茶叶品质化学和仪器鉴定研究
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摘要
茶叶品质感官鉴定和评价虽然是目前的主要方法，但其经验性很强，而且容易受到审评员的心理和生理因素影响。寻找茶叶品质化学和仪器鉴定方法是茶叶研究者和生产经营者的共同愿望。尽管茶叶品质的化学和仪器鉴定研究已经取得重要进展，但是由于有些技术的开发仍然有待进一步成熟；有些技术虽然比较成熟，但由于设备昂贵或操作繁杂，在实际应用中还存在各种困难。针对这些情况，本研究以HLPC、GC和色差分析等普及性较广的技术，并结合主成分分析(PCA)、回归分析等方法，寻找主要茶类品质鉴定的有效手段，为茶叶品质理化鉴定或开发相关鉴定装备提供重要信息。
对17个红茶样品的化学分析和茶汤色差鉴定结果表明，红茶感官评价因子之间及其与感官评价总分(TQS)之间存在显著相关关系。茶叶咖啡因、N、氨基酸、多酚类、没食子儿茶素(GC)、表没食子儿茶素(EGC)、儿茶素(C)、表儿茶素(EC)、表儿茶素没食子酸酯(ECG)、儿茶素没食子酸酯(CG)、总儿茶素类、茶黄素(TF)、茶黄素3’没食子酸酯(TF3；G)以及色差参数ΔL，Δa，Δb、ΔE与TQS存在显著相关关系。与TQS呈显著相关的参数可以分为4组，即含第一组为N化合物，第二组为酚类化合物，第三组为色素类，第四组为茶汤色泽指标。借助PCA分别从检测参数中提取出4项与第一至第四主成分密切相关的变量，以其为自变量，以TQS为依变量建立4个回归模型，均具有统计学意义。
同HPLC、GC和色差技术分析了23个绿茶样品滋味成分、挥发性成分和茶汤色差指标，用PCA提取7个与绿茶汤色、滋味和香气相关的变量，并与TQS构建回归方程，得TQS=105.82-0.56(ΔE)-0.15(total catechins)+0.32(geraniol)+0.53(GCG)+0.44(linalool oxideⅠ)-0.54(ascorbic acid)+0.24(n-valeraldehyde)(p=0.003，预测标准误差=2.97)。该预测模型性简化了绿茶品质的化学和仪器评价方法。
对17个茉莉花茶样品的分析研究和线性相关分析表明，茶汤的N、咖啡因(caffeine)、儿茶素(C)、表儿茶素(EC)、儿茶素没食子酸酯(CG)、儿茶素类总量(Total catechins)、萜品醇(terpineol)、橙花醇(nerol)、茶汤色差指标ΔL、Δb、ΔE与TQS存在显著相关关系；检测的36个变量参数经PCA分析，提取了12个重要变量，构建了预测茉莉花茶TQS的10个回归模型，具有显著统计学意义，分别适合于不同研究条件下对茉莉花茶TQS的预测。
在前述研究基础上，对来自10个中国的绿茶和10个韩国的绿茶化学成分和色差指标进行分析，并用PCA方法提取3个与第1-2主成分密切相关的变量进行三维作图分类。结果表明，茶叶化学和汤色指标可以部分地将两国的茶叶区分。
Sensory assessment is the major method for identification and evaluation of tea. However, it is completely experiential and is affected by the psychological and physiological status of the tea tasters. It is a common aspiration of the researchers, producers and managers to search for chemical and instrumental methods for evaluation of tea quality. Though progresses were made in this field, some of the technologies are still to be consummated and some them are difficult to be used in practice because of expensive equipment or complicated operations. HLPC, GC, color difference technologies and principal component analysis (PCA) method were used to construct mathematical models for estimation of tea quality so as to get useful information for developing equipments for evaluation of teas.
