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为实现卷烟主流烟气中痕量有机硫化物的高准确度测定，建立了反吹系统耦合气相色谱-串联质谱（GC-MS-MS）测定卷烟主流烟气中35种有机硫化物的同时分析方法，优化了前处理条件和反吹时间的仪器参数；将该方法应用于32种烤烟型和6种混合型卷烟样品，分析其主流烟气中35种有机硫化物的释放量及差异规律。结果表明：(1)反吹系统的引入可显著减少高沸点组分在色谱分离柱的残留，降低样品间交叉污染的风险并提升连续进样时目标物保留时间的一致性。(2)卷烟样品主流烟气中共检出25种有机硫化物。其中，19种在所有样品主流烟气中均有检出，主成分分析（PCA）结果显示两种类型卷烟可显著区分；热图和t检验结果显示，噻吩、噻唑、糠基硫醇、四氢噻吩-3-酮、2-乙酰基噻唑、4-甲基-5-乙烯基噻唑、5-甲基噻吩-2-甲醛、5-(2-羟乙基)-4-甲基噻唑在混合型卷烟样品主流烟气中的单位焦油释放量显著高于烤烟型卷烟（p<0.01），烤烟型卷烟样品主流烟气中4-（甲硫基）丁腈的单位焦油释放量均值为混合型卷烟的2.9倍（p<0.01）。(3)6种有机硫化物仅在部分卷烟样品的主流烟气中检出。除了2-硫代糠酸甲酯和2-甲基-3-甲硫基吡嗪在混合型卷烟样品主流烟气中的检出率分别为67%和83%外，糠基甲基二硫醚、二丁基硫醚、8-巯基马来酮和二糠基硫醚在卷烟样品主流烟气中的检出率均不超过40%。
Abstract：To determine the trace organic sulfides in mainstream cigarette smoke with high accuracy, a simultaneous analytical method was developed using a blowback system coupled with gas chromatography-tandem mass spectrometry(GC-MS-MS) to quantify 35 potential organic sulfides in mainstream cigarette smoke, with optimized pretreatment conditions and the time of blowback in the instrumental parameters. This method was then used to analyze the releases of 35 organic sulfides in 32 Virginia type and 6 blended type cigarette samples and the differences among them. The results showed that: 1)The introduction of the blowback system significantly reduced the retention of high boiling point components in the chromatographic separation columns, lowered the risk of cross contamination across samples, and enhanced the retention time consistency during continuous injections. 2) A total of 25 organic sulfides were detected in mainstream smoke of the cigarette samples, and 19 of which were identified in all the samples. The results of principal component analysis(PCA) showed that there was clear distinction between the two types of cigarettes. Heatmap analysis and t-test results revealed that the average releases per unit tar of thiophene, thiazole, furfuryl mercaptan, tetrahydrothiophen-3-one,2-acetylthiazole, 4-methyl-5-vinylthiazole, 5-methylthiophene-2-carboxaldehyde and 5-(2-hydroxyethyl)-4-methylthiazole were significantly higher in mainstream smoke of blended type cigarettes than those in Virginia type cigarettes(p<0.01), while the average release per unit tar of 4-(methylthio)butyronitrile in mainstream smoke of Virginia type cigarettes was 2.9 times of that in blended cigarettes(p<0.01). 3)Six organic sulfides were detected only in mainstream smoke of some cigarette samples, with the detection rates of methyl 2-thiofuroate and 2-methyl-3-methylthiopyrazine in mainstream smoke of blended cigarette samples reached 67% and 83% respectively, and those of furfuryl methyl disulfide, dibutyl sulfide,8-mercaptomenthone and difurfuryl sulfide in mainstream smoke of cigarette samples were no more than 40%.
[1]赖内修斯G.香味化学与工艺学[M]. 2版.张建勋，译.北京：中国科学技术出版社，2012.Reineccius G. Flavor chemistry and technology[M]. 2nd ed. ZHANG Jianxun,trans. Beijing:China Science and Technology Press,2012.
[2] Zhu J C,Niu Y W,Huang M,et al. Characterization of key sulfur aroma compounds and enantiomer distribution in Yingjia Gongjiu[J]. LWT-Food Science and Technology,2022,167:113799.
