非衍生化液相色谱-串联质谱法测定动物源性食品中8种生物胺

Determination of eight biogenic amines in animal-derived foodstuffs by high performance liquid chromatographytandem mass spectrometry without derivatization

采用液相色谱-串联质谱技术建立了同时测定动物源性食品中组胺(HIS)、色胺(TRP)、2-苯乙胺(2-PHE)、腐胺(PUT)、尸胺(CAD)、酪胺(TYR)、亚精胺(SPD)和精胺(SPM)8种生物胺(BAs)的分析方法。样品用乙腈-甲酸水溶液提取,用强阳离子交换柱(MCX)净化。在不进行衍生化的条件下,采用亲水作用色谱(HILIC)柱、以5mmol/L的乙酸铵溶液和甲醇为流动相分离8种生物胺。结果表明,8种生物胺的线性范围为0.001～100μg/L,相关系数(r2)均大于0.99。方法的检出限(LODs,信噪比为3)在0.001～1μg/kg之间,定量限(LOQs,信噪比为10)在0.003～5μg/kg之间。在8种基质中3个加标水平的回收率都在73.9%～106.3%之间,加标含量范围为0.003～50μg/kg,相对标准偏差(RSD,n=6)在5.65%～18.6%之间。方法的灵敏度和回收率高,选择性好,能满足日常动物源性食品检测工作的要求。

A method for the determination of histamine （ HIS）, tryptamine （ TRP）, 2-phenyle-thylamine （2-PHE）, putrescine （PUT）, cadaverine （CAD）, tyramine （TYR）, spermidine （SPD）, spermine （SPM） in animal-derived foodstuffs was established using high performance liquid chromatography-tandem mass spectrometry. The samples were extracted with acetoni- trile-formic acid aqueous solution, and purified with strong cationic exchange （MCX） cartridge. Without derivatization, the eight biogenic amines （BAs） were separated by hydrophilic interaction chromatographic （HILIC） column with the mobile phases of 5 mmol/L ammonium acetate and methanol. The linearities were excellent in the range of 0. 001 - 100μg/L with the correlation coefficients above 0.99. The limits of detection （ LODs, S/N = 3） of the method were between 0. 001μg/kg and 1 μg/kg, and the limits of quantification （ LOQs, S/N = 10） were between 0. 003μg/kg and 5 μg/kg. The recoveries of BAs spiked in eight matrices were between 73.9% and 106.3% at the spiked levels ranged from 0. 003 μg/kg to 50 μg/kg. The relative standard deviations （RSDs, n = 6） were in the ranges of 5.65% -18.6%. The method can meet the requirements of the daily work for the determination of BAs in animal-derived foodstuffs.