基于HPLC结合多元统计方法分析不同种类酒中有机酸的差异

以市售不同种类酒（白酒、露酒、配制酒、果酒（配制型）、黄酒）样品为研究对象，利用高效液相色谱（HPLC）法对酒样中的13种有机酸进行检测，并对其进行聚类分析（CA）、正交偏最小二乘-判别分析（OPLS-DA）和主成分分析（PCA）。结果表明，有机酸在各自质量浓度范围内线性关系良好，检测限（LOD）为0.10～3.67 mg/L，定量限（LOQ）为0.31～5.05 mg/L，加标回收率为87.39%～105.24%，保留时间结果相对标准偏差（RSD）为0.03%～0.46%，峰面积结果相对标准偏差（RSD）为0.13%～1.50%。该方法测定不同酒样中有机酸组成及含量差异明显，乳酸主要存在于黄酒，己酸主要存在于浓香型及其衍生香型白酒，葡萄糖酸和柠檬酸主要存在于果酒及部分露酒。CA和OPLS-DA可有效将不同种类酒样归为4类：白酒、配制酒；黄酒；露酒；果酒（配制型）。PCA结果表明，影响黄酒分布的特征有机酸为乳酸和丁二酸，浓香型及其衍生香型白酒为丁酸、己酸和戊酸，果酒（配制型）为柠檬酸、葡萄糖酸和苹果酸，部分露酒为甲酸。

Differential analysis of organic acids in different kinds of alcoholic beverage based on HPLC combined with multivariate statistical methods

Taking different kinds of commercial alcoholic beverage (Baijiu, Lujiu, blended liquor, integrated fruit wine, and Huangjiu) samples as research objects, 13 organic acids in the samples were detected by HPLC method, and cluster analysis (CA), orthogonal partial least squares-discriminant analysis (OPLS-DA), and principal component analysis (PCA) were performed. The results showed that the linear relationship of organic acids was good in the range of mass concentration, the limits of detection (LOD) were 0.10-3.67 mg/L, the limits of quantitation (LOQ) were 0.31-5.05 mg/L, and the average recovery rates were 87.39%-105.24%, and the relative standard deviation (RSD) of results of retention time and peak area were 0.03%-0.46% and 0.13%-1.50%, respectively. The composition and content of organic acids in the different samples determined by the method were obviously different. The lactic acid mainly existed in Huangjiu, the hexanoic acid mainly existed in strong-flavor (Nongxiangxing) Baijiu and its derivative flavor Baijiu, and the gluconic acid and citric acid mainly existed in fruit wines and some Lujiu. The different kinds of alcoholic beverages could be effectively classified as Baijiu and blended liquor, Huangjiu, Lujiu, and integrated fruit wine by CA and OPLS-DA. The PCA results showed that the characteristic organic acids affecting the distribution of Huangjiu were lactic acid and succinic acid, strong-flavor Baijiu and its derivative flavor Baijiu were butyric acid, hexanoic acid and valeric acid, integrated fruit wine was citric acid, gluconic acid and malic acid, and some Lujiu was formic acid.