Chemical Patterns of Polyphenols and Free Amino Acids in Teas Affected by Processing Methods
-
摘要: 多酚类物质和游离氨基酸是茶叶重要品质成分。本研究将金观音、黄观音、福云6号等7个福建茶树品种春梢鲜叶原料分别加工成4种茶类（绿茶、白茶、红茶和乌龙茶），并分析比较了鲜叶原料及其所制茶类的茶多酚、游离氨基酸总量、儿茶素类和游离氨基酸组分的模式差异。结果表明，基于供试茶样（茶多酚×游离氨基酸）含量的二维“点集”分布视图可将4种茶类及其鲜叶原料划分成3个主要类群：绿茶、白茶和一芽二、三叶鲜叶样；乌龙茶和中、小开面二至四叶鲜叶样；红茶样。鲜叶原料采摘标准是乌龙茶有别于其他茶类的首要影响因素。通过供试茶样儿茶素类和游离氨基酸的靶标检测，采用主成分分析（PCA）可进一步比较白茶与其他茶类化学轮廓的模式差异。茶叶在加工过程中简单儿茶素较酯型儿茶素更易趋于氧化减少，萎凋工序则有助于白茶游离氨基酸（苏氨酸和亮氨酸）的形成或保留。Abstract: Polyphenols and free amino acids are important components in terms of tea quality. In this study, specific fresh spring shoots harvested from bushes of 7 different tea cultivars (Camellia sinensis), including Jinguanyin, Huangguanyin and Fuyun 6, were processed into green, white, black and oolong teas.Polyphenols, catechins, and total free amino acids (FAAs) in the fresh leaves as well as the teas made from them were determined for comparison. Based on the scatter plot for the polyphenols and FAAs contents of the 4 teas, 3 distinguishable patterns emerged. They were grouped as Type I, which included the green and white teas along with the fresh 2nd/3rd-leaf-1 bud leaves, Type Ⅱ, which consisted of the oolong teas and the fresh 2nd-to-4th-leaf-1 banjhi bud leaves, and Type Ⅲ, which was the black tea. Maturity of shoots was found to bea key factor that differentiated oolong tea from others. On the other hand, aprincipal component analysis (PCA) using data on catechins or FAAs would be necessary for a satisfactory differentiation on white tea. The non-ester type catechins were more prone to oxidization than the ester type catechins during tea processing, and withering contributed to the increase of FAAs, especially threonine and leucine, in the white tea.
-
Key words:
- tea processing /
- tea varieties /
- chemical patterns /
- polyphenols /
- free amino acids
-
图 1 供试茶样茶多酚 (TPs) 和游离氨基酸 (FAAs) 含量
注：图中茶多酚、游离氨基酸平均含量分别为[红茶：(10.37±2.29eC)%、(4.73±0.35bAB)%]，[绿茶：(18.40±1.42abA)%、(5.19±0.81abAB)%]，[幼嫩叶：(18.76±1.30aA)%、(4.72±0.56bB)%]，[白茶：(16.98±1.39bcAB)%、(5.90±0.82aA)%]，[成熟叶：(16.29±0.57cdAB)%、(1.72±0.42cC)%]，[乌龙茶：(15.10±0.86dB)%、(1.98±1.00cC)%]，数据后不同大、小写字母表示差异达极显著 (P＜0.01) 或显著 (P＜0.05) 水平。
Figure 1. Scatter plot of polyphenols and FAAs in tea samples
图 2 基于供试茶样儿茶素类含量的主成分分析
注：变量采用Par-scaling标度化预处理。图 3同。
Figure 2. Scatter plot of PCA scores on catechin contents of tea samples
图 3 基于供试游离氨基酸含量的主成分分析
Figure 3. Scatter plot of PCA scores on FAAs contents of tea samples
表 1 4种茶类及其鲜叶原料样品编码
Table 1. Sample codes of teas and their leafraw materials
茶树品种 采摘标准 鲜叶 绿茶 白茶 红茶 乌龙茶 金观音 幼嫩叶 Y1 G1 W1 B1 黄观音 幼嫩叶 Y2 G2 W2 B2 - 福云6号 幼嫩叶 Y3(1) G3(1) W3(1) B3(1) - 福云6号 幼嫩叶 Y3(2) G3(2) W3(2) B3(2) - 福鼎大毫茶 幼嫩叶 Y4 G4 W4 - - 福安大白茶 幼嫩叶 Y5 G5 W5 - - 金观音 成熟叶 M1 - - - O1 黄观音 成熟叶 M2 - - - O2 铁观音 成熟叶 M3 - - - O3 黄棪 成熟叶 M4 - - - O4 注：福云6号茶树品种加工2个批次；乌龙茶样品为毛茶样。全部茶样共计30份，“-”表示未加工该茶类样品。 