Chemical composition, color difference of black tea infusions and their relationship with sensory quality assessed by tea tasters were analyzed. There was significant correlation between the individual quality attributes. Content of caffeine, nitrogen, amino acids, polyphenols, gallocatechin (GC), epigallocatechin (EGC), catechin (C), epicatechin (EC), epicatechin gallate (ECG), catechin gallate (CG), total catechins, theaflavin (TF) and theaflavin-3'-gallate (TF3'G) and infusion colour indicator ofΔL,Δa,Δb andΔE were significantly correlated to total quality score (TQS). The parameters correlated significantly with the TQS were classified into 4 groups. Group 1 is compounds with nitrogen element; group 2 phenol compounds; group 3 tea pigments and group 4 infusion color indicators. Four principal components were screened from the 4 groups as independent variables for constructing regression equations for estimation of black tea quality by principal component analysis. The regression of the TQS upon the principal components gives a highly significant relationship.
Parameters of liquor color difference, taste related constituents and aroma related volatiles in 23 Chinese green tea (Camellia sinensis) samples were analyzed by color difference meter, high performance liquid and gas chromatographs respectively. Seven variables were extracted by principal component analysis from the data sets corresponding to the liquor color, taste and aroma and linear regression of total quality score (TQS) upon the 7 extracted variables produced a significant relationship: TQS=105.82-0.56 (AE)-0.15 (total catechins)+0.32 (geraniol) +0.53 (GCG) +0.44 (linalool oxide I) -0.54 (ascorbic acid)+0.24 (n-valeraldehyde) (p=0.003, standard error of the estimation =2.97). The regressive relationship simplifies the process of chemical and instrumental assessment of sensory quality of green tea and could be used for green tea quality assessment.
Infusion chemical composition, color difference indicators and volatile constituents of seventeen jasmine scented tea samples and their correlation to sensory total quality score given by tea tasting panel were studied by techniques of high performance liquid chromatograph (HPLC), color difference metre and gas chromatograph. Spearman's linear correlation analysis showed that concentration of nitrogen, caffeine, catechin (C), epicatechin (EC), catechin gallate (CG), total catechins, terpineol, nerol and infusion light-black indicator AL, yellow-blue indicatorΔb, total color difference indicatorΔE were significantly correlated to sensory total quality score, respectively. Ten regression equations of the total quality score upon 12 components extracted from 36 tested indicators by principal component analysis (PCA) were obtained and they could properly estimate total quality score of jasmine scented teas.
Based on the above results, chemical and color difference analysis together with PCA were used to identify and classify 10 Chinese green teas and 10 Korean green teas by 3-D plot. The results showed that the Chinese and Korean teas were partially identified and classified by the method.
对17个红茶样品的化学分析和茶汤色差鉴定结果表明，红茶感官评价因子之间及其与感官评价总分(TQS)之间存在显著相关关系。茶叶咖啡因、N、氨基酸、多酚类、没食子儿茶素(GC)、表没食子儿茶素(EGC)、儿茶素(C)、表儿茶素(EC)、表儿茶素没食子酸酯(ECG)、儿茶素没食子酸酯(CG)、总儿茶素类、茶黄素(TF)、茶黄素3’没食子酸酯(TF3；G)以及色差参数ΔL，Δa，Δb、ΔE与TQS存在显著相关关系。与TQS呈显著相关的参数可以分为4组，即含第一组为N化合物，第二组为酚类化合物，第三组为色素类，第四组为茶汤色泽指标。借助PCA分别从检测参数中提取出4项与第一至第四主成分密切相关的变量，以其为自变量，以TQS为依变量建立4个回归模型，均具有统计学意义。
同HPLC、GC和色差技术分析了23个绿茶样品滋味成分、挥发性成分和茶汤色差指标，用PCA提取7个与绿茶汤色、滋味和香气相关的变量，并与TQS构建回归方程，得TQS=105.82-0.56(ΔE)-0.15(total catechins)+0.32(geraniol)+0.53(GCG)+0.44(linalool oxideⅠ)-0.54(ascorbic acid)+0.24(n-valeraldehyde)(p=0.003，预测标准误差=2.97)。该预测模型性简化了绿茶品质的化学和仪器评价方法。
对17个茉莉花茶样品的分析研究和线性相关分析表明，茶汤的N、咖啡因(caffeine)、儿茶素(C)、表儿茶素(EC)、儿茶素没食子酸酯(CG)、儿茶素类总量(Total catechins)、萜品醇(terpineol)、橙花醇(nerol)、茶汤色差指标ΔL、Δb、ΔE与TQS存在显著相关关系；检测的36个变量参数经PCA分析，提取了12个重要变量，构建了预测茉莉花茶TQS的10个回归模型，具有显著统计学意义，分别适合于不同研究条件下对茉莉花茶TQS的预测。
