改进的QuEChERS结合RPLC-TMS测定水产品中生物胺的研究

Determination of biogenic amines in aquatic products by modified Qu ECh ERS method and liquid chromatography-mass spectrometry

采用改进的QuEChERS方法，利用液相色谱-串联质谱（RPLC—TMS）检测，建立了几种水产品中生物胺的分析方法。样品用乙腈＋甲醇（9＋1）提取，无水硫酸钠除去水分，经乙二胺-N-丙基硅烷（PSA）和C18混合粉末净化，采用HILIC柱，以乙腈／1％甲酸水溶液为流动相梯度洗脱进行液相色谱分离。质谱分析采用电喷雾正离子电离，多反应监测模式，外标法定量。结果显示6种生物胺在10～200ng／mL范围线性关系良好。方法的定量限（LOQ，信噪比为10）为0．10mg／kg。加标水平在0．10mg／kg时，鱼、虾、蟹及鱿鱼四种阴性基质中加标的回收率在74．18％~90．15％之间，相对标准偏差（RSD，11=6）在2．22％～8．04％之间。结果表明本方法简便、快速、安全、适用于水产品中生物胺含量的定性和定量检测。

A modified QuEChERS method followed by liquid chromatography-tandem mass spectrometric analysis was developed for the determination of biogenic amines in aquatic products. The samples was diluted with acetonitrile/methanol solution （9/1）and cleaned up with primary secondary amine （PSA）and Octadecylsilane （C18） sorbent.The separation of biogenic amines was performed by hydrophilic interaction liquid chromatography （HILIC） column and gradiently eluting with acetonitrile/formic acid- water （1%） without derivatization. Biogenic amines were analyzed by positive electrosprary ionization （ESI^＋） tandem mass spectrometry under multiple reaction monitoring（MRM）mode.Quantification was achieved using external standard method.The linearities were excellent in the range of 10-200 ng/mL.The limits of quantification（ LOQ,S/N = 10）were 0.10 mg/kg.The recoveries of biogenic amines spiked in matrices were between 74.18% and 90.15% at the spiked levels of 0.10 mg/kg.The relative standard deviations （ RSDs, n = 6） were in the range of 2.22% -8.04%.The method （ quick, easy, safe） could meet the requirements of the daily work for the determination of biogenic amines in aquatic products.