凝胶净化/超高效液相色谱电喷雾质谱法检测调味油中11种禁用偶氮染料及罗丹明B

摘要

An analytical method was developed for the simultaneous determination of 11 banned azo-dyes (Sudan red I , Sudan red II , Sudan red III, Sudan red IV, Sudan red 7B, Sudan red G, Sudan yellow, Sudan orange G, Sudan blue II, toluidine red, para red) and rhodamine B in seasoning oil based on gel permeation chromatography followed by ultra performance liquid chromatogra-phy - tandem mass spectrometry ( UPLC - MS/MS). The seasoning oil samples were extracted with cyclohexane - ethyl acetate (1 : 1) , and then purified by gel permeation chromatography to remove the high molecular weight of interferences (e. g. fat, oil and natural pigments). Twelve target compounds were separated on an ACQUITY UPLC(R) BEH C18 column with 0. 1% formic acid and acetoni-trile as mobile phase by gradient elution, and detected by MS/MS under positive mode with multiple reaction monitoring (MRM). Good linearities for 12 dyes were achieved over the range of 1 -50 μg/L. The quantitation limits of 12 dyes in seasoning oil samples were in the range of 0. 2 -2. 5 μg/kg. The mean recoveries at three spiked level(5, 20, 40 μg/L) ranged from 54% to 125% , with relative standard deviations ( RSDs) of 2. 5% - 17. 2% . The method was used to analyze 35 seasoning oil samples taken randomly from the local market, and rhodamine B was found in 2 of the samples. The established method could be applied in the simultaneous extraction and purification of 11 azo-dyes and rhodamine B in seasoning oil matrix, and is suitable for the routine detection of illegally additive dyes in seasoning oil due to its simplicity and high sensitivity.%建立了凝胶渗透色谱(GPC)净化/超高效液相色谱-电喷雾串联四极杆质谱(UPLC - MS/MS)同时检测调味油中11种脂溶性偶氮类工业染料(苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ、苏丹红7B、苏丹红G、苏丹黄、苏丹橙G、苏丹蓝Ⅱ、甲苯胺红、对位红)和罗丹明B的分析方法.样品经乙酸乙酯-环己烷(1∶1)提取,采用凝胶渗透色谱(GPC)去除大分子油脂、天然色素等于扰物质；以乙腈-0.1％甲酸为流动相,目标化合物在梯度洗脱条件下经C18柱分离后采用多离子反应监测(MRM)正离子模式进行检测.结果表明:调味油中12种工业染料的线性范围为1～50 μg/L,定量下限(LOQ)为0.2～2.5 μg/kg,在5、20、40μg/L3个加标水平下的回收率为54％ ～ 125％,相对标准偏差为2.5％～17.2％.随机抽取市售35份样品进行检测,其中两份样品检出罗丹明B.该方法操作简便、灵敏度高,实现了11种禁用偶氮染料和罗丹明B的同时提取和净化,适合于调味油中非法添加脂溶性偶氮工业染料和罗丹明B的筛查与确证.