fatty acid esters (3-MCPDE) in food and processed materials has recently become a topic of concern because of the toxicity of their metabolites. 3-MCPDE structurally similar to glyceride, which makes it difficult to separate or extract them from oils and fritters. A method based on ultra performance convergence chromatography-tandem mass spectrometry (UPC²-MS/MS) was established for the determination of 15 3-MCPDE in vegetable oils and fritters. Amino-packed columns were used to purify the samples. The analytical conditions were optimized, and the matrix effect was investigated. The sample was treated by column chromatography to remove glyceride and free fatty acids, which induce strong matrix effects. The amino-packed column was eluted with hexane and hexane-ethyl acetate (6:4, v/v). Every 1 mL of the eluent was analyzed using a UPC² and ACQUITY QDa detector. Elution curves were drawn based on the testing data and used to determine the collection volume. The collection volumes for 3-chloro-1,2-propanediol diesters and monoesters according to the elution curves were 7-14 mL and 3-9 mL. The collected eluent was mixed and dried under nitrogen flow at a temperature of 60℃. A hexane-isopropanol (98:2, v/v, 1 mL) mixture was used to dissolve the residue. The resulting solution was separated on a Viridis HSS C18 SB column (150 mm×2.1 mm, 1.8 μm) under gradient elution. Supercritical carbon dioxide and methanol (containing 40% acetonitrile and 0.1% formic acid) were used as the mobile phases, and the flow rate was 1 mL/min. The separated compounds were analyzed by tandem MS with an electrospray ionization (ESI) source in positive and multiple reaction monitoring modes. Water (containing 97% isopropanol and 0.2% ammonia water) was used as the auxiliary pump mobile phase, and the flow rate was 0.2 mL/min. The method showed good linear relationships in the range of 0.5-100 μg/L (r² ≥ 0.9973). The limits of detection (LODs) and limits of quantification (LOQs) were 0.01-0.68 μg/L (S/N=3) and 0.04-1.74 μg/L (S/N=10), respectively. The average recoveries (n=9) at the three spiked levels were in the range of 81.6%-98.5%. The relative standard deviations were in the range of 1.8%-6.4%. The matrix effects in the case of the oils and fritters were weak. The developed method was used to detect 44 oil samples and eight fritter samples. Meanwhile, some suspect 3-MCPDE compounds outside the scope of the investigation were analyzed based on their primary and secondary mass spectra. The detection rates of 3-MCPDE in oils and fritters were 84.1% and 87.5%, and their amounts were in the range of 0.024-4.481 mg/kg and 0.018-1.144 mg/kg, respectively. The detection rates of 3-MCPDE in rapeseed oil were higher compared to those for other kinds of oil. The method is specific, fast, simple, accurate, reliable, and environmentally friendly, in addition to being more sensitive than other methods and showing better matrix compatibility for oils. This method has been successfully used to determine the types and amounts of 3-MCPDE in vegetable oils and fritters. The research findings provided accurate data to assess the exposure risk of 3-MCPDE. The results of our experiment also provided valuable information for elucidating the formation mechanism of 3-MCPDE. The proposed method can be used to analyze waste edible oil based on large amounts of analysis data. However, this method has some limitations. The resolution ratio of the mass spectrometer used in this method is too low for the qualitative analysis of unknown compounds. The qualitative results for the suspect 3-MCPDE compounds are not particularly accurate, and a large variety of monomer standards are required for the quantitative determination of 3-MCPDE. The 3-MCPDE standards are expensive, and there is limited choice of these standards; moreover, they are difficult to synthesize. The poor ionization yield of 3-chloro-1,2-propanediol monoesters under the ESI conditions resulted in high LODs. Hence, it is necessary to develop a method for increasing the ionization of monoesters, for example, via derivatization.

Key words:

