采用液相色谱-质谱联用法(Liquid Chromatography-tandem Mass Spectrometry,LC-MS/MS)结合多元统计分析对12种香型白酒中的18种吡嗪类化合物进行分析,并用S型曲线、Feller加和模型、香气活度值(Odor Activity Value,OAV)法和σ-τ模型研究三甲基吡嗪与乙酸乙酯、丁酸乙酯、己酸乙酯和乳酸乙酯之间的感知交互作用.LC-MS/MS方法在检测范围内线性关系良好(R2≥0.995),检出限为0.69～43.47 μg/L,定量限为2.10～95.21 μg/L,日内精密度≤4.71％、日间精密度≤4.11％,加标回收率82.22％～103.71％.酱香型白酒吡嗪总量最高,为10411.71～32 628.30 μg/L,其次是兼、芝麻和董香型白酒,四甲基吡嗪和三甲基吡嗪是白酒中含量最高的2种吡嗪类化合物.正交偏最小二乘判别分析(Orthogonal Partial Least Squares Discriminant Analysis,OPLS-DA)模型可对 12 种香型白酒进行大致分类,变量重要性投影值(Variable Importance in the Projection,VIP)分析筛选出9种关键差异吡嗪类化合物,2-甲基吡嗪的VIP值最高,为1.33.感知交互作用的研究结果表明三甲基吡嗪与乙酸乙酯、丁酸乙酯和己酸乙酯之间存在加成或协同作用,与乳酸乙酯之间是掩盖作用.该研究可为白酒的风味品质调控提供理论参考.
Analysis of Pyrazines in Baijiu and Their Perceptual Interactions with Esters
Eighteen pyrazines in 12 aromatic Baijiu were analyzed using liquid chromatography-tandem mass spectrometry(LC-MS/MS)combined with multivariable statistical analysis,,and the perceptual interactions among trimethylpyrazine and ethyl acetate,ethyl butyrate,ethyl hexanoate,and ethyl lactate were investigated using the S-curve method,Feller's additive model,odor activity value(OAV)method,and σ-τ model.The LC-MS/MS method showed good linear relationships within the detection ranges(R2≥ 0.995),with the limits of detection being 0.69～43.47 μg/L,the limits of quantification being 2.10～95.21 μg/L,the intra-day precision≤ 4.71％,the inter-day precision ≤ 4.11％,and the spiking recoveries being 82.22％～103.71％.Sauce-flavor Baijiu samples had the highest total contents of pyrazines(10 411.71～32 628.30 μg/L),followed by Jian-flavor Baijiu,Sesame-flavor Baijiu,and Dong-flavor Baijiu.Tetramethylpyrazine and trimethylpyrazine were the two kinds of pyrazines with the highest contents in Baijiu.The orthogonal partial least squares discriminant analysis(OPLS-DA)model could roughly classify the 12 flavor Baijiu,and the variable importance in the projection(VIP)analysis allowed 9 key differential pyrazines to be screened out,with 2-methylpyrazine having the highest VIP value(1.33).The results of perceptual interactions showed that there was an additive or synergistic effect between trimethylpyrazine and ethyl acetate,ethyl butyrate or ethyl hexanoate,with a masking effect occurring between trimethylpyrazine and ethyl lactate.This study can provide a theoretical reference for regulating flavor quality of Baijiu.
Baijiupyrazinesliquid chromatography-tandem mass spectrometryperceptual interaction
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