下载: 导出CSV
表 2 4种茶类及其鲜叶原料的儿茶素类含量
Table 2. Catechin contents in teas and their raw materials
[单位/(mg·g-1干重)] 组分 嫩叶 绿茶 白茶 红茶 成熟叶 乌龙茶 GA 1.66±1.39aA 1.59±1.29aA 2.42±1.78aA 5.03±2.00aA 1.02±0.22aA 1.10±0.12aA C 3.53±0.63aA 3.36±0.40aA 2.14±0.49bB 0.51±0.34cC 3.24±0.72aA 3.11±0.63aA EC 8.54±2.16aA 8.45±1.83aA 4.27±1.45bB 2.27±2.45bB 9.17±0.72aA 9.70±0.96aA EGC 32.98±15.48abAB 31.06±14.32abAB 14.46±9.14bAB 1.26±1.59bB 38.59±5.78aA 34.96±8.97abAB GCG 9.07±9.22aA 8.28±6.89aA 6.75±6.49aA 4.11±2.75aA 17.83±4.91aA 13.80±0.87aA EGCG 71.97±14.63aA 70.02±15.01abAB 56.01±15.54bcAB 4.01±2.15dC 55.31±6.94bcAB 48.37±11.89cB ECG 20.84±3.99aA 20.65±3.43abA 17.29±2.94bA 4.09±2.84dC 10.34±0.84cB 9.91±1.13cBC 注：不同种类茶样没食子酸及各儿茶素采用平均含量±标准偏差表示；根据方差齐次性检验结果，分别采用LSD法和Tamhane′s T2法对各成分平均含量进行多重比较。同行数据后不同大、小写字母表示差异达极显著 (P＜0.01) 或显著 (P＜0.05) 水平。表 3同。
下载: 导出CSV
表 3 4种茶类及其鲜叶原料的游离氨基酸含量
Table 3. FAAS contents in teas and their raw materials
[单位/(mg·g-1干重)] 组分 嫩叶 绿茶 白茶 红茶 成熟叶 乌龙茶 Asp 1.52±0.62aA 1.77±0.90aA 1.39±0.58aA 1.05±0.14aA 0.85±0.36aA 0.90±0.38aA Glu 2.06±0.8aA 2.53±1.13aA 1.08±0.4aA 1.73±0.36aA 1.17±0.34aA 1.06±0.12aA Ser 0.56±0.10aA 0.73±0.20aA 1.83±1.53aA 1.17±0.46aA 0.32±0.10aA 0.65±0.16aA His 0.92±0.49bB 0.89±0.45bB 1.28±0.85bAB 2.21±0.82aA 0.79±0.34bB 0.98±0.22bB Gly 0.42±0.42aA 0.65±0.75aA 0.67±0.76aA 0.74±0.53aA 0.33±0.19aA 0.62±0.37aA Thr 0.18±0.10bB 0.29±0.05aAB 0.37±0.11aA 0.32±0.10aAB 0.17±0.09bB 0.30±0.11aAB Arg 0.67±0.41aA 0.78±0.50aA 0.85±0.61aA 0.70±0.35aA 0.14±0.06aA 0.17±0.08aA Ala 0.25±0.05abA 0.31±0.07abA 0.81±0.30aA 0.54±0.17abA 0.16±0.09bA 0.31±0.11abA THE 13.83±4.31abA 15.97±4.15aA 13.03±4.54abAB 9.74±0.51bcABC 5.35±2.73cC 6.85±3.45cBC Tyr 0.35±0.50aA 0.03±0.04aA 0.47±0.44aA 0.32±0.52aA 0.13±0.09aA 0.34±0.34aA Cys 0.26±0.34aA 0.36±0.41aA 1.16±1.35aA 1.26±0.85aA 0.53±0.51aA 0.86±0.40aA Val 0.03±0.04aA 0.15±0.24aA 0.48±0.40aA 0.40±0.36aA 0.03±0.01aA 0.13±0.10aA Met 1.07±1.19aA 0.96±1.09aA 0.62±0.82aA 0.80±0.98aA 0.79±0.37aA 0.68±0.32aA Phe 0.05±0.07aA 0.25±0.43aA 0.63±0.57aA 0.37±0.31aA 0.07±0.03aA 0.38±0.24aA Ile 0.02±0.02aA 0.11±0.20aA 0.35±0.29aA 0.19±0.13aA 0.03±0.02aA 0.12±0.05aA Leu 0.04±0.05cB 0.19±0.22bcAB 0.47±0.22aA 0.31±0.21abAB 0.13±0.14bcB 0.18±0.12bcAB Lys 0.05±0.06aA 0.16±0.20aA 0.53±0.39aA 0.32±0.21aA 0.13±0.11aA 0.32±0.14aA
下载: 导出CSV
-
[1] LI X L, HE Y. Discriminating varieties of tea plant based on Vis/NIR spectral characteristics and using artificial neural networks[J]. Biosyst Eng, 2008, 99(3):313-321. doi: 10.1016/j.biosystemseng.2007.11.007 [2] LIN J, ZHANG P, PAN Z Q, et al. Discrimination of oolong tea (Camellia sinensis) varieties based on feature extraction and selection from aromatic profiles analysed by HS-SPME/GC-MS[J]. Food Chem, 2013, 141(1):259-265. doi: 10.1016/j.foodchem.2013.02.128 [3] CHENG Q, YANG F, WANG D H, et al. Discrimination