高效液相色谱-串联质谱法测定食品中曲酸

Determination of kojic acid in foods using high performance liquid chromatography-tandem mass spectrometry

建立了食品中新型防腐剂曲酸的高效液相色谱-串联质谱的定量测定方法。动物禽肉、鱼虾甲壳类、酱菜类、水果蔬菜、面制品等固体样品经乙腈提取;酱及酱油、醋、酒、饮料、糖浆等液体样品经水稀释,乙酸锌和亚铁氰化钾沉淀蛋白;以C18柱为分离柱,流动相为乙腈和5 mmol/L乙酸铵甲酸溶液,采用电喷雾串联四极杆质谱进行检测。选择1个母离子和2个子离子进行选择反应监测,以13C6-曲酸作为内标,选择信号最强的子离子进行定量测定。固体类基质中的定量限(按信噪比(S/N)大于10计)为0.1 mg/kg;液体类基质中的定量限为2.5 mg/kg。在0.1～2.0 mg/L范围内呈现良好的线性关系,相关系数r>0.99。各种基质在3个添加水平的平均回收率在72.6%～114%之间,相对标准偏差均小于11.4%。本方法简单实用,准确可靠,适用范围包括了食品中可能使用曲酸这种食品添加剂的大部分基质,可以满足进出口食品中曲酸的定性和定量要求。

The quantification method for the determination of kojic acid in foods using high per- formance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was developed. For solid samples, the kojic acid was extracted with acetonitrile; for liquid samples, they were diluted with water, then deproteinized by the deposition with zinc acetate and potassium ferro- cyanide. The analytes were determined by HPLC-MS/MS on a C18 column with 5 mmol/L ammonium acetate/formic acid solution as mobile phases. The analysis of kojic acid was per- formed under selected reaction monitoring （SRM） mode by selecting one parent ion and two daughter ions as qualitative ions with [ 13^ C6 ]-kojic acid as the internal standard, and the most abundant daughter ion as quantitative ion. The limits of quantification （S/N 〉 10 ） were 0. l mg/kg for the solid samples, and 2.5 mg/kg for the liquid samples. The good linearity （ r 〉 0.99） was achieved for the target compound over the range of 0. 1 - 2.0 mg/L. The recoveries at three levels for kojic acid were from 72.6% to 114% with the relative standard deviations no more than 11. 4%. The method is simple and practical, and can be applied to most of matrices which may contain kojic acid as food additives. It can meet the qualitative and quantitative requirements for import and export foods.