基于UPLC-MS/MS技术的9个白茶实物标准样主要化学成分分析

doi:10.13304/j.nykjdb.2024.0284

中国农业科技导报 ›› 2024, Vol. 26 ›› Issue (12): 50-62.DOI: 10.13304/j.nykjdb.2024.0284

基于UPLC-MS/MS技术的9个白茶实物标准样主要化学成分分析

陈丽琴¹(), 周子维², 蔡亚威³, 张朝辉¹, 江胜滔², 艾克拜尔·热合曼¹(), 陈艳¹()

^1.宁德师范学院医学院，福建省毒物与药物毒理学重点实验室，福建宁德 352100
^2.宁德师范学院生物科学与工程学院，宁德师范学院茶叶审评中心，福建宁德 352100
^3.福建省裕荣香茶业有限公司，福建福鼎 355209

收稿日期:2024-04-09 接受日期:2024-07-13 出版日期:2024-12-15 发布日期:2024-12-17
通讯作者: 艾克拜尔·热合曼,陈艳
作者简介:陈丽琴 E-mail：543801435@qq.com
基金资助:
宁德师范学院引进人才科研启动项目(2018Y01);宁德师范学院创新团队项目(2022T03);宁德师范学院科研发展基金项目(2021FZ01)

Main Chemical Compounds Analysis of 9 White Tea Standard Samples Based on UPLC-MS/MS Technology

Liqin CHEN¹(), Ziwei ZHOU², Yawei CAI³, Zhaohui ZHANG¹, Shengtao JIANG², Aikebaer Reheman¹(), Yan CHEN¹()

^1.Fujian Key Laboratory of Toxicant and Drug Toxicology，Medical College，Ningde Normal University，Fujian Ningde 352100，China
^2.Tea Sensory Evaluation Research Center，College of Bioscience and Engineering，Ningde Normal University，Fujian Ningde 352100，China
^3.Fujian Yurongxiang Tea Co. ，Ltd. ，Fujian Fuding 355209，China

Received:2024-04-09 Accepted:2024-07-13 Online:2024-12-15 Published:2024-12-17
Contact: Aikebaer Reheman,Yan CHEN

摘要/Abstract

摘要：

为了更加客观、系统地评价不同花色和等级的白茶产品，以白茶标准样为试验材料，采用超高效液相色谱-三重四级杆质谱联用仪（ultra-performance liquid chromatography tandem mass spectrometry，UPLC-MS/MS）检测技术，对不同花色及同一花色不同等级的白茶标准样品的儿茶素、茶氨酸等主要化学物质进行检测和分析。结果表明，随着等级的降低，毫香毫味的感官总体逐步减弱，滋味由清鲜到清甜，再到醇厚。对不同等级的白茶比较发现，与白茶等级呈极显著正相关的组分有精氨酸（Arg）、天冬氨酸（Asp）、苏氨酸（Thr），其中Asp随着等级的降低逐渐减少，是决定不同等级白毫银针、白牡丹、贡眉、寿眉滋味差异的关键化学物质。对不同花色样品的主要化学物质进行偏最小二乘判别分析（partial least squares-discriminant analysis， PLS-DA）发现，丙氨酸（Ala）、茶氨酸（L-Thea）、组氨酸（His）、赖氨酸（Lys）以及表儿茶素没食子酸酯、表没食子儿茶素没食子酸酯等12个组分的变量重要性投影（variable important projection，VIP）值≥1.0。对同一花色不同等级样品主要化学物质的PLS-DA发现，VIP≥1.0的物质有脯氨酸（Pro）、组氨酸（His）、茶氨酸（L-Thea）以及苯丙氨酸（Phe）。以上研究结果为我国白茶产品风味品质评价和分析提供理论参考，对于不同花色及同一花色不同等级的白茶产品质量等级判别具有重要参考价值。

关键词: 白茶花色, 白茶等级, 氨基酸, 儿茶素, 化学物质

Abstract:

