固相萃取-液相色谱-串联质谱法测定药用蜂蜜中双酚类化合物

Determination of Bisphenols in Medicinal Honey Using Solid-phase Extraction-liquid Chromatography-tandem Mass Spectrometry

目的:以羧基化石墨多壁碳纳米管为固相萃取材料,建立液相色谱-串联三重四级杆质谱测定药用蜂蜜中双酚A、双酚F和双酚S的方法。方法:比较了羧基化多壁碳纳米管(MWCNTs-COOH)、HLB(N-乙烯吡咯烷酮-二乙烯基苯亲水亲脂平衡型填料)和羧基化石墨多壁碳纳米管(GMWCNTs-COOH)对药用蜂蜜中双酚A、双酚F和双酚S的吸附效率。样品用20%乙腈水溶液提取,通过羧基化石墨多壁碳纳米管固相萃取净化,以甲醇-水为流动相,C18色谱柱分离,采用MRM负离子模式检测,内标法定量。结果:3种固相萃取柱对双酚A、双酚F和双酚S的吸附效率依次为:GMWCNTs-COOH>MWCNTs-COOH>HLB。双酚A和双酚F方法检出限为0.3μg/kg,定量限为1.0μg/kg;双酚S方法检出限为0.05μg/kg,定量限为0.15μg/kg。将该方法应用于药用蜂蜜中的双酚A、双酚F和双酚S的测定,加标回收率为87.7%~105.2%,RSD为2.4%~5.3%。结论:该方法操作简便、准确、稳定,适用于药用蜂蜜中双酚A、双酚F和双酚S的检测。

Objective:A method for the determination of bisphenol A,bisphenol F and bisphenol S in medicinal honey by using carboxylated graphite multiwalled carbon nanotubes as solid-phase extraction and liquid chromatography tandem mass spectrometry.Methods:Comparison of the adsorption efficiencies of three materials including carboxylated multiwalled carbon nanotubes(MWCNTs-COOH),HLB(N-vinylpyrrolidone-divinylbenzene hydrophilic and lipophilic balanced filler)and carboxylated graphite multiwalled carbon nanotubes(GMWCNTs-COOH)used as solid-phase extraction for bisphenol A,bisphenol F and bisphenol S in medicinal honey.The sample was extracted with 20%acetonitrile,purified by carboxylated graphite multiwalled carbon nanotubes.The separation was performed using a C18 column with methanol-water as mobile phase.Detected was operated by electrospray ionization mass spectrometry in negative mode and multi-reaction monitoring mode,and quantified by internal standard method.Results:The adsorption efficiencies of the three solid phase extraction columns for bisphenol A,biosphenol F and bisphenol S are as follows:GMWCNTs-COOH>MWCNTs-COOH>HLB.The detection limit of bisphenol A and bisphenol F is 0.3μg/kg,and the quantitative limit was 1.0μg/kg.The detection limit of bisphenol S was 0.05μg/kg,and the quantitative limit was 0.15μg/kg.The method was used to determine bisphenol A,bisphenol F and bisphenol S in medicinal honey.The recovery was 87.7%-105.2%,and the relative standard deviation was 2.4%-5.3%.Conclusion:The method is convenient,accurate and stable,and can be used for the determination of bisphenol A,bisphenol F and bisphenol S in medicinal honey.