顶空-气相色谱-质谱联用法结合化学计量学分析赣州烤烟样品中的挥发性化合物
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摘要
【目的】挥发性香气成分作为烟气组分的前体物质,影响着烟草感官评吸质量,通过对赣州烤烟样品中的挥发性化合物含量进行分析,挖掘不同产地烟叶中挥发性化合物的含量规律并进行产地预报分类,从而实现对烟草的质量控制。【方法】通过静态顶空-气相色谱-质谱联用测定赣州6个产烟区县(石城、瑞金、安远、会昌、兴国、信丰)共62个烤烟样品中的54种挥发性化合物含量,采用主成分分析(Principal component analysis, PCA)对样品产地进行分类,用遗传算法(Genetic algorithm, GA)进行变量筛选,用线性判别分析(Linear discriminant analysis, LDA)、反传-人工神经网络(Back propagation-artificial neural network, BPANN)、最小二乘-支持向量机(Least squares-support vector machines, LS-SVM)3种有监督模式识别方法进行产地预报。【结果】直接对样品进行PCA,分类效果并不理想;采用GA对挥发性化合物含量进行变量筛选后得到11个变量,分类效果得到显著改善,结合分类结果分析了来自不同区县的样品中挥发性化合物的含量规律。BP-ANN和LS-SVM的预报正确率分别达到96.8%和98.4%,展现了较好的实际使用价值,据此建立了赣州烤烟样品的产地鉴别模型。【结论】该方法可以较为准确地判定赣州烤烟样品的来源,同时可以找到不同产地烤烟挥发性化合物的含量规律,亦可用于全国各地烤烟的香型风格监测和质量控制。
【Objective】 As precursor substances of flue gas components, volatile aroma components can affect the quality of tobacco sensory evaluation. The aims of this study were to analyze the content of volatile compounds in fluecured tobacco samples from Ganzhou, to explore the content regulation of volatile compounds in tobacco leaves of different producing areas, and to predict the origin classification of samples so as to achieve quality control of tobacco. 【Methods】54 kinds of volatile compounds of 62 flue-cured tobacco samples from 6 tobacco-producing counties(Shicheng, Ruijin,Anyuan, Huichang, Xingguo, Xinfeng) in Ganzhou were measured by static headspace-gas chromatography-mass spectrometry method(HS-GC-MS). Subsequently, principal component analysis(PCA) was used for classification of sample origins, genetic algorithm(GA) was used for variable screening, and three supervised pattern recognition methods, namely, linear discriminant analysis(LDA), back propagation-artificial neural network(BP-ANN) and least squares-support vector machines(LS-SVM)were used for origin prediction. 【Results】 The classification effect by PCA, which was contributed to explore the content regulation of volatile compounds of samples in Ganzhou, was significantly improved after obtaining 11 volatile compounds(variables) by GA. The prediction accuracy rates of BP-ANN and LS-SVM reached 96.8% and 98.4%, respectively, which showed good practical application value. On this basis, the identification model for the origin of flue-cured tobacco of Ganzhou was established. 【Conclusion】 The method proposed in this paper can accurately determine the origins of flue-cured tobacco samples from Ganzhou, find the content regulation of volatile compounds among different origins, and be used for the monitoring of flavor patterns and the quality control of flue-cured tobacco across the country.
