基于气相色谱-质谱技术与多元统计分析对不同栗香特征绿茶判别分析
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摘要
采用气相色谱-质谱联用技术结合多元统计分析主成分分析(principal component analysis,PCA)、偏最小二乘法-判别分析(partial least squares-discriminant analysis,PLS-DA)和系统聚类分析(hierarchical clusteranalysis,HCA)对18个不同栗香特征的绿茶开展研究。结果表明,PCA、PLS-DA和HCA均可直观地对3种不同栗香特征的绿茶进行有效区分;PLS-DA中,18个栗香茶样基于其香气特征实现良好分离,其中R2Y=0.843、Q2=0.694,说明该模型对3种栗香特征绿茶具有良好的稳定性和较好的预测能力;HCA中,3种栗香绿茶在聚类距离12处被清晰地分成3类,其中板栗香型和嫩栗香型距离更接近,聚类效果和感官辨识基本一致。此外,基于变量投影重要性大于1,筛选出了38种区分不同栗香特征的重要挥发性组分。
The volatile constitutions of 18 green tea samples with three different types of characteristic chestnut-like aroma were characterized based on gas chromatography-mass spectrometry(GC-MS) combined with multivariate statistical data analysis including principal component analysis(PCA), hierarchical cluster analysis(HCA) and partial least squares-discriminant analysis(PLS-DA). The results showed that PCA, PLS-DA and HCA could achieve good differentiation of three chestnut flavored green teas. In the PLS-DA analysis, 18 chestnut-like green tea samples were well separated according to their aroma characteristics,and the well-explained variance(R2 Y =0.843) and cross-validated predictive capability(Q2 = 0.694) indicated the model's good feasibility. In the HCA analysis, three kinds of chestnut fragrant green tea could be clearly divided into three categories at a distance of 12, of which the chestnut-like and tender chestnut-like tea samples were closer, matching the results of sensory evaluation. In addition, 38 volatile components were identified based on variable importance in projection(VIP) score > 1, which were responsible for the discrimination of green teas with three different flavor characteristics.
The volatile constitutions of 18 green tea samples with three different types of characteristic chestnut-like aroma were characterized based on gas chromatography-mass spectrometry(GC-MS) combined with multivariate statistical data analysis including principal component analysis(PCA), hierarchical cluster analysis(HCA) and partial least squares-discriminant analysis(PLS-DA). The results showed that PCA, PLS-DA and HCA could achieve good differentiation of three chestnut flavored green teas. In the PLS-DA analysis, 18 chestnut-like green tea samples were well separated according to their aroma characteristics,and the well-explained variance(R2 Y =0.843) and cross-validated predictive capability(Q2 = 0.694) indicated the model's good feasibility. In the HCA analysis, three kinds of chestnut fragrant green tea could be clearly divided into three categories at a distance of 12, of which the chestnut-like and tender chestnut-like tea samples were closer, matching the results of sensory evaluation. In addition, 38 volatile components were identified based on variable importance in projection(VIP) score > 1, which were responsible for the discrimination of green teas with three different flavor characteristics.
引文
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[27]唐军,廖享,童红,等.基于气质与PLS-DA对新疆薰衣草精油判别分析[J].计算机与应用化学,2014,31(6):702-704.DOI:10.11719/com.app.chem20140613.
[28]舒畅.龙井茶特征香气成分分析及鉴定研究[D].上海:上海应用技术学院,2016.
[29]沈生荣,杨贤强.不同等级龙井茶香气成分的研究[J].福建茶叶,1989(4):25-30.
[30]吴勇.萜烯类化合物与茶叶香气[J].化学工程与装备,2009(11):123-125.DOI:10.3969/j.issn.1003-0735.2009.11.042.
[31]叶国注,江用文,尹军峰,等.板栗香型绿茶香气成分特征研究[J].茶叶科学,2009,29(5):385-394.
[2]吕连梅,董尚胜.茶叶香气的研究进展[J].茶叶,2002(4):181-184.DOI:10.3969/j.issn.0577-8921.2002.04.013.
[3]杨贤强,沈生荣,陈席卿.炒青绿茶制造中香气组份变化的研究[J].食品科学,1989,10(8):1-7.DOI:10.3969/j.issn.1000-3150.2009.08.004.
[4]杨亚军.评茶员培训教材[M].北京:金盾出版社,2009.
[5]DING X,WU C,HUANG J,et al.Characterization of interphase volatile compounds in Chinese Luzhou-flavor liquor fermentation cellar analyzed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry(HS-SPME/GC/MS)[J].LWT-Food Science and Technology,2016,66:124-133.DOI:10.1016/j.lwt.2015.10.024.
[6]ALASALVAR C,TOPAL B,SERPEN A,et al.Flavor characteristics of seven grades of black tea produced in Turkey[J].Journal of Agricultural&Food Chemistry,2012,60(25):6323-6232.DOI:10.1021/jf301498p.
[7]HU Y,KONG W,YANG X,et al.GC-MS combined with chemometric techniques for the quality control and original discrimination of Curcumae longae rhizome:analysis of essential oils[J].Journal of Separation Science,2014,37(4):404-411.DOI:10.1002/jssc.201301102.
