分散固相萃取-高效液相色谱-串联质谱法测定红酒中14种生物胺及其代谢产物

Detection of 14 biogenic amines and their metabolites in red wine by dispersive solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry

目的建立红酒中组胺、尸胺、色胺、腐胺、精胺、酪胺、亚精胺、2-苯乙胺及其代谢产物多巴胺、肾上腺素、去甲肾上腺素、高香草酸、5-羟基吲哚乙酸与3,4-二羟基苯乙酸的分散固相萃取-高效液相色谱-串联质谱分析方法(dSPE-HPLC-MS/MS)。方法样品中的生物胺及其代谢产物采用自制的纳米TiO;修饰共价有机框架材料(CSTF-COFs)吸附富集,再经Zorbax SB-Aq(2.1 mm×100 mm,1.8μm)色谱柱分离,流动相为含有0.1%甲酸的乙腈溶液和含有0.1%甲酸的水溶液,在电喷雾离子源(ESI)正离子多反应监测(MRM)模式下检测。结果14种生物胺及其代谢产物在0.2μg/L~2000μg/L浓度内具有良好的线性(r>0.9980),检出限为0.03μg/L~5.18μg/L,定量限为0.1μg/L~17.1μg/L,相对标准偏差(RSDs)为2.6%~6.7%,加标回收率为80.1%~107%。结论本法可用于红酒中14种生物胺及其代谢产物的快速筛查与确证分析。

Objective To develop a method for the determination of catecholamine,dopamine(DA),nore-pinephrine(NE)and epinephrine(E),and their metabolites i.e.,putrescine(PUT),cadaverine(CAD),spermidine(SPD),spermine(SP),tyramine(TYR),phenylethylamine(PHE),histamine(HIS),tryptamine(TR),5-hydroxy-3-indoleacetic acid(5-HIAA),3,4-dihydroxyphenylacetic acid(DOPAC)and homovanillic acid(HVA)in red wine by dispersive solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry(dSPE-LC-MS/MS).Methods The target analytes in samples were extracted by using dSPE with clover-shaped nanotitania functionalized COFs(CSTF-COFs)as sorbents.Chromatographic separation was performed on a Zorbax SB-Aq analytical column(2.1 mm×100 mm,1.8μm)with 0.1%formic acid(V/V)in water and 0.1%formic acid(V/V)in acetonitrile as mobile phase,and the mass spectrometric analysis was performed by using electrospray ionization source in positive mode.Results Good linearity was observed in the range of 0.2μg/L-2000μg/L with correlation coefficients(r)higher than 0.9980.The limits of detection(LODs)in red wine samples were in the range of 0.03μg/L-5.18μg/L and the limits of quantification(LOQs)were in the range of 0.1μg/L-17.1μg/L.The relative standard deviations(RSDs)were in the range of 2.6%~6.7%,and recoveries were between 80.1%and 107%.Conclusion The developed method can be used for the rapid screening and confirmatory analysis of 14 biogenic amines and metabolites in red wine samples.