【Objective】 As precursor substances of flue gas components, volatile aroma components can affect the quality of tobacco sensory evaluation. The aims of this study were to analyze the content of volatile compounds in fluecured tobacco samples from Ganzhou, to explore the content regulation of volatile compounds in tobacco leaves of different producing areas, and to predict the origin classification of samples so as to achieve quality control of tobacco. 【Methods】54 kinds of volatile compounds of 62 flue-cured tobacco samples from 6 tobacco-producing counties(Shicheng, Ruijin,Anyuan, Huichang, Xingguo, Xinfeng) in Ganzhou were measured by static headspace-gas chromatography-mass spectrometry method(HS-GC-MS). Subsequently, principal component analysis(PCA) was used for classification of sample origins, genetic algorithm(GA) was used for variable screening, and three supervised pattern recognition methods, namely, linear discriminant analysis(LDA), back propagation-artificial neural network(BP-ANN) and least squares-support vector machines(LS-SVM)were used for origin prediction. 【Results】 The classification effect by PCA, which was contributed to explore the content regulation of volatile compounds of samples in Ganzhou, was significantly improved after obtaining 11 volatile compounds(variables) by GA. The prediction accuracy rates of BP-ANN and LS-SVM reached 96.8% and 98.4%, respectively, which showed good practical application value. On this basis, the identification model for the origin of flue-cured tobacco of Ganzhou was established. 【Conclusion】 The method proposed in this paper can accurately determine the origins of flue-cured tobacco samples from Ganzhou, find the content regulation of volatile compounds among different origins, and be used for the monitoring of flavor patterns and the quality control of flue-cured tobacco across the country.
引文
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[8]刘传和,刘岩.4种芒果香气品质分析[J].广东农业科学,2016,43(10):123-127.doi:10.16768/j.issn.1004-874X.2016.10.022.LIU C H,LIU Y.Aroma quality of four cultivars of mango fruits[J].Guangdong Agricultural Sciences,2016,43(10):123-127.doi:10.16768/j.issn.1004-874X.2016.10.022.
[9]CACHO J I,CAMPILL N,VINAS P,HERNáNDEZ-CóRDOBAM.A simple device for headspace sorptive extraction prior to gas chromatography-mass spectrometry analysis[J].Talanta,2019,195:796-799.doi:10.1016/j.talanta.2018.12.001.
[10]倪永年.化学计量学在分析化学中的应用[M].北京:科学出版社,2004.NI Y N.The application of chemometrics in analytical chemistry[M].Beijing:Science Press,2004.
[11]陈义强,范坚强,包可翔,陈少滨.不同移栽期烟草生育期气温因子主成分与烟叶品质相关性分析[J].广东农业科学,2017,44(11):1-6.doi:10.16768/j.issn.1004-874X.2017.11.001.CHEN Y Q,FAN J Q,BAO K X,CHEN S B.Principal component of temperature factors during the growth period of different transplanting date on tobaccoand its relation leaves quality[J].Guangdong Agricultural Sciences,2017,44(11):1-6.doi:10.16768/j.issn.1004-874X.2017.11.001.
[12]张亚平,张晓宇,周顺,何庆,王孝峰,佘世科,徐迎波,宁敏.卷烟纸组分对常规和细支卷烟烟气释放量及感官质量的影响[J].烟草科技,2017,50(11):48-57.doi:10.16135/j.issn1002-0861.2017.0052.ZHANG Y P,ZHANG X Y,ZHOU S,HE Q,WANG X F,SHE S K,XUY B,NING M.Effects of cigarette paper components on smoke release and sensory quality of normal and slim cigarettes[J].Tobacco Science&Technology,2017,50(11):48-57.doi:10.16135/j.issn1002-0861.2017.0052.
[13]杨超,丁根胜,万里兴,黄新民,杨盛刚,穆林,惠建权.基于烟叶化学成分的卷烟叶组感官质量和风格研究[J].烟草科技,2018,51(8):85-91.doi:10.16135/j.issn1002-0861.2017.0331.YANG C,DING G S,WAN L X,HUANG X M,YANG S G,MU L,HUI J Q.Relationships of main chemical components in tobacco blend of cigarette with its sensory quality and style[J].Tobacco Science&Technology,2018,51(8):85-91.doi:10.16135/j.issn1002-0861.2017.0331.
[14]李广才,余玉梅,胡建军,周冀衡.湖南烤烟主要化学成分与评吸质量的非线性关系解析[J].中国烟草学报,2012,18(4):17-26.doi:10.3969/j.issn.1004-5708.2012.04.003.LI G C,YU Y M,HU J J,ZHOU J H.Non-linear relationship between chemical compositions and smoking quality in flue-cured tobacco in Hunan province[J].Acta Tabacaria Sinica,2012,18(4):17-26.doi:10.3969/j.issn.1004-5708.2012.04.003.
