Determination of a Variety of Organotin Compounds in Edible Vegetable Oil by Liquid Chromatography-Tandem Mass Spectrometry
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摘要: 有机锡化合物已广泛应用于食品包装材料及其生产过程中，对人体健康存在着潜在的危害。特别是食用植物油因甘油三酯（脂肪）含量较高，约占植物油的95%以上，给分析检测带来较大的基体干扰。本文采用低温冷冻提取结合固相萃取技术，建立了高效液相色谱-串联质谱法同时测定食用植物油样品中二丁基二氯化锡、二苯基二氯化锡、三丁基氯化锡、三苯基氯化锡同时分析的方法。实验对比了甲醇、乙腈、乙醇三种有机萃取溶剂分别在低温冷冻提取和常规液液振荡提取条件下的提取效率，并考察了PSA、中性氧化铝、弗罗里硅土及活性炭四种净化材料对食用油提取液的净化效果。确定了食用油中有机锡化合物的最佳提取净化方案为：以10 mL甲醇为提取溶剂在低温冷冻条件下充分提取两次，并通过50 mg活性炭净化提取液。为评价该方法的准确性，对食用油样品进行三个不同水平的添加回收实验，各有机锡化合物的平均回收率在74.2%~99.5%之间，接近或优于现行国标及相关研究（70%~120%），可应用于菜籽油、花生油、芝麻油、大豆油、玉米油及调和油等不同基质的食用植物油中有机锡化合物的同时测定。
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关键词:
- 有机锡化合物 /
- 高效液相色谱-串联质谱法 /
- 食用植物油 /
- 低温冷冻提取 /
- 分散固相萃取
Abstract: Most organotin compounds, which have been widely used in food packaging materials and production process show serious toxicity effects on human health. A high content of fat brought large matrix interference to the analysis and detection of edible vegetable oil. Methanol was selected as the extraction solvent, and the edible vegetable oil in low temperature was easily solidified. A simple and low-cost method based on high performance Liquid Chromatography-Tandem Mass Spectrometry for the simultaneous determination of four organotins in edible vegetable oil samples was developed. Four organotins including dibutyltin dichloride, tributyltin chloride, diphenyltin dichloride and triphenyltin chloride were simultaneously extracted with methanol using the low-temperature precipitation process. After being concentrated, the extracts were purified by matrix solid-phase dispersion using graphitized carbon black. Ethanol, methanol, and acetonitrile were investigated to extract organotins from edible vegetable oil samples. The recoveries of the four organotins extracted by liquid-liquid extraction and freezing extraction were also compared. The proposed method is comparable to, or even an improvement on the current national standard and related research. The adsorption abilities of some materials including primary secondary amine, alumina N, florisil, and graphitized carbon black were also studied. In order to evaluate the accuracy of the new method, the recovery was investigated. The ranges in the recoveries for the four organotins present at three levels ranged from 74.2% to 99.5%. Current work is comparable or better than those of national standards and the reported methods. The results show that the sample preparation method enables the simultaneous determination of the four organotins in peanut oil, soybean oil, corn oil, rape oil and edible blended oil samples. -
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表 1 四种有机锡化合物的MRM扫描参数
Table 1. Parameters for four organotin compounds in MRM scan mode
化合物 母离子
(m/z)子离子
(m/z)碰撞能
(eV)裂解电压
(V)DPhT 319.0 274.9 15 120 319.0 196.9 15 120 DBT 279.1 232.6 5 80 279.1 176.8 5 80 TPhT 351.0 196.8 30 180 351.0 119.6 30 180 TBT 291.1 235.1 5 60 291.1 179.1 5 60 
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表 2 四种有机锡化合物的线性、检出限、回收率及精密度 (n=5)
Table 2. The linearity, detection limits, average recoveries and precision of the method (n=5)
有机锡化合物 标准曲线 线性范围
(μg/L)R2 检出限
(mg/kg)添加量
(μg)平均回收率
(%)RSD
(%)DPhT y=21.609x+335.27 200~5000 0.9967 0.1 0.2 74.2 7.51 1.0 82.2 6.86 2.0 84.1 6.33 DBT y=22.997x-430.98 200~5000 0.9991 0.1 0.2 76.1 6.27 1.0 80.3 4.08 2.0 81.8 4.54 TPhT y=342.28x+1318.6 10~250 0.9997 0.005 0.01 82.6 7.69 0.05 85.9 5.32 0.10 94.7 8.26 TBT y=178.56x+764.61 10~250 0.9986 0.005 0.01 83.1 5.91 0.05 96.3 4.76 0.10 99.5 3.44
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