在前述研究基础上，对来自10个中国的绿茶和10个韩国的绿茶化学成分和色差指标进行分析，并用PCA方法提取3个与第1-2主成分密切相关的变量进行三维作图分类。结果表明，茶叶化学和汤色指标可以部分地将两国的茶叶区分。
Sensory assessment is the major method for identification and evaluation of tea. However, it is completely experiential and is affected by the psychological and physiological status of the tea tasters. It is a common aspiration of the researchers, producers and managers to search for chemical and instrumental methods for evaluation of tea quality. Though progresses were made in this field, some of the technologies are still to be consummated and some them are difficult to be used in practice because of expensive equipment or complicated operations. HLPC, GC, color difference technologies and principal component analysis (PCA) method were used to construct mathematical models for estimation of tea quality so as to get useful information for developing equipments for evaluation of teas.
Chemical composition, color difference of black tea infusions and their relationship with sensory quality assessed by tea tasters were analyzed. There was significant correlation between the individual quality attributes. Content of caffeine, nitrogen, amino acids, polyphenols, gallocatechin (GC), epigallocatechin (EGC), catechin (C), epicatechin (EC), epicatechin gallate (ECG), catechin gallate (CG), total catechins, theaflavin (TF) and theaflavin-3'-gallate (TF3'G) and infusion colour indicator ofΔL,Δa,Δb andΔE were significantly correlated to total quality score (TQS). The parameters correlated significantly with the TQS were classified into 4 groups. Group 1 is compounds with nitrogen element; group 2 phenol compounds; group 3 tea pigments and group 4 infusion color indicators. Four principal components were screened from the 4 groups as independent variables for constructing regression equations for estimation of black tea quality by principal component analysis. The regression of the TQS upon the principal components gives a highly significant relationship.
Parameters of liquor color difference, taste related constituents and aroma related volatiles in 23 Chinese green tea (Camellia sinensis) samples were analyzed by color difference meter, high performance liquid and gas chromatographs respectively. Seven variables were extracted by principal component analysis from the data sets corresponding to the liquor color, taste and aroma and linear regression of total quality score (TQS) upon the 7 extracted variables produced a significant relationship: TQS=105.82-0.56 (AE)-0.15 (total catechins)+0.32 (geraniol) +0.53 (GCG) +0.44 (linalool oxide I) -0.54 (ascorbic acid)+0.24 (n-valeraldehyde) (p=0.003, standard error of the estimation =2.97). The regressive relationship simplifies the process of chemical and instrumental assessment of sensory quality of green tea and could be used for green tea quality assessment.
Infusion chemical composition, color difference indicators and volatile constituents of seventeen jasmine scented tea samples and their correlation to sensory total quality score given by tea tasting panel were studied by techniques of high performance liquid chromatograph (HPLC), color difference metre and gas chromatograph. Spearman's linear correlation analysis showed that concentration of nitrogen, caffeine, catechin (C), epicatechin (EC), catechin gallate (CG), total catechins, terpineol, nerol and infusion light-black indicator AL, yellow-blue indicatorΔb, total color difference indicatorΔE were significantly correlated to sensory total quality score, respectively. Ten regression equations of the total quality score upon 12 components extracted from 36 tested indicators by principal component analysis (PCA) were obtained and they could properly estimate total quality score of jasmine scented teas.