[15]周芸,过伟民,李小兰,周晓,王学杰,郭建华,韩加所,张仕祥,戴华鑫,牟文君.清香型产区烤烟游离氨基酸与感官质量的关联分析[J].烟草科技,2018,51(11):28-35.ZHOU Y,GUO W M,LI X L,ZHOU X,WANG X J,GUO J H,HAN J S,ZHANG S X,DAI H X,MU W J.Correlation between free amino acids and sensory quality for flue-cured tobacco of fresh flavor type tobaccoplanting areas[J].Tobacco Science&Technology,2018,51(11):28-35.doi:10.16135/j.issn1002-0861.2017.0557.
[16]YC/T 31-1996烟草及烟草制品试样的制备和水分测定烘箱法[S].1996.YC/T 31-1996.Tobacco and tobacco products-preparation of test sample and determination of water content-oven method[S].1996.
[17]谢剑平.烟草与烟气化学成分[M].北京:化学工业出版社,2010.XIE J P.Tobacco and smoke chemical composition[M].Beijing:Chemical Industry Press,2010.
[18]SINKOV N A,HARYNUK J J.Three-dimensional cluster resolution for guiding automatic chemometric model optimization[J].Talanta,2013,103:252-259.doi:10.1016/j.talanta.2012.10.040.
[19]LEARDI R.Application of genetic algorithm-PLS for feature selection in spectral data sets[J].Journal of Chemometrics,2000,14:643-655.doi:10.1002/1099-128X(200009/12)14:5/6<643::AID-CEM621>3.0.CO;2-E.
[20]NI Y N,MEI M H,KOKOT S.Resolution of high performance liquid chromatographic fingerprints of Rhizoma curcumae by application of chemometrics[J].Journal of Liquid Chromatography&Related Technologies,2011,34:1952-1964.doi:10.1080/10826076.2011.582215.
[21]TEYE E,HUANG X Y,DAI H,CHEN Q S.Rapid differentiation of Ghana cocoa beans by FT-NIR spectroscopy coupled with multivariate classification[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2013,114:183-189.doi:10.1016/j.saa.2013.05.063.
[22]付茂红,钟娟,谭忠元,彭文璟,杨杰,周金燕,谭红.改进型人工神经网络优化Iturin A发酵培养基研究[J].广东农业科学,2015,17:102-107.doi:10.16768/j.issn.1004-874x.2015.17.006.FU M H,ZHONG J,TAN Z Y,PENG W J,YANG J,ZHOU J Y,TAN H.Optimization of fermentation medium for Iturin A by improved artificial neural network approach[J].Guangdong Agricultural Sciences,2015,42(17):102-107.doi:10.16768/j.issn.1004-874x.2015.17.006.
[23]LIU F,HE Y,WANG L.Determination of effective wavelengths for discrimination of fruit vinegars using near infrared spectroscopy and multivariate analysis[J].Analytica Chimica Acta,2008,615:10-17.doi:10.1016/j.aca.2008.03.030.
[2]刘绍华,白家峰,冉盼盼,马扩彦,许春平.美拉德反应时间对烟草花蕾发酵液挥发性香味成分的影响[J].广东农业科学,2017,44(8):96-105.doi:10.16768/j.issn.1004-874X.2017.08.016.LIU S H,BAI J F,RAN P P,MA K Y,XU C P.Effects of Maillard reaction time on volatile aroma components in tobacco bud fermentation broth[J].Guangdong Agricultural Sciences,2017,44(8):96-105.doi:10.16768/j.issn.1004-874X.2017.08.016.
