冷冻诱导前处理结合高效液相色谱-串联质谱法测定肉类食品中12种有机磷酸酯

Determination of 12 kinds of organophosphate esters in meats by cold-induced pretreatment combined with high performance liquid chromatography-tandem mass spectrometry

中文关键词:  高效液相色谱-串联质谱法  冷冻诱导前处理  有机磷酸酯  肉类

英文关键词:high performance liquid chromatography-tandem mass spectrometry  cold-induced pretreatment  organophosphate esters  meats

中文摘要:

      目的 建立一种冷冻诱导前处理结合高效液相色谱-串联质谱法快速高效检测肉类食品中12种有机磷酸酯(organophosphate esters, OPEs)的方法。方法 肉样经冷冻干燥后用乙腈提取, 提取液经十八烷基键合硅胶(C18)和N-丙基乙二胺(N-propylethylenediamine, PSA)吸附剂净化后, 加水调节样品中乙腈:水比例至35:65 (V:V), 随后–20 ℃下冷冻诱导分离富集OPEs。采用高效液相色谱-串联质谱结合稳定性同位素内标对目标化合物进行定量测定。对冷冻诱导前处理流程进行优化, 并验证该方法的线性关系、检出限、回收率、精密度和基质效应。结果 标准溶液在0.1~100.0 ng/mL范围内线性良好, 相关系数(r)均大于等于0.9993; 在1 ng/g和5 ng/g两个加标水平下, 12种OPEs平均回收率为82.6%~115.9%, 相对标准偏差小于等于15.9%; 检出限范围为0.1~19.2 pg/g, 定量限为0.2~64.0 pg/g; 采用所建立方法测定了市售肉类生鲜食品及预制菜, 实际样品中可普遍检出OPEs, 且预制菜样中OPEs污染更为严重。结论 所建立的检测方法简单、快速, 灵敏度高, 试剂耗材用量少, 适用于大批量食物样本的监测。

英文摘要:

      Objective To establish a rapid and efficient method for the determination of 12 kinds of organophosphate esters (OPEs) in meat products by cold-induced pretreatment combined with high performance liquid chromatography-tandem mass spectrometry. Methods Freeze-dried meat samples were extracted with acetonitrile and then purified using C18 and N-propylethylenediamine (PSA) adsorbents; further, the acetonitrile/water ratio of the solution was adjusted to 35:65 (V:V) and then the solution was frozen in a ?20 ℃ refrigerator to separate and enrich OPEs. The target compounds were quantified using high performance liquid chromatography-tandem mass spectrometry coupled with stable isotope internal standards. The cold-induced procedure was optimized and the linear relation, limits of detection, recovery, precision and matrix effect of the method were validated. Results Standard solutions exhibited excellent linearity across 0.1–100.0 ng/mL. The correlation coefficients (r) were all greater than or equal to 0.9993. For the tested 12 kinds of OPEs, the average recovery rates at spiking levels of 1 ng/g and 5 ng/g ranged from 82.6% to 115.9%, with relative standard deviations of lower than or equal to 15.9%. The limits of detection for OPEs ranged from 0.1 to 19.2 pg/g, while the limits of quantitation ranged from 0.2 to 64.0 pg/g. The established method was used for the measurement of fresh and pre-cooked meats and OPEs were ubiquitous in the tested real samples. Moreover, the contamination levels of OPEs in pre-cooked foods were much higher than that in fresh foods. Conclusion The established analytical method is simple, rapid and highly sensitive; and only a small quantity of reagents and consumables is needed, making it suitable for monitoring large-scale food samples.