of Minnan oolong tea varieties by NIR spectroscopy[J]. Spectrosc Spect Anal, 2014, 34(3):656-659. https://www.ncbi.nlm.nih.gov/pubmed/25208385 [4] LEE J E, LEE B J, CHUNG J O, et al. Geographical and climatic dependencies of green tea (Camellia sinensis) metabolites:A H-1 NMR-based metabolomics study[J]. J Agric Food Chem, 2010, 58(19):10582-10589. doi: 10.1021/jf102415m [5] YE N S, ZHANG L Q, GU X X. Discrimination of green teas from different geographical origins by using HS-SPME/GC-MS and pattern recognition methods[J]. Food Anal Methods, 2012, 5(4):856-860. doi: 10.1007/s12161-011-9319-9 [6] XU W P, SONG Q S, LI D X, et al. Discrimination of the production season of Chinese green tea by chemical analysis in combination with supervised pattern recognition[J]. J Agric Food Chem, 2012, 60(28):7064-7070. doi: 10.1021/jf301340z [7] ALCAZAR A, BALLESTEROS O, JURADO J M, et al. Differentiation of green, white, black, oolong, and Pu-erh teas according to their free amino acids content[J]. J Agric Food Chem, 2007, 55(15):5960-5965. doi: 10.1021/jf070601a [8] FUJIWARA M, ANDO I, ARIFUKU K. Multivariate analysis for H-1-NMR spectra of two hundred kinds of tea in the world[J]. Anal Sci, 2006, 22(10):1307-1314. doi: 10.2116/analsci.22.1307 [9] 彭继宇, 宋星霖, 刘飞, 等.基于波谱技术的茶树生长与茶叶品质信息快速检测研究进展[J].光谱学与光谱分析, 2016, 36(3):775-782. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201603041.htm [10] QIN Z H, PANG X L, CHEN D, et al. Evaluation of Chinese tea by the electronic nose and gas chromatography-mass spectrometry:Correlation with sensory properties and classification according to grade level[J]. Food Res Int, 2013, 53(2):864-874. doi: 10.1016/j.foodres.2013.02.005 [11] CHEN Q S, ZHAO J W, VITTAYAPADUNG S. Identification of the green tea grade level using electronic tongue and pattern recognition[J]. Food Res Int, 2008, 41(5):500-504. doi: 10.1016/j.foodres.2008.03.005 [12] ZHAO J W, CHEN Q S, CAI J R, et al. Automated tea quality classification by hyperspectral imaging[J]. Appl Opt, 2009, 48(19):3557-3564. doi: 10.1364/AO.48.003557 [13] 吴平.茶叶分类进展研究——兼论六堡茶的归属[J].茶叶科学, 2014, 34(4):408-416. http://www.cnki.com.cn/Article/CJFDTOTAL-CYKK201404018.htm [14] WU Q J, DONG Q H, SUN W J, et al. Discrimination of Chinese teas with different fermentation degrees by stepwise linear discriminant analysis (S-LDA) of the chemical compounds[J]. J Agric Food Chem, 2014, 62(38):9336-9344. doi: 10.1021/jf5025483 [15] TAN J F, DAI W D, LU M L, et al. Study of the dynamic changes in the non-volatile chemical constituents of black tea during fermentation processing by a non-targeted metabolomics approach[J]. Food Res Int, 2016, 79:106-113. doi: 10.1016/j.foodres.2015.11.018 [16] HAN Z X, RANA M M, LIU G F, et al. Green tea flavour determinants and their changes over manufacturing processes[J]. Food Chem, 2016, 212:739-748. doi: 10.1016/j.foodchem.2016.06.049 [17] LIN S Y, CHEN Y L, LEE C L, et al. Monitoring volatile compound profiles and chemical compositions during the process of manufacturing semi-fermented oolong tea[J]. J Hortic Sci Biotechnol, 2013, 88(2):159-164. doi: 10.1080/14620316.2013.11512951 [18] 陈林, 陈键, 陈泉宾, 等.