顶空固相微萃取-气相色谱-质谱法测定药香型白酒中萜烯类化合物

Quantification of Volatile Terpenoids in Chinese Medicinal Liquor Using Headspace-Solid Phase Microextraction Coupled with Gas Chromatography-Mass Spectrometry

应用顶空固相微萃取与气相色谱-质谱联用技术定量药香型白酒中的痕量萜烯类化合物。实验考察萃取头、样品酒精度、萃取温度和萃取时间对萜烯类化合物萃取效果的影响。最优顶空固相微萃取条件为将酒样稀释到酒精度10%,采用50/30μm碳分子筛/聚二乙烯苯/聚二甲基硅氧烷(DVB/CAR/PDMS)萃取头在60℃条件下萃取45min。该方法具有良好的线性,所有化合物的线性相关系数良好,R2≥0.9921,检测限为0.01～3.62μg/L,定量限为0.03～12.05μg/L,相对标准偏差小于15%,加标回收率为81.01%～118.94%。用该方法对药香型白酒的成品酒、原酒中的萜烯类化合物进行测定,共定量41种挥发萜烯类化合物,结果发现大曲香醅原酒中的萜烯总含量要多于小曲酒醅原酒中萜烯总含量,D-樟脑等17萜烯只在大曲香醅原酒中检测到,在小曲酒醅原酒中没有检测到,排除蒸馏时酸、热等带来的影响,推测这17种萜烯主要来源于大曲香醅,相反卡拉烯只在小曲酒醅原酒中检测到,推测其来源于小曲酒醅。顶空固相微萃取适合药香型白酒中的萜烯类化合物定量分析。

An HS-SPME coupled with GC-MS method was developed and applied for the quantification of volatile terpenoids in Chinese medicinal liquor. The effects of SPME fiber type, percentage of ethanol, extraction temperature, and adsorption time on the extraction of volatile terpenoids were evaluated. The optimal SPME extraction parameters were determined as follows： samples were diluted to an alcoholicity of 10% and extracted with 50/30 ~tm DVB/CAR/PDMS fiber for 45 min at 60 ~C. The proposed method exhibited good linearity. An excellent correlation coefficient was observed for 41 analytes, no less than 0.9921. The limits of detection were in the range of 0.0t to 3.62 ~tg/L and the limits of quantification varied from 0.03 to 12.05 lag/L. Both the repeatability and precision RSD values were below 15%. The spike recoveries of 41 volatile terpenoids were in the range of 81.01% to 118.94 %. A total of 41 volatile terpenoids were quantified by this method in base and fished samples of Chinese medicinal liquor＂ Dongjiu＂. Total terpenoid content was higher in Daqu base liquor compared to Xiaoqu base liquor. Seventeen terpenoids including D-camphor were found in Daqu base liquor rather than Xiaoqu base liquor. Regardless of the affecting factors coming from distillation such as acid and heat, the 17 terpenoids were speculated to be mainly derived from Daqu fermented grains, while calamine was found only in Xiaoqu base liquor, suggesting that it is derived from Xiaoqu fermented grains. This study indicates that the HS-SPME coupled with GC-MS method is suitable for the quantitative analysis of terpenoids in Chinese medicinal liquor.