To evaluate white tea products of different types and grades objectively and systematically， ultra-performance liquid chromatography tandem mass spectrometry （UPLC-MS/MS） technology was used to detect and analyze main chemical compounds such as catechins and theanine in white tea standard samples of different types and different grades of the same type， using Chinese white tea standard samples as the test material. The results showed that， with the decrease of grade， the overall “fragrance and flavor” gradually weaken， and the taste changes from clean and umami to clean and sweet， and then to mellow and thick. Compared with different grades of white tea， it was found that there was a significant positive correlation between the grades of white tea and arginine （Arg）， aspartic acid （Asp）， threonine （Thr）. Among them， Asp decreased with the decrease of grade， so Asp was the key main chemical compounds that determined the taste differences of different grades of Baihao Yinzhen， Baimudan， Gongmei and Shoumei. Partial least squares-discriminant analysis （PLS-DA） of main chemical compounds in samples of different types revealed that the variable importance projection （VIP） values of 12 compounds including alanine （Ala）， theanine （L-Thea）， histidine （His）， lysine （Lys）， as well as epicatechin gallate （ECG） and epigallocatechin gallate （EGCG）， were greater than or equal to 1.0. Analysis of main chemical compounds in samples of the same type with different grades revealed that characteristic main chemical compounds exhibited were proline （Pro）， His， L-Thea and phenylalanine （Phe）. Above results provided theoretical reference for the evaluation and analysis of the flavor quality of white tea products in China， and had reference value for the quality level discrimination of white tea products with different types and different grades of the same type.

Key words: types of white tea, grades of white tea, amino acids, catechin, chemical compounds

中图分类号:

S571.1

陈丽琴, 周子维, 蔡亚威, 张朝辉, 江胜滔, 艾克拜尔·热合曼, 陈艳. 基于UPLC-MS/MS技术的9个白茶实物标准样主要化学成分分析[J]. 中国农业科技导报, 2024, 26(12): 50-62.

Liqin CHEN, Ziwei ZHOU, Yawei CAI, Zhaohui ZHANG, Shengtao JIANG, Aikebaer Reheman, Yan CHEN. Main Chemical Compounds Analysis of 9 White Tea Standard Samples Based on UPLC-MS/MS Technology[J]. Journal of Agricultural Science and Technology, 2024, 26(12): 50-62.

图/表 11

表1 白茶标准样品信息

Table 1 Information of standard samples of white tea

序号Number	种类Type	等级Grade	编码Code
1	白毫银针Baihaoyinzhen	特级Supper grade	T_YZ
2	白毫银针Baihaoyinzhen	一级First grade	1_YZ
3	白牡丹Baimudan	特级Supper grade	T_MD
4	白牡丹Baimudan	一级First grade	1_MD
5	白牡丹Baimudan	二级Second grade	2_MD
6	贡眉Gongmei	特级Supper grade	T_GM
7	贡眉Gongmei	一级First grade	1_GM
8	寿眉Shoumei	一级First grade	1_SM
9	寿眉Shoumei	二级Second grade	2_SM

表2 不同花色和等级白茶香气和滋味

Table 2 Aroma and taste of white tea with different types and grades

清纯、毫香显露

Clean and pure， obvious tip aroma

清鲜醇爽、毫味足

Clean and fresh， rich in tippy hair taste

1_YZ

清纯、毫香显

Clean and pure， obvious tip aroma

鲜醇爽、毫味显

Fresh，mellow anf brisk， obvious tippy hair taste

T_MD

鲜嫩、纯爽毫香显

Fresh and tender， pure and brisk， obvious tip aroma

清甜醇爽、毫味足

Clean and sweet， mellow anf brisk

rich in tippy hair taste

1_MD

尚鲜嫩、纯爽有毫香

Approach fresh and mellow， pure and brisk with tip aroma

较清甜、醇爽

More clean and sweet， mellow anf brisk

2_MD

浓纯、略有毫香

Strong and pure， slightly tip aroma

尚清甜、醇厚

Approach clean and sweet， mellow and thick

T_GM

鲜嫩、有毫香

Fresh and mellow with tip aroma

清甜、醇爽

Clean and sweet， mellow anf brisk

1_GM

鲜纯、有嫩香

Fresh and pure with tender aroma

醇厚、尚爽

Mellow and thick， approachbrisk

1_SM

纯

Pure

醇厚、尚爽

Mellow and thick， approachbrisk

2_SM

纯

Pure

醇厚

Mellow and thick

表3 不同等级标准样品儿茶素类和咖啡因含量 (mg·g-1)

