电喷雾萃取电离质谱法用于掺假白酒的快速分析

doi:10.6023/A13070738

化学学报 ›› 2013, Vol. 71 ›› Issue (12): 1625-1632.DOI: 10.6023/A13070738 上一篇下一篇

研究论文

电喷雾萃取电离质谱法用于掺假白酒的快速分析

欧阳永中^a, 李操^a, 周亚飞^a, 周振^b

a 东华理工大学江西省质谱科学与仪器重点实验室南昌 330013;
b 上海大学环境污染与健康研究所上海 200444

投稿日期:2013-07-14 发布日期:2013-10-02
通讯作者: 李操 E-mail:licao0823@126.com
基金资助:
项目受国家杰出青年科学基金（No. 21225522）、国家自然科学基金（No. 21265001）、江西省科技支撑计划（No. 2010BNB00900，20113BCB24024）和南昌市2012年科技计划项目（No. 2012-sys-003）资助.

Rapid Analysis of Adulterated Chinese Liquor by Extractive Electrospray Ionization Mass Spectrometry

Ouyang Yongzhong^a, Li Cao^a, Zhou Yafei^a, Zhou Zhen^b

a Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China Institute of Technology, Nanchang 330013;
b Institute of Environmental Pollution and Health, Shanghai University, Shanghai 200444

Received:2013-07-14 Published:2013-10-02
Supported by:
Project supported by the National Science Fund for Distinguished Young Scholars (No. 21225522), Natural Science Foundation of China (No. 21265001), Jiangxi Science & Technology Pillar Program (No. 2010BNB00900, 20113BCB24024) and Nanchang Science & Technology Program of Jiangxi Province in 2012 (No. 2012-sys-003).

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摘要/Abstract

采用自行研制的电喷雾萃取电离源(EESI)与LTQ-XL质谱仪耦合，并结合主成分分析(PCA)和聚类分析(CA)，建立了一种能在无需样品预处理的条件下直接、快速、准确鉴别茅台等八种掺假白酒(混掺水和工业酒精，且通过酒精计调控掺假酒的酒精度与真酒保持一致)的新方法. 同时，利用串联质谱能够对目标组分进行准确鉴定. 研究结果表明，EESI-LTQ-MS检测单个样品的时间小于1 min，且重现性好，PCA区分正确率高达96.5%. 通过设置未知样分析进一步验证了该方法的可行性. 此外，还结合单光子电离飞行时间质谱法(SPI-TOF-MS)对检测谱图进行对比分析. 阐述了EESI和SPI两种电离技术在挥发性有机物分析上具有各自的优势，且两种检测手段具有互补的特点. 为市场上酒类饮品真假的快速鉴别及品质鉴定建立了一个综合的分析方法，对于快速筛选伪劣酒类产品具有非常重要的应用价值.

关键词: 电喷雾萃取电离, 质谱, 鉴别, 主成分分析, 聚类分析, 单光子电离, 掺假白酒

A novel analytical platform based on a home-made extractive electrospray ionization (EESI) source coupled with LTQ-XL mass spectrometer has been developed for fast and accurate identification of eight different kinds of adulterated Chinese liquors such as Maotai. Alcohol concentration in each liquor sample was measured by an alcohol meter and was adjusted to the same value by adding water and industrial alcohol. Measurements were done in positive ion detection mode under optimized experimental conditions. The ESI voltage was set to +4 kV, the pressure of the sheath gas (N₂) was 1.2 MPa, the temperature of the heated capillary was set to 150 ℃, and the primary ions were created by electrospraying methanol/water/acetic acid mixture (4:4:2, V:V:V) at 5 μL·min^-1. Normalized mass spectra of authentic and counterfeit liquors were differentiated by principal component analysis (PCA). Reproducibility of the method was characterized by cluster analysis (CA). Several constituents of liquor vapor were identified by tandem mass spectrometry (MS/MS). To perform MS/MS experiments, ions of interest were isolated with a mass-to-charge window width of 1.4 u. and then subjected to collision-induced dissociation (CID) with 16%～24% collision energy for 30 ms. The analysis time for a single sample was less than 1 min. The accuracy of identification predicted by PCA was 96.5%. The feasibility of this method was verified by testing several unknown samples. In addition to EESI-LTQ-MS, volatile compounds in Maotai vapor were also studied by single photon ionization time-of-flight mass spectrometry (SPI-TOF-MS), and molecular fingerprints obtained by these two methods were compared. These two detection means showed their respectively outstanding advantages and synergy for the analysis of volatile organic compounds (VOCs). The introduced method provides an important tool for the quality control of alcoholic beverages with high speed and simplicity of analysis on the market.

Key words: extractive electrospray ionization, mass spectrometry, identification, principal component analysis, cluster analysis, single photon ionization, adulterated Chinese liquor

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欧阳永中, 李操, 周亚飞, 周振. 电喷雾萃取电离质谱法用于掺假白酒的快速分析[J]. 化学学报, 2013, 71(12): 1625-1632.

Ouyang Yongzhong, Li Cao, Zhou Yafei, Zhou Zhen. Rapid Analysis of Adulterated Chinese Liquor by Extractive Electrospray Ionization Mass Spectrometry[J]. Acta Chimica Sinica, 2013, 71(12): 1625-1632.

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电喷雾萃取电离质谱法用于掺假白酒的快速分析

Rapid Analysis of Adulterated Chinese Liquor by Extractive Electrospray Ionization Mass Spectrometry

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