做青工艺对乌龙茶香气组成化学模式的影响[J].茶叶科学, 2014, 34(4):387-395. http://www.cnki.com.cn/Article/CJFDTOTAL-CYKK201404014.htm [19] 许凌, 周卫龙, 高海燕, 等. GB/T 8303-2013茶磨碎试样的制备及其干物质含量测定[S]. 北京: 中国质检出版社 (中国标准出版社), 2014. [20] 周卫龙, 徐建峰, 许凌. GB/T 8313-2008茶叶中茶多酚和儿茶素类含量的检测方法[S]. 北京: 中国标准出版社, 2008. [21] 徐建峰, 周卫龙, 陆小磊, 等. GB/T 8314-2013茶游离氨基酸总量的测定[S]. 北京: 中国质检出版社 (中国标准出版社), 2014. [22] 王丽丽, 陈键, 宋振硕, 等.茶叶中没食子酸、儿茶素类和生物碱的HPLC检测方法研究[J].福建农业学报, 2014, 29(10):987-994. doi: 10.3969/j.issn.1008-0384.2014.10.011 [23] 宋振硕, 王丽丽, 陈键, 等.茶鲜叶萎凋过程中游离氨基酸的动态变化规律[J].茶叶学报, 2015, 56(4):206-213. http://www.cnki.com.cn/Article/CJFDTOTAL-CYKJ201504004.htm [24] 叶乃兴.茶叶品质性状的构成与评价[J].中国茶叶, 2010, 32(8):10-11. http://www.cnki.com.cn/Article/CJFDTOTAL-CAYA201008006.htm [25] TOUNEKTI T, JOUBERT E, HERNANDEZ I, et al. Improving the polyphenol content of tea[J]. Crit Rev Plant Sci, 2013, 32(3):192-215. doi: 10.1080/07352689.2012.747384 [26] HARA Y. Tea catechins and their applications as supplements and pharmaceutics[J]. Pharmacol Res, 2011, 64(2):100-104. doi: 10.1016/j.phrs.2011.03.018 [27] HIGDON J V, FREI B. Tea catechins and polyphenols:Health effects, metabolism, and antioxidant functions[J]. Crit Rev Food Sci Nutr, 2003, 43(1):89-143. doi: 10.1080/10408690390826464 [28] 陈林, 陈键, 张应根, 等.清香型乌龙茶品质形成中游离氨基酸指纹图谱变化规律[J].农业工程学报, 2012, 28(17):244-252. doi: 10.3969/j.issn.1002-6819.2012.17.036 [29] CHEN L, CHEN Q, ZHANG Z Z, et al. A novel colorimetric determination of free amino acids content in tea infusions with 2, 4-dinitrofluorobenzene[J]. J Food Compost Anal, 2009, 22(2):137-141. doi: 10.1016/j.jfca.2008.08.007 [30] 杨伟丽, 肖文军, 邓克尼.加工工艺对不同茶类主要生化成分的影响[J].湖南农业大学学报:自然科学版, 2001, 27(5):384-386. http://www.cnki.com.cn/Article/CJFDTOTAL-HNND200105016.htm [31] 王贵芳. 丹桂在四茶类加工中主要生化成分的变化研究[D]. 福州: 福建农林大学, 2008. [32] LÜ S D, WU Y S, WEI J F, et al. Application of gas chromatography-mass spectrometry and chemometrics methods for assessing volatile profiles of Pu-erh tea with different processing methods and ageing years[J]. RSC Adv, 2015, 5(107):87806-87817. doi: 10.1039/C5RA15381F [33] 陈林, 陈键, 张应根, 等.清香型乌龙茶品质形成过程主要生化成分的动态变化规律[J].福建农业学报, 2012, 27(8):857-862. http://www.fjnyxb.cn/CN/abstract/abstract1979.shtml [34] 王文杰, 徐卫兵, 雷攀登, 等.我国制茶工艺技术的发展与方向[J].中国茶叶加工, 2012, (3):4-7. http://www.cnki.com.cn/Article/CJFDTOTAL-CYJG201203004.htm [35] LI S M, LO C Y, PAN M H, et al. Black tea:chemical analysis and stability[J]. Food Funct, 2013, 4(1):10-18. doi: 10.1039/C2FO30093A -
点击查看大图
图(3) / 表(3)
计量
- 文章访问数: 1601
- HTML全文浏览量: 155
- PDF下载量: 301
- 被引次数: 0