Table 3 Content of catechins and caffeine components in standard samples of white tea

编号 Code	儿茶素 C	表儿茶素 EC	表没食子儿茶素EGC	表没食子儿茶素没食子酸酯EGCG	表儿茶素没食子酸酯 ECG	咖啡因 Caffeine	总儿茶素 Total catechin
T_YZ	0.55±0.02 e	1.12±0.09 d	2.76±0.34 d	60.78±5.08 bc	30.60±1.49 ab	41.63±13.23 ab	95.81±2.13
1_YZ	0.55±0.01 e	1.18±0.04 d	3.12±0.34 d	52.39±1.08 de	27.33±1.62 bc	49.28±1.52 ab	84.57±0.70
T_MD	0.67±0.01 bc	1.89±0.03 c	9.97±0.48 c	52.64±1.16 de	22.88±0.77 d	46.69±0.93 ab	88.05±0.49
1_MD	0.65±0.02 cd	2.38±0.07 b	13.06±1.12 b	40.19±3.06 fg	17.41±1.61 e	42.05±2.28 ab	73.69±1.26
2_MD	0.77±0.02 a	3.26±0.03 a	17.88±0.40 a	46.81±1.23 ef	18.02±0.61 e	39.97±1.12 ab	46.74±0.52
T_GM	0.70±0.02 b	2.21±0.11 b	10.37±0.03 c	71.02±4.24 a	31.47±1.52 a	50.56±1.47 a	115.77±1.82
1_GM	0.70±0.03 b	2.48±0.14 b	11.46±0.22 bc	67.77±1.88 ab	28.54±1.90 ab	44.93±0.94 ab	110.95±0.97
1_SM	0.66±0.01 bc	3.20±0.24 a	16.28±1.25 a	55.52±2.70 cd	24.33±1.02 cd	44.82±0.93 ab	99.99±1.06
2_SM	0.60±0.01 de	2.31±0.03 b	11.13±0.63 c	36.44±1.32 g	14.80±0.99 e	36.21±0.68 b	65.28±0.59

图1 不同种类及不同等级白茶标准样的酯型儿茶素和非酯型儿茶素含量注：*和**分别表示在P<0.05和P<0.01水平差异显著。GM—贡眉；MD—白牡丹；SM—寿眉；YZ—白毫银针；0—特级；1—一级；2—二级。

Fig. 1 Contents of ester type and non-ester type catechins in standard samples of different types and different grades of white teaNote：* and ** indicate significant differences at P<0.05 and P<0.01 levels， respectively. GM—Gongmei；MD—Baimudan；SM—Shoumei；YZ—Baihaoyinzhen；0—Supper grade；1—First grade；2—Second grade。

表4 白茶不同等级标准样品游离氨基酸组分含量 (mg·g-1)

Table 4 Contents of free amino acid components in standard samples of different grades of white tea