[8]MELUCCI D,BENDINI A,TESINI F,et al.Rapid direct analysis to discriminate geographic origin of extra virgin olive oils by flash gas chromatography electronic nose and chemometrics[J].Food Chemistry,2016,204:263-273.DOI:10.1016/j.foodchem.2016.02.131.
[9]林杰.茶叶香气的图谱分析及在茶叶品质真实性鉴定中的应用[D].杭州:浙江大学,2013.
[10]JUMTEE K,KOMURA H,BAMBA T,et al.Predication of Japanese green tea(Sen-cha)ranking by volatile profiling using gas chromatography mass spectrometry and multivariate analysis[J].Journal of Bioscience and Bioengineering,2011,112(3):252-255.DOI:10.1016/j.jbiosc.2011.05.008.
[11]曹学丽,宋沙沙,龙立梅.绿茶品质及其审评方法的研究进展[J].食品科学技术学报,2014,32(1):47-52.DOI:10.3969/j.issn.2095-6002.2014.01.009.
[12]WU Y,LV S,CHEN W,et al.Comparative analysis of volatiles difference of Yunnan sun-dried Pu-erh green tea from different tea mountains:Jingmai and Wuliang mountain by chemical fingerprint similarity combined with principal component analysis and cluster analysis[J].Chemistry Central Journal,2016,10(1):11.DOI:10.1186/s13065-016-0159-y.
[13]朱荫,杨停,施江,等.西湖龙井茶香气成分的全二维气相色谱-飞行时间质谱分析[J].中国农业科学,2015,48(20):4120-4146.DOI:10.3864/j.issn.0578-1752.2015.20.013.
[14]龙立梅,宋沙沙,李柰,等.3种名优绿茶特征香气成分的比较及种类判别分析[J].食品科学,2015,36(2):114-119.DOI:10.7506/spkx1002-6630-201502022.
[15]袁海波,尹军峰,叶国柱,等.茶叶香型及特征物质研究进展(续)[J].中国茶叶,2009,31(8):14-15.DOI:10.3969/j.issn.1000-3150.2009.09.004.
[16]吕连梅,董尚胜.茶叶香气的研究进展[J].茶叶,2002,28(4):181-184.DOI:10.3969/j.issn.0577-8921.2002.04.013.
[17]宛晓春.茶叶生物化学[M].北京:中国农业出版社,2003.
[18]叶国注,袁海波,江用文,等.Bayes逐步判别法在绿茶板栗香化学识别上的应用[J].茶叶科学,2009,29(1):27-33.
[19]LV S,WU Y S,SONG Y Z,et al.Multivariate analysis based on GCMSfingerprint and volatile composition for the quality evaluation of Pu-erh green tea[J].Food Analytical Methods,2015,8(2):321-333.DOI:10.1007/s12161-014-9900-0.
[20]LV S,WU Y,ZHOU J,et al.The study of fingerprint characteristics of Dayi Pu-erh tea using a fully automatic HS-SPME/GC-MS and combined chemometrics method[J].PLoS ONE,2014,9(12):e116428.DOI:10.1371/journal.pone.0116428.
[21]WU Y,LV S,LIAN M,et al.Study of characteristic aroma components of baked Wujiatai green tea by HS-SPME/GC-MScombined with principal component analysis[J].CyTA:Journal of Food,2016,14:1-10.DOI:10.1080/19476337.2015.1123298.
[22]刘彬球,陈孝权,吴晓刚,等.PCA和PLS-DA用于晒青毛茶级别分类研究[J].茶叶科学,2015,35(2):179-184.DOI:10.3969/j.issn.1000-369X.2015.02.014.
[23]许洪庆,吕大树,张亚恒,等.二氯甲烷提取物致香成分GC/MS指纹图谱在烤烟香型鉴别中的应用[J].烟草科技,2017,50(1):31-40.DOI:10.16135/j.issn1002-0861.2016.0342.
[24]王世成,范津杉,王颜红,等.液相色谱-大气压化学电离质谱分析鉴别地沟油中的氧化成分[J].分析化学,2014,42(5):741-746.DOI:10.3724/SP.J.1096.2014.30858.
[25]熊淑雯,章开,陈东,等.指纹图谱技术结合PLS-DA在黄连上清丸质量控制中的应用[J].南昌大学学报(医学版),2015,55(6):15-19.DOI:10.13764/j.cnki.ncdm.2015.06.004.
[26]ZHU Y,SHAO C Y,LV H P,et al.Enantiomeric and quantitative analysis of volatile terpenoids in different teas(Camellia sinensis)[J].Journal of Chromatography A,2017,1490:177-190.DOI:10.1016/j.chroma.2017.02.013.
[27]唐军,廖享,童红,等.基于气质与PLS-DA对新疆薰衣草精油判别分析[J].计算机与应用化学,2014,31(6):702-704.DOI:10.11719/com.app.chem20140613.
[28]舒畅.龙井茶特征香气成分分析及鉴定研究[D].上海:上海应用技术学院,2016.
[29]沈生荣,杨贤强.不同等级龙井茶香气成分的研究[J].福建茶叶,1989(4):25-30.
[30]吴勇.萜烯类化合物与茶叶香气[J].化学工程与装备,2009(11):123-125.DOI:10.3969/j.issn.1003-0735.2009.11.042.
[31]叶国注,江用文,尹军峰,等.板栗香型绿茶香气成分特征研究[J].茶叶科学,2009,29(5):385-394.