1. [1] European Food Safety Authority. Risks for Human Health Related to the Presence of 3- and 2-Monochloropropanediol (MCPD), and Their Fatty Acid Esters, and Glycidyl Fatty Acid Esters in Food. (2016-05-10). https://efsa.onlinelibrary.wiley.com/doi/full/10.2903/j.efsa.2016.4426
2. [2] Xiang X L, Zhao B, Li C S, et al. China Oils and Fats, 2017, 42(7):59 向晓玲, 赵波, 李春松, 等. 中国油脂, 2017, 42(7):59
3. [3] Ren W X, Liu Y L, Ma Y X, et al. China Oils and Fats, 2018, 43(4):57 任我行, 刘玉兰, 马宇翔, 等. 中国油脂, 2018, 43(4):57
4. [4] Franke K, Strijowski U, Fleck G, et al. LWT-Food Sci Technol, 2009, 42(10):1751
5. [5] Beekman J, MacMahon S. Food Addit Contam A, 2020, 37(1):48
6. [6] Zhang Y B.[MS Dissertation]. Wuxi:Jiangnan University, 2018 张渊博.[硕士学位论文]. 无锡:江南大学, 2018
7. [7] Inagaki R, Ito F, Shimamura Y, et al. Food Addit Contam A, 2019, 36(2):236
8. [8] Wong Y H, Lai O M, Abas F, et al. J Am Oil Chem Soc, 2017, 94(6):759
9. [9] Beekman J K, Grassi K, MacMahon S. Food Addit Contam A, 2020, 37(3):374
10. [10] Arisseto A P, Marcolino P F C, Vicente E. Food Addit Contam A, 2015, 32(9):1431
11. [11] Cui X, Ding J, Zou J H, et al. Food Science, 2014, 35(12):93 崔霞, 丁颢, 邹建宏, 等. 食品科学, 2014, 35(12):93
12. [12] Graziani G, Gaspari A, Chianese D, et al. Food Addit Contam A, 2017, 34(11):1893
13. [13] Lu Y P, Jin S M, Jiang X M, et al. China Oils and Fats, 2015, 40(11):79 卢跃鹏, 金绍明, 江小明, 等. 中国油脂, 2015, 40(11):79
14. [14] Hua C L, Zhang L J, Wang H T, et al. China Oils and Fats, 2016, 41(6):52 华从伶, 张连军, 王海涛, 等. 中国油脂, 2016, 41(6):52
15. [15] Xiong L, Zhou H, Liang J. Modern Preventive Medicine, 2017, 44(21):3883 熊丽, 周鸿, 梁健. 现代预防医学, 2017, 44(21):3883
16. [16] Jiang Z A, Lv F, Zhang X L, et al. Acta Scientiae Circumstantiae, 2018, 38(7):2941 姜子岸, 吕芬, 张晓岚, 等. 环境科学学报, 2018, 38(7):2941
17. [17] Xing H Z, Fang B, Chang Q Y, et al. Journal of Chinese Institute of Food Science and Technology, 2019, 19(5):39 邢寒竹, 方冰, 常巧英, 等. 中国食品学报, 2019, 19(5):39
18. [18] Zhang L J.[MS Dissertation]. Wuxi:Jiangnan University, 2015 张立娟.[硕士学位论文]. 无锡:江南大学, 2015
19. [19] Liu M, Gao B Y, Qin F, et al. Food Chem Toxicol, 2012, 50(10):3785
20. [20] Liu M, Huang G R, Wang T T Y, et al. Toxicol Sci, 2016, 151(1):181
21. [21] Huang C Q, Chen Q K, Chen L, et al. Chinese Journal of Chromatography, 2019, 37(10):1048 黄超群, 陈钦可, 陈丽, 等. 色谱, 2019, 37(10):1048
22. [22] Zelinkova Z, Giri A, Wenzl T. Food Control, 2017, 77(1):65
23. [23] Hrncirik K, Zelinkova Z, Ermacora A. Eur J Lipid Sci Technol, 2011, 113:361
24. [24] Zhou H R, Jin Q Z, Wang X G, et al. Food Control, 2014, 36(1):111
25. [25] Li H L, Chen D W, Miao H, et al. J Chromatogr A, 2015, 1410:99
26. [26] LiuW J.[MS Dissertation]. Fuzhou:Fujian Medical University, 2017 刘文菁.[硕士学位论文]. 福州:福建医科大学, 2017
27. [27] Hori K, Matsubara A, Uchikata T, et al. J Chromatogr A, 2012, 1250:99
28. [28] Haines T D, Adlaf K J, Pierceall R M, et al. J Am Oil Chem Soc, 2011, 88:1
29. [29] Liu H H, Chen H L, Xu X X, et al. Chinese Journal of Food Hygiene, 2016, 28(3):327 刘红河, 陈慧玲, 许欣欣, 等. 中国食品卫生杂志, 2016, 28(3):327
30. [30] Custodio-Mendoza J A, Lorenzo R A, Valente I M, et al. J Chromatogr A, 2018, 1548:19
31. [31] MacMahon S, Ridge C D, Begley T H. J Agric Food Chem, 2014, 62:11647
32. [32] Hori K, Koriyama N, Omori H, et al. LWT-Food Sci Technol, 2012, 48:204
33. [33] Zhang X H, Qi C, Tao G J, et al. China Oils and Fats, 2018, 43(11):127 张星河, 齐策, 陶冠军, 等. 中国油脂, 2018, 43(11):127
34. [34] Lin C H, Xie X Q, Fan N L, et al. Chinese Journal of Chromatography, 2015, 33(4):397 林春花, 谢贤清, 范乃立, 等. 色谱, 2015, 33(4):397
35. [35] Li W L, Li X M, Li G R, et al. Chinese Journal of Chromatography, 2016, 34(8):795 李武林, 李雪敏, 李根容, 等. 色谱, 2016, 34(8):795
36. [36] Shang Y.[MS Dissertation]. Wuxi:Jiangnan University, 2016 尚月.[硕士学位论文]. 无锡:江南大学, 2016
37. [37] Fu W S, Wu S M, Hua J, et al. Chinese Journal of Analytical Chemistry, 2014, 42(4):469 傅武胜, 吴少明, 华娟, 等. 分析化学, 2014, 42(4):469
38. [38] Waters Corporation. Fast and Simple Free Fatty Acids Analysis Using UPC²-MS. (2013-07-02). https://www.waters.com/waters/library.htm?locale=en_US&cid=134658367& lid=134753626

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯

通讯作者: 杨光勇, E-mail:314808113@qq.com

English

Determination of 15 3-chloro-1,2-propanediol fatty acid esters in vegetable oils and fritters by ultra performance convergence chromatography-tandem mass spectrometry

Corresponding author: YANG Guangyong, 314808113@qq.com

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯

通讯作者: 杨光勇, E-mail:314808113@qq.com

English

Determination of 15 3-chloro-1,2-propanediol fatty acid esters in vegetable oils and fritters by ultra performance convergence chromatography-tandem mass spectrometry

Corresponding author: YANG Guangyong, 314808113@qq.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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