类型Type	组分 Component	T_YZ	1_YZ	T_MD	1_MD	2_MD	T_GM	1_GM	1_SM	2_SM
鲜味 Fresh flavour	茶氨酸 L-Thea	1.63±0.04 ef	1.53±0.05 f	2.13±0.07 b	1.73±0.02 d	2.61±0.05 a	1.74±0.40 d	1.99±0.09 c	1.65±0.05 de	0.72±0.09 g
	谷氨酸 Glu	1.04±0.02 b	0.99±0.02 b	0.85±0.03 b	0.78±0.03 b	0.81±0.03 a	0.85±0.02 a	0.76±0.08 a	0.82±0.02 b	0.53±0.13 c
	天冬氨酸 Asp	1.50±0.04 a	1.31±0.04 b	1.03±0.03 d	0.72±0.03 e	0.66±0.03 ef	1.14±0.04 c	0.94±0.11 d	0.54±0.02 f	0.25±0.05 g
	脯氨酸 Pro	1.46±0.04 a	1.32±0.04 ab	0.87±0.06 e	1.05±0.04 cd	0.48±0.04 f	0.99±0.09 cd	0.78±0.09 de	0.93±0.05 de	1.27±0.21 bc
	氨基丁酸 GABA	1.12±0.02 bc	1.09±0.03 c	1.23±0.03 ab	0.93±0.00 d	1.12±0.03 bc	1.25±0.03 a	1.13±0.12 ab	0.86±0.01 d	0.50±0.06 e
	丙氨酸 Ala	1.95±0.48 a	1.10±0.06 b	1.23±0.05 ab	1.21±0.05 ab	1.28±0.05 a	1.24±0.04 ab	1.32±0.10 a	1.26±0.03 a	1.23±0.05 ab
甜味 Sweet taste	丝氨酸Ser	1.10±0.07 cd	1.02±0.04 cd	1.33±0.05 a	1.04±0.04 cd	1.27±0.07 ab	1.09±0.45 bcd	1.02±0.15 abc	0.91±0.05 d	0.73±0.16 e
	苏氨酸 Thr	0.64±0.01 a	0.59±0.02 b	0.49±0.02 c	0.36±0.02 d	0.38±0.01 d	0.53±0.03 b	0.43±0.05 c	0.27±0.00 e	0.08±0.02 f
	天冬酰胺 Asn	0.84±0.06 a	0.76±0.01 a	0.56±0.03 bc	0.53±0.01 cd	0.41±0.03 e	0.60±0.06 b	0.49±0.09 bc	0.43±0.02 de	0.49±0.02 cde
	谷氨酰胺 Gln	0.06±0.00 b	0.06±0.00 b	0.70±0.01 b	0.05±0.00 b	0.08±0.01 a	0.08±0.00 a	0.07±0.02 a	0.06±0.00 b	0.02±0.01 c
	脯氨酸 Pro	1.46±0.04 a	1.32±0.04 ab	0.87±0.06 e	1.05±0.04 cd	0.48±0.04 f	0.99±0.09 cd	0.78±0.09 de	0.93±0.05 de	1.27±0.21 bc
	丙氨酸 Ala	1.95±0.48 a	1.10±0.06 b	1.23±0.05 ab	1.21±0.05 ab	1.28±0.05 a	1.24±0.04 ab	1.32±0.10 a	1.26±0.03 a	1.23±0.05 ab
苦味 Bitter taste	精氨酸 Arg	2.11±0.07 a	1.84±0.05 b	1.38±0.05 d	1.01±0.04 e	0.92±0.03 ef	1.63±0.05 c	1.30±0.12 d	0.76±0.03 f	0.33±0.07 g
	组氨酸 His	0.28±0.06 b	0.41±0.02 a	0.31±0.02 b	0.21±0.01 c	0.34±0.04 b	0.44±0.02 a	0.35±0.06 b	0.15±0.01 c	0.06±0.01 g
	亮氨酸 Leu	0.82±0.01 a	0.79±0.03 ab	0.62±0.02 cd	0.56±0.02 cde	0.52±0.02 de	0.62±0.03 cd	0.57±0.10 bc	0.46±0.01 e	0.36±0.04 f
	异亮氨酸 Ile	0.82±0.02 a	0.80±0.04 ab	0.65±0.03 cd	0.56±0.01 cde	0.52±0.02 de	0.63±0.03 cd	0.59±0.10 bc	0.47±0.02 e	0.37±0.04 f
	苯丙氨酸 Phe	0.42±0.01 d	0.44±0.01 d	0.50±0.01 b	0.46±0.00 cd	0.68±0.02 a	0.41±0.01 d	0.46±0.05 bc	0.42±0.01 d	0.29±0.04 e
	缬氨酸 Val	1.08±0.04 a	1.06±0.05 ab	0.84±0.04 cd	0.87±0.02 cd	0.69±0.03 d	0.88±0.07 bc	0.81±0.12 bc	0.75±0.05 cd	0.81±0.11 d
	Met	0.06±0.00 a	0.06±0.00 a	0.04±0.00 bc	0.04±0.00 bc	0.03±0.00 c	0.04±0.00 b	0.04±0.01 b	0.04±0.00 bc	0.04±0.01 b
酸味 Sour odour	天冬氨酸 Asp	1.50±0.04 a	1.31±0.04 b	1.03±0.03 d	0.72±0.03 e	0.66±0.03 ef	1.14±0.04 c	0.94±0.11 d	0.54±0.02 f	0.25±0.05 g
酸味 Sour odour	谷氨酰胺 Gln	0.06±0.00 b	0.06±0.00 b	0.70±0.01 b	0.05±0.00 b	0.08±0.01 a	0.08±0.00 a	0.07±0.02 a	0.06±0.00 b	0.02±0.01 c
芳香 Aromatous	缬氨酸 Val	1.08±0.04 a	1.06±0.05 ab	0.84±0.04 cd	0.87±0.02 cd	0.69±0.03 d	0.88±0.07 bc	0.81±0.12 bc	0.75±0.05 cd	0.81±0.11 d
	亮氨酸 Leu	0.82±0.01 a	0.79±0.03 ab	0.62±0.02 cd	0.56±0.02 cde	0.52±0.02 de	0.62±0.03 cd	0.57±0.10 bc	0.46±0.01 e	0.36±0.04 f
	苯丙氨酸 Phe	0.42±0.01 d	0.44±0.01 d	0.50±0.01 b	0.46±0.00 cd	0.68±0.02 a	0.41±0.01 d	0.46±0.05 bc	0.42±0.01 d	0.29±0.04 e
	精氨酸 Arg	2.11±0.07 a	1.84±0.05 b	1.38±0.05 d	1.01±0.04 e	0.92±0.03 ef	1.63±0.05 c	1.30±0.12 d	0.76±0.03 f	0.33±0.07 g
	赖氨酸 Lys	1.14±0.08 a	1.07±0.03 b	0.86±0.10 c	0.79±0.08 cd	1.11±0.04 b	0.90±0.04 c	0.79±0.05 d	0.81±0.03 cd	0.51±0.02 e

