全二维气相色谱/飞行时间质谱用于中药挥发油和酒中香味成分的研究
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摘要
全二维气相色谱(GC×GC)是九十年代发展起来的分离复杂混合物的一种全新手段。自1991年其思想及其装置问世后，得到了迅速的发展。
本论文首先以石油产品为样品研究了全二维气相色谱／飞行时间质谱(GC×GC／TOFMS)的特性，讨论了柱系统的匹配、温度程序、调制条件等对分离的影响，为GC×GC分析复杂样品提供了技术基础。
在上述研究的基础上，本论文将GC×GC／TOFMS应用于中药挥发油。以广藿香、莪术、连翘、姜黄和片姜黄挥发油为例，通过优化柱系统和操作条件，鉴定出了大部分的组分，累计含量均超过90％。以广藿香、莪术挥发油等样品为例，比较了GC和GC×GC的分离能力，比较了GC／MS与GC×GC／TOFMS的定性能力，证明了GC×GC／TOFMS在中药挥发油分离分析领域占有强大的优势。不仅如此，GC×GC／TOFMS对每一被鉴定的组分都给出了第一维保留时间、第二维保留时间、结构、相似度、反相似度、可能性、信噪比、纯度等信息，使得定性可靠性大大加强。
本论文最后以酒为例，通过优化前处理方法和色谱条件，鉴定出酒中472种香味成分，再次证明了GC×GC／TOFMS在复杂体系分离分析领域占有强大的优势。
GCxGC is a novel separation method for complex samples emerging in the 1990's. After the idea was prompted and implemented, it is experiencing rapid development.
In the thesis, we firstly demonstrated characteristics of GCxGC/TOFMS using petroleum samples, discussed influence of column match, temperature program, and modulation conditions on separation, and gave a strategy of system optimization.
On the above basis, GC GC/TOFMS was applied to study volatile oils of Traditional Chinese Medicines (TCMs). Pogostemon cablin Benth, zedoary, Forsythia suspensa Vahl, curcuma and ginger Huang volatile oils were as samples. The chromatographic conditions of GC GC including column system, modulation time and temperature program were optimized for each sample. Total content of the components tentatively identified was more than 90 %. Pogostemon cablin Benth, zedoary volatile oils were as samples. The separation power of GCxGC and GC, and identification power of GCxGC/TOFMS and GC/MS were compared under the same conditions. The enhanced sensitivity and superior resolution of GCxGC were demonstrated. Moreover GCxGC/TOFMS provided more identification information including retention times on 1st and 2nd dimensions, similarity, reverse, probability, purity and signal/noise and so on, which make the reliability of analysis greatly increased. All of these showed that GCxGC/TOFMS is a powerful instrument in the analysis of volatile oils of TCMs.
Liquor was as a sample at last, after optimizing pretreatment method and the chromatographic conditions an analytical method of liquor was established. There are 472 flavor constituents with similarity of over 800. It is documented that GCxGC/TOFMS is a powerful instrument in the analysis of complex samples again.
本论文首先以石油产品为样品研究了全二维气相色谱／飞行时间质谱(GC×GC／TOFMS)的特性，讨论了柱系统的匹配、温度程序、调制条件等对分离的影响，为GC×GC分析复杂样品提供了技术基础。
在上述研究的基础上，本论文将GC×GC／TOFMS应用于中药挥发油。以广藿香、莪术、连翘、姜黄和片姜黄挥发油为例，通过优化柱系统和操作条件，鉴定出了大部分的组分，累计含量均超过90％。以广藿香、莪术挥发油等样品为例，比较了GC和GC×GC的分离能力，比较了GC／MS与GC×GC／TOFMS的定性能力，证明了GC×GC／TOFMS在中药挥发油分离分析领域占有强大的优势。不仅如此，GC×GC／TOFMS对每一被鉴定的组分都给出了第一维保留时间、第二维保留时间、结构、相似度、反相似度、可能性、信噪比、纯度等信息，使得定性可靠性大大加强。
本论文最后以酒为例，通过优化前处理方法和色谱条件，鉴定出酒中472种香味成分，再次证明了GC×GC／TOFMS在复杂体系分离分析领域占有强大的优势。
GCxGC is a novel separation method for complex samples emerging in the 1990's. After the idea was prompted and implemented, it is experiencing rapid development.
In the thesis, we firstly demonstrated characteristics of GCxGC/TOFMS using petroleum samples, discussed influence of column match, temperature program, and modulation conditions on separation, and gave a strategy of system optimization.
On the above basis, GC GC/TOFMS was applied to study volatile oils of Traditional Chinese Medicines (TCMs). Pogostemon cablin Benth, zedoary, Forsythia suspensa Vahl, curcuma and ginger Huang volatile oils were as samples. The chromatographic conditions of GC GC including column system, modulation time and temperature program were optimized for each sample. Total content of the components tentatively identified was more than 90 %. Pogostemon cablin Benth, zedoary volatile oils were as samples. The separation power of GCxGC and GC, and identification power of GCxGC/TOFMS and GC/MS were compared under the same conditions. The enhanced sensitivity and superior resolution of GCxGC were demonstrated. Moreover GCxGC/TOFMS provided more identification information including retention times on 1st and 2nd dimensions, similarity, reverse, probability, purity and signal/noise and so on, which make the reliability of analysis greatly increased. All of these showed that GCxGC/TOFMS is a powerful instrument in the analysis of volatile oils of TCMs.
Liquor was as a sample at last, after optimizing pretreatment method and the chromatographic conditions an analytical method of liquor was established. There are 472 flavor constituents with similarity of over 800. It is documented that GCxGC/TOFMS is a powerful instrument in the analysis of complex samples again.
引文
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3 C.J. Venkatramani, J. Xu, J.B. Phillips. Separation orthogonality in temperature-programmed comprehensive two-dimensional gas chromatography. Anal. Chem.. 1996, 68:1486-1492
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5 J.B. Phillips, R.B. Gaines. A robust thermal modulator for comprehensive two-dimensional gas chromatography. J. High resol. Chromatogr.. 1999,22:3-10
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