[3] Wang X,Liu X,Liu Z,et al. Unlocking the secrets of stinky fermented foods:A comprehensive overview of processes, flavor characteristics, fermentation microbiomes, and metabolic pathways[J]. Food Bioscience,2025,68:106408.
[4] Han X,Gao X,Yu M,et al. Sensory directed analysis for key odor-active compounds in by-products flavorings enhanced by enzymatic hydrolysis and Maillard reaction[J]. Journal of Food Composition and Analysis,2025,142:107487.
[5] Rodgman A,Perfetti T A. The chemical components of tobacco and tobacco smoke[M]. 2nd ed. New York:CRC Press,2013.
[6] Philippe R J. Dimethyl sulfide in cigarette smoke—On the origin of the sulfur compounds of cigarette smoke and on their possible contribution to its overall flavor and aroma[J]. Beitraege zur Tabakforschung,1966,3(9):577-582.
[7] Palmer A M,Daylor F. Sulfur compounds in cigarette smoke condensate[EB/OL].(2012-11-14)[2025-05-19].https：//idl.ucsf.edu/tobacco/docs/htjw0131.
[8] Schmid E R, Bachlechner G, Varmuza K, et al.Determination of polycyclic aromatic hydrocarbons,polycyclic aromatic sulfur and oxygen heterocycles in cigarette smoke condensate[J]. Fresenius Zeitschrift für Analytische Chemie,1985,322(2):213-219.
[9] Ochiai N,Mitsui K,Sasamoto K,et al. Multidimensional gas chromatography in combination with accurate mass,tandem mass spectrometry, and element-specific detection for identification of sulfur compounds in tobacco smoke[J]. Journal of Chromatography A,2014,1358:240-251.
[10] Guan T,Fu S,Wu X,et al. Bioturbation effect of artificial inoculation on the flavor metabolites and bacterial communities in the Chinese Mao-tofu fermentation[J]. Food Chemistry:X,2024,21:101133.
[11] Zhu H,Yang H,Zhou X,et al. Effect of DAP and glutamine supplementation on sulfur-containing volatiles and sensory properties of Chardonnay wine fermented with Saccharomyces cerevisiae yeast[J]. Journal of Food Science,2023,88(4):1392-1408.
[12] Wieczorek M N, Majcher M A, JeleńH H.Identification of aroma compounds in raw and cooked broccoli[J]. Flavour and Fragrance Journal,2021,36(5):576-583.
[13] Qin Y,Wang B,Liu S,et al. Robust,comprehensive,sensitive analysis of flavour additives with carboxyl and hydroxyl groups in cigarette smoke combining silylation and gas chromatography-tandem mass spectrometry with an improved backflushing system[J]. Journal of Chromatography A,2022,1675:463171.
[14] Guo Q,Pan L N,Qin Y Q,et al. Combined use of analyte protectants and precolumn backflushing for a robust, high-throughput quantitative determination of aroma compounds in cigarette mainstream smoke by gas chromatography-tandem mass spectrometry[J]. Microchemical Journal,2022,175:107121.
[15] GB/T 16450—2004常规分析用吸烟机定义和标准条件[S].GB/T 16450—2004 Routine analytical cigarette-smoking machine—Definitions and standard conditions[S].
[16] Leffingwell J C,Young H J, Bernasek E. Tobacco flavoring for smoking products[M]. Winston-Salem:R J Reynolds Tobacco Company,1972.
[17] Leffingwell J C. Tobacco flavoring for smoking productsⅡ[EB/OL].(2012-04-17)[2023-04-11]. http：//industrydocuments.library.ucsf.edu/tobacco/docs/yzvw0019.
基本信息:
DOI：10.16135/j.issn1002-0861.2025.0325
中图分类号:O657.63;TS411
引用信息:
[1]陈志燕,秦亚琼,李志华,等.反吹系统耦合GC-MS-MS测定卷烟主流烟气中35种有机硫化物[J].烟草科技,2025,58(11):14-25.DOI:10.16135/j.issn1002-0861.2025.0325.
基金信息:
中国烟草总公司科技计划项目“基于风味组学和分子对接的烟气甜感关键成分组群研究”（110202403007）; 广西中烟工业有限责任公司科技项目“卷烟烟气甜感物质基础研究”（GXZYCX2023C010）