分子印迹固相萃取/液-质谱联用法测定烟熏鲟鱼中苯并芘

目前常规苯并芘检测方法存在着专一性不强、灵敏度低等问题,为精确测定市售烟熏鲟鱼中痕量3,4-苯并芘(3,4-BaP),本试验合成了3,4-BaP分子印迹固相萃取(BISPE)填料,并以此建立了固相萃取-超高效液相色谱串联质谱(SPE-UPLC-MS/MS)的方法。制备的3,4-BaP分子印迹填料为分散的球状颗粒,其外径在20~90μm不等,应用BISPE成功富集了烟熏鲟鱼中的3,4-BaP,并比较了Sep-pak,HLB和Florisil的萃取效率。经方法学验证,该方法线性好(R2=0.9998),检出限(LoD)0.98μg/kg,定量限(LoQ)3.16μg/kg,日内和日间精密度的相对标准偏差分别为3.26%~4.77%和3.78%~5.26%,回收率为89.7%~95.3%,RSD为2.89%~3.44%,符合痕量分析的要求。对市售50个批次烟熏鲟鱼进行测试发现,3,4-BaP阳性检出率为24%。结果表明,该方法适用于烟熏鲟鱼中3,4-BaP的检测,相关数据能为职能部门提供相关依据,进而为消费者食品安全提供保障。

Determination of Benzo[a]pyrene in Smoked Sturgeon (Acipenser sinensis) Using Molecular-imprinted Solid-phase Extraction Liquid Chromatography Tandem Mass Spectrometry Method

The current normal method for the determination of benzo(a)pyrene is not specific,and its sensitivity is not very good.The 3,4-benzo(a)pyrene(3,4-BaP)is an organic compound with the formula C20H12.3,4-BaP is a harmful compound,because it generates carcinogenic and mutagenic metabolites which can intercalate into DNA and interference with transcription.In this study,the molecular imprinted sorbent was synthesized and packed into a solid-phase extraction(SPE)cartridge for the enrichment of 3,4-BaP in smoked sturgeon(Acipenser sinensis)bought from local market.An analytical method was also developed for accurate determination of 3,4-BaP on the basis of ultra-performance liquid chromatography tandem mass spectrometry.The molecular imprinted sorbents are dispersed spherical particles,with diameter from 20 to 90μm.It was successfully applied in the enriching of 3,4-BaP,and its performance was compared with Sep-pak,HLB,and Florisil SPE.The method was validated,and the results showed that the calibration curve is linear with R2=0.9998.The limit of detection(LoD)and limit of quantitation(LoQ)are 0.98 and 3.16μg/kg,respectively.The RSDs of intra-day and inter-day accuracy are 3.26%-4.77%and 3.78%-5.26%,respectively.The recovery ranged from 89.7%to 95.3%,with RSD 2.89%-3.44%.Afterwards,the method was successfully applied to determine the 3,4-BaP in 50 batches of smoked sturgeon.The results indicated that 12 positive samples were found.The content of 3,4-BaP in the worst sample reached 21.9μg/kg.The contents of 3,4-BaP in the other samples are lower than 3.58μg/kg.In conclusion,this method is good at determining 3,4-BaP in smoked sturgeon.The relevant data could be used as reference for the functional departments for ensuring the food safety for consumers.