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Abstract：
4-(methylintrosamino)-1-(3-pyridyl)-1-butanone (NNK) and N\'-nitrosonornicotine (NNN) are the most prevalent and toxic tobacco specific nitrosamines (TSNAs). Due to their carcinogenicity, knowledge of the composition of NNK and NNN in tobacco is necessary. Herein, a sensitive and rapid method, which employs autoclave extraction-supercritical fluid chromatography/tandem mass spectrometry (SFC-MS/MS), has been developed for the analysis of NNK and NNN in tobacco. Both water-soluble and matrix-bound NNK and NNN were extracted with 100 mM ammonium acetate in an autoclave (130 °C, 4 h), and the aqueous extract was subjected to solvent replacement prior to SFC-MS/MS analysis. NNK and NNN were effectively separated within 5 min by using supercritical CO2 as the main mobile phase coupled with a co-solvent of methanol. Excellent linearity was obtained with coefficients of determination (R2) greater than 0.9997 in the range of 1-160 ng/mL and 5-800 ng/mL for NNK and NNN, respectively. The recoveries were in the range of 92.5-110.0% at different spiked levels of real samples. 12 tobacco samples which include 3 typical tobacco varieties of burley, flue-cured, and oriental tobaccos had been analyzed, and the fraction of matrix-bound NNK was determined as well. In addition, a comparison between the proposed SFC-MS/MS method and a validated liquid chromatography tandem mass spectrometry (LC-MS/MS) internal standard method was conducted. Both techniques exhibit comparable analysis results, but peak splitting of NNN was observed by LC-MSMS due to the existence of E/Z isomers, while SFC-MS/MS offers great improvement through elution condition optimization, demonstrating the applicability of SFC-MS/MS as an alternative tool for NNK and NNN analysis.
摘要：
4-（甲基氨基氨基）-1-（3-吡啶基）-1-丁酮（NNK）和N'-亚硝胺（NNN）是最普遍和有毒的烟草特异性亚硝胺（TSNA）。由于它们的致癌性，了解烟草中NNK和NNN的组成是必要的。在这里，一种灵敏快速的方法，采用高压釜萃取-超临界流体色谱/串联质谱（SFC-MS/MS），已开发用于分析烟草中的NNK和NNN。在高压釜（130°C，4h),在进行SFC-MS/MS分析之前,对水性提取物进行溶剂置换。通过使用超临界CO2作为主要流动相并与甲醇共溶剂偶联，NNK和NNN在5分钟内有效分离。对于NNK和NNN，在1-160ng/mL和5-800ng/mL的范围内，测定系数（R2）大于0.9997，获得了出色的线性，分别。在实际样品的不同加标水平下，回收率在92.5-110.0％的范围内。12份烟草样品，其中包括3个典型的白肋烟品种，烤烟,对东方烟草进行了分析，和基质结合的NNK的分数也被确定。此外,进行了拟议的SFC-MS/MS方法与经过验证的液相色谱串联质谱（LC-MS/MS）内标方法之间的比较。两种技术都表现出可比的分析结果，但是由于E/Z异构体的存在，通过LC-MSMS观察到NNN的峰分裂，虽然SFC-MS/MS通过优化洗脱条件提供了很大的改进，证明SFC-MS/MS作为NNK和NNN分析的替代工具的适用性。