[3]BOON Y H,ZAIN N N M,MOHAMAD S,OSMAN H,RAOOV,M.Magnetic poly(beta-cyclodextrin-ionic liquid)nanocomposites for micro-solid phaseextraction of selected polycyclic aromatic hydrocarbons in rice samples prior to GC-FID analysis[J].Food Chemistry,2019,278:322-332.doi:10.1016/j.foodchem.2018.10.145
[4]BAJER T,SURMOVA S,EISNER A,KAREL V,PETRA B.Use of simultaneous distillation-extraction,supercritical fluid extraction and solid-phase microextraction for characterisation of the volatile profile of Dipteryx odorata(Aubl.)Willd[J].Industrial Crops and Products,2018,119:313-321.doi:10.1016/j.indcrop.2018.01.055.
[5]HATAMI T,JOHNER J C F,ZABOT G L,MEIRELES M A A.Supercritical fluid extraction assisted by cold pressing from clove buds:Extraction performance,volatile oil composition,and economic evaluation[J].Journal of Supercritical Fluids,2019,144:39-47.doi:10.1016/j.supflu.2018.10.003.
[6]AL-TAHER F,NEMZER B.Determination and quantitation of residual solvents in natural food ingredients using a static headspace gas chromatography with flame ionization detection and mass spectrometric detection method[J].Journal of Food Protection,2018,81(10):1573-1581.doi:10.4315/0362-028X.JFP-18-142.
[7]CAMELEYRE M,LYTRA G,BARBE J C.Static headspace analysis using low-pressure gas chromatography and mass spectrometry,application to determining multiple partition coefficients:a practical tool for understanding red wine fruity volatile perception and the sensory impact of higher alcohols[J].Analytical Chemistry,2018,90(18):10812-10818.doi:10.1021/acs.analchem.8b01896.
[8]刘传和,刘岩.4种芒果香气品质分析[J].广东农业科学,2016,43(10):123-127.doi:10.16768/j.issn.1004-874X.2016.10.022.LIU C H,LIU Y.Aroma quality of four cultivars of mango fruits[J].Guangdong Agricultural Sciences,2016,43(10):123-127.doi:10.16768/j.issn.1004-874X.2016.10.022.
[9]CACHO J I,CAMPILL N,VINAS P,HERNáNDEZ-CóRDOBAM.A simple device for headspace sorptive extraction prior to gas chromatography-mass spectrometry analysis[J].Talanta,2019,195:796-799.doi:10.1016/j.talanta.2018.12.001.
[10]倪永年.化学计量学在分析化学中的应用[M].北京:科学出版社,2004.NI Y N.The application of chemometrics in analytical chemistry[M].Beijing:Science Press,2004.
[11]陈义强,范坚强,包可翔,陈少滨.不同移栽期烟草生育期气温因子主成分与烟叶品质相关性分析[J].广东农业科学,2017,44(11):1-6.doi:10.16768/j.issn.1004-874X.2017.11.001.CHEN Y Q,FAN J Q,BAO K X,CHEN S B.Principal component of temperature factors during the growth period of different transplanting date on tobaccoand its relation leaves quality[J].Guangdong Agricultural Sciences,2017,44(11):1-6.doi:10.16768/j.issn.1004-874X.2017.11.001.
[12]张亚平,张晓宇,周顺,何庆,王孝峰,佘世科,徐迎波,宁敏.卷烟纸组分对常规和细支卷烟烟气释放量及感官质量的影响[J].烟草科技,2017,50(11):48-57.doi:10.16135/j.issn1002-0861.2017.0052.ZHANG Y P,ZHANG X Y,ZHOU S,HE Q,WANG X F,SHE S K,XUY B,NING M.Effects of cigarette paper components on smoke release and sensory quality of normal and slim cigarettes[J].Tobacco Science&Technology,2017,50(11):48-57.doi:10.16135/j.issn1002-0861.2017.0052.