表4 白茶不同等级标准样品游离氨基酸组分含量 (mg·g-1)

Table 4 Contents of free amino acid components in standard samples of different grades of white tea

类型Type	组分 Component	T_YZ	1_YZ	T_MD	1_MD	2_MD	T_GM	1_GM	1_SM	2_SM
鲜味 Fresh flavour	茶氨酸 L-Thea	1.63±0.04 ef	1.53±0.05 f	2.13±0.07 b	1.73±0.02 d	2.61±0.05 a	1.74±0.40 d	1.99±0.09 c	1.65±0.05 de	0.72±0.09 g
	谷氨酸 Glu	1.04±0.02 b	0.99±0.02 b	0.85±0.03 b	0.78±0.03 b	0.81±0.03 a	0.85±0.02 a	0.76±0.08 a	0.82±0.02 b	0.53±0.13 c
	天冬氨酸 Asp	1.50±0.04 a	1.31±0.04 b	1.03±0.03 d	0.72±0.03 e	0.66±0.03 ef	1.14±0.04 c	0.94±0.11 d	0.54±0.02 f	0.25±0.05 g
	脯氨酸 Pro	1.46±0.04 a	1.32±0.04 ab	0.87±0.06 e	1.05±0.04 cd	0.48±0.04 f	0.99±0.09 cd	0.78±0.09 de	0.93±0.05 de	1.27±0.21 bc
	氨基丁酸 GABA	1.12±0.02 bc	1.09±0.03 c	1.23±0.03 ab	0.93±0.00 d	1.12±0.03 bc	1.25±0.03 a	1.13±0.12 ab	0.86±0.01 d	0.50±0.06 e
	丙氨酸 Ala	1.95±0.48 a	1.10±0.06 b	1.23±0.05 ab	1.21±0.05 ab	1.28±0.05 a	1.24±0.04 ab	1.32±0.10 a	1.26±0.03 a	1.23±0.05 ab
甜味 Sweet taste	丝氨酸Ser	1.10±0.07 cd	1.02±0.04 cd	1.33±0.05 a	1.04±0.04 cd	1.27±0.07 ab	1.09±0.45 bcd	1.02±0.15 abc	0.91±0.05 d	0.73±0.16 e
	苏氨酸 Thr	0.64±0.01 a	0.59±0.02 b	0.49±0.02 c	0.36±0.02 d	0.38±0.01 d	0.53±0.03 b	0.43±0.05 c	0.27±0.00 e	0.08±0.02 f
	天冬酰胺 Asn	0.84±0.06 a	0.76±0.01 a	0.56±0.03 bc	0.53±0.01 cd	0.41±0.03 e	0.60±0.06 b	0.49±0.09 bc	0.43±0.02 de	0.49±0.02 cde
	谷氨酰胺 Gln	0.06±0.00 b	0.06±0.00 b	0.70±0.01 b	0.05±0.00 b	0.08±0.01 a	0.08±0.00 a	0.07±0.02 a	0.06±0.00 b	0.02±0.01 c
	脯氨酸 Pro	1.46±0.04 a	1.32±0.04 ab	0.87±0.06 e	1.05±0.04 cd	0.48±0.04 f	0.99±0.09 cd	0.78±0.09 de	0.93±0.05 de	1.27±0.21 bc
	丙氨酸 Ala	1.95±0.48 a	1.10±0.06 b	1.23±0.05 ab	1.21±0.05 ab	1.28±0.05 a	1.24±0.04 ab	1.32±0.10 a	1.26±0.03 a	1.23±0.05 ab