Based on the above results, chemical and color difference analysis together with PCA were used to identify and classify 10 Chinese green teas and 10 Korean green teas by 3-D plot. The results showed that the Chinese and Korean teas were partially identified and classified by the method.
引文
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张方舟，黄玮(2004)．乌龙茶的包装和贮运技术．中国茶叶，26(5)：6．
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Cloughley JB(1980). The effect of fermentation temperature on the quality parameters and price evaluation of Central African black teas. Journal of the Science of Food and Agriculture, 31:911-919.
Hilton PJ and Ellis RT (1972). Estimation of the market value of central African tea by theaflavin analysis. Journal of the Science of Food and Agriculture, 23: 227-232.
Horie H. and Kohata K (1998). Application of capillary electrophoresis to tea quality estimation. Journal of Chromatography A, 802:219-223.
Ivarsson P, Homin S, Hojer NE, Krantz-Rulcker C and Winquist F(2001) Discrimination of tea by means of a voltammetric electronic tongue and different applied waveforme. Sensors and Actuators B, 76: 449-454.
Ivarsson P, Kikkawa Y, Winquist F, Krantz-Rulcker C, Hojer NE, Hayashi K, Toko K and Lundstrom Ⅰ (2001) Comparison of a voltammetric electronic tongue and a lipid membrane taste sensor. Analytica Chimica Acta, 449: 59-68.
Legin A, Rudnitskaya A, Vlasov Y, Natale CD, Davide F and D'Amico A (1997). Tasting of beverages using an electronic tongue. Sensors and Actuators B, 44: 291-296.
Liang YR and Xu YR (2001). Effect of pH on cream particle formation and extraction yield of black tea. Food Chemistry, 74: 155-160.
Liang YR, MA WY, Lu JL & Wu Y (2001). Comparison of chemical compositions of Illex latifolia Thumb and Camellia sinensis L. Food Chemistry, 75:339-343.
Obanda M, Owuor PO and Taylor SJ (1997) Flavanol composition and caffeine content of green leaf as quality potential indicators of Kenyan black teas. Journal of the Science of Food and Agriculture, 72:209-215.
Roberts EAH and Smith RF (1963). The phenolic substances of manufactured tea. Ⅸ. The speetrophotometric evaluation of tea liquors. Journal of the Science of Food and Agriculture, 14: 689-700.
Wright LP, Mphangwe NIK, Nyirenda HE and Apostolides Z (2000). Analysis of caffeine and flavan-3-ol composition in the fresh leaf of Camellia sinensis for predicting the quality of black tea produced in Central and Southern Africa. Journal of the Science of Food and Agriculture, 80:1923-1830.
钟罗主编(1989)．茶叶理化分析方法．上海：上海科学技术出版社，Pp358-389．
Cloughley JB (1980). The effect of fermentation temperature on the quality parameters and price evaluation of Central African black teas. Journal of the Science of Food and Agriculture, 31: 911-919.
Hilton PJ and Ellis RT(1972). Estimation of the market value of central African tea by theaflavin analysis. Journal of the Science of Food and Agriculture, 23: 227-232.
Hori H and Kohata K(1998). Application of capillary electrophoresis to tea quality estimation. Journal of Chromatography A, 802: 219-223.
Ivarsson P, Homin S, Hojer NE, Krantz-Rulcker C and Winqnist F(2001). Discrimination of tea by means of a voltammetric electronic tongue and different applied waveforme. Sensors and Actuators B, 2001,76, 449-454.
Ivarsson P, Kikkawa Y, Winquist F, Krantz-Rulcker C, Hojer NE, Hayashi K, Toko K and Ltmdstrom I(2001). Comparison of a voltammetfic electronic tongue and a lipid membrane taste sensor. Analytica Chimica Acta, 449: 59-68.
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