[13]杨超,丁根胜,万里兴,黄新民,杨盛刚,穆林,惠建权.基于烟叶化学成分的卷烟叶组感官质量和风格研究[J].烟草科技,2018,51(8):85-91.doi:10.16135/j.issn1002-0861.2017.0331.YANG C,DING G S,WAN L X,HUANG X M,YANG S G,MU L,HUI J Q.Relationships of main chemical components in tobacco blend of cigarette with its sensory quality and style[J].Tobacco Science&Technology,2018,51(8):85-91.doi:10.16135/j.issn1002-0861.2017.0331.
[14]李广才,余玉梅,胡建军,周冀衡.湖南烤烟主要化学成分与评吸质量的非线性关系解析[J].中国烟草学报,2012,18(4):17-26.doi:10.3969/j.issn.1004-5708.2012.04.003.LI G C,YU Y M,HU J J,ZHOU J H.Non-linear relationship between chemical compositions and smoking quality in flue-cured tobacco in Hunan province[J].Acta Tabacaria Sinica,2012,18(4):17-26.doi:10.3969/j.issn.1004-5708.2012.04.003.
[15]周芸,过伟民,李小兰,周晓,王学杰,郭建华,韩加所,张仕祥,戴华鑫,牟文君.清香型产区烤烟游离氨基酸与感官质量的关联分析[J].烟草科技,2018,51(11):28-35.ZHOU Y,GUO W M,LI X L,ZHOU X,WANG X J,GUO J H,HAN J S,ZHANG S X,DAI H X,MU W J.Correlation between free amino acids and sensory quality for flue-cured tobacco of fresh flavor type tobaccoplanting areas[J].Tobacco Science&Technology,2018,51(11):28-35.doi:10.16135/j.issn1002-0861.2017.0557.
[16]YC/T 31-1996烟草及烟草制品试样的制备和水分测定烘箱法[S].1996.YC/T 31-1996.Tobacco and tobacco products-preparation of test sample and determination of water content-oven method[S].1996.
[17]谢剑平.烟草与烟气化学成分[M].北京:化学工业出版社,2010.XIE J P.Tobacco and smoke chemical composition[M].Beijing:Chemical Industry Press,2010.
[18]SINKOV N A,HARYNUK J J.Three-dimensional cluster resolution for guiding automatic chemometric model optimization[J].Talanta,2013,103:252-259.doi:10.1016/j.talanta.2012.10.040.
[19]LEARDI R.Application of genetic algorithm-PLS for feature selection in spectral data sets[J].Journal of Chemometrics,2000,14:643-655.doi:10.1002/1099-128X(200009/12)14:5/6<643::AID-CEM621>3.0.CO;2-E.
[20]NI Y N,MEI M H,KOKOT S.Resolution of high performance liquid chromatographic fingerprints of Rhizoma curcumae by application of chemometrics[J].Journal of Liquid Chromatography&Related Technologies,2011,34:1952-1964.doi:10.1080/10826076.2011.582215.
[21]TEYE E,HUANG X Y,DAI H,CHEN Q S.Rapid differentiation of Ghana cocoa beans by FT-NIR spectroscopy coupled with multivariate classification[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2013,114:183-189.doi:10.1016/j.saa.2013.05.063.
[22]付茂红,钟娟,谭忠元,彭文璟,杨杰,周金燕,谭红.改进型人工神经网络优化Iturin A发酵培养基研究[J].广东农业科学,2015,17:102-107.doi:10.16768/j.issn.1004-874x.2015.17.006.FU M H,ZHONG J,TAN Z Y,PENG W J,YANG J,ZHOU J Y,TAN H.Optimization of fermentation medium for Iturin A by improved artificial neural network approach[J].Guangdong Agricultural Sciences,2015,42(17):102-107.doi:10.16768/j.issn.1004-874x.2015.17.006.
[23]LIU F,HE Y,WANG L.Determination of effective wavelengths for discrimination of fruit vinegars using near infrared spectroscopy and multivariate analysis[J].Analytica Chimica Acta,2008,615:10-17.doi:10.1016/j.aca.2008.03.030.