苦味 Bitter taste	精氨酸 Arg	2.11±0.07 a	1.84±0.05 b	1.38±0.05 d	1.01±0.04 e	0.92±0.03 ef	1.63±0.05 c	1.30±0.12 d	0.76±0.03 f	0.33±0.07 g
	组氨酸 His	0.28±0.06 b	0.41±0.02 a	0.31±0.02 b	0.21±0.01 c	0.34±0.04 b	0.44±0.02 a	0.35±0.06 b	0.15±0.01 c	0.06±0.01 g
	亮氨酸 Leu	0.82±0.01 a	0.79±0.03 ab	0.62±0.02 cd	0.56±0.02 cde	0.52±0.02 de	0.62±0.03 cd	0.57±0.10 bc	0.46±0.01 e	0.36±0.04 f
	异亮氨酸 Ile	0.82±0.02 a	0.80±0.04 ab	0.65±0.03 cd	0.56±0.01 cde	0.52±0.02 de	0.63±0.03 cd	0.59±0.10 bc	0.47±0.02 e	0.37±0.04 f
	苯丙氨酸 Phe	0.42±0.01 d	0.44±0.01 d	0.50±0.01 b	0.46±0.00 cd	0.68±0.02 a	0.41±0.01 d	0.46±0.05 bc	0.42±0.01 d	0.29±0.04 e
	缬氨酸 Val	1.08±0.04 a	1.06±0.05 ab	0.84±0.04 cd	0.87±0.02 cd	0.69±0.03 d	0.88±0.07 bc	0.81±0.12 bc	0.75±0.05 cd	0.81±0.11 d
	Met	0.06±0.00 a	0.06±0.00 a	0.04±0.00 bc	0.04±0.00 bc	0.03±0.00 c	0.04±0.00 b	0.04±0.01 b	0.04±0.00 bc	0.04±0.01 b
酸味 Sour odour	天冬氨酸 Asp	1.50±0.04 a	1.31±0.04 b	1.03±0.03 d	0.72±0.03 e	0.66±0.03 ef	1.14±0.04 c	0.94±0.11 d	0.54±0.02 f	0.25±0.05 g
酸味 Sour odour	谷氨酰胺 Gln	0.06±0.00 b	0.06±0.00 b	0.70±0.01 b	0.05±0.00 b	0.08±0.01 a	0.08±0.00 a	0.07±0.02 a	0.06±0.00 b	0.02±0.01 c
芳香 Aromatous	缬氨酸 Val	1.08±0.04 a	1.06±0.05 ab	0.84±0.04 cd	0.87±0.02 cd	0.69±0.03 d	0.88±0.07 bc	0.81±0.12 bc	0.75±0.05 cd	0.81±0.11 d
	亮氨酸 Leu	0.82±0.01 a	0.79±0.03 ab	0.62±0.02 cd	0.56±0.02 cde	0.52±0.02 de	0.62±0.03 cd	0.57±0.10 bc	0.46±0.01 e	0.36±0.04 f
	苯丙氨酸 Phe	0.42±0.01 d	0.44±0.01 d	0.50±0.01 b	0.46±0.00 cd	0.68±0.02 a	0.41±0.01 d	0.46±0.05 bc	0.42±0.01 d	0.29±0.04 e
	精氨酸 Arg	2.11±0.07 a	1.84±0.05 b	1.38±0.05 d	1.01±0.04 e	0.92±0.03 ef	1.63±0.05 c	1.30±0.12 d	0.76±0.03 f	0.33±0.07 g
	赖氨酸 Lys	1.14±0.08 a	1.07±0.03 b	0.86±0.10 c	0.79±0.08 cd	1.11±0.04 b	0.90±0.04 c	0.79±0.05 d	0.81±0.03 cd	0.51±0.02 e

图2 不同花色、不同等级白茶标准样的游离氨基酸总量注：*和**分别表示在P<0.05和P<0.01水平差异显著。GM—贡眉；MD—白牡丹；SM—寿眉；YZ—白毫银针；0—特级；1—一级；2—二级。

Fig. 2 Total amount of free amino acids in standard samples of different types and grades of white teaNote：* and ** indicate significant differences at P<0.05 and P<0.01 level， respectively. GM—Gongmei；MD—Baimudan；SM—Shoumei；YZ—Baihaoyinzhen；0—Supper grade；1—First grade；2—Second grade.

图3 白茶标准样主要化学物质及与等级间的相关性热图注：*和**分别表示在P<0.05和P<0.01水平相关显著；C—儿茶素；EC—表儿茶素；EGC—表没食子儿茶素；EGCG—表没食子儿茶素没食子酸酯；ECG—表儿茶素没食子酸酯；CAF—咖啡因；Ala—丙氨酸；Pro—脯氨酸；Asn—天冬酰胺；Val—缬氨酸；Met—蛋氨酸；L-Thea—茶氨酸；Phe—苯丙氨酸；Tyr—酪氨酸；Gln—谷氨酰胺；Ser—丝氨酸；Trp—色氨酸；Lys—赖氨酸；GABA—氨基丁酸；His—组氨酸；Arg—精氨酸；Asp—天冬氨酸；Ile—异亮氨酸；Leu—亮氨酸；Thr—苏氨酸；Glu—谷氨酸；G—等级。

Fig. 3 Heat map of correlation analysis among main chemical compounds and grades of white tea standard samplesNote：* and ** indicate significant correlations at P<0.05 and P<0.01 levels， respectively； C—catechin hydrate；EC—epicatechin；EGC—epigallocatechin；EGCG—epigallocatechin gallate；ECG—epicatechin gallate；CAF—caffeine；Ala—Alpha linolenic acid；Pro—Proline；Asn—Asparagine；Val—Valine；Met—Methionine；L-Thea—L-Theanine；Phe—Phenylalanine；Tyr—Tyrosine；Gln—Glutamine；Ser—Serine；Trp—Tryptophan；Lys—Lysine；GABA—Aminobutyric acid；His—Histidine；Arg—Arginine；Asp—Aspartic acid；Ile—Isoleucine；Leu—Leucine；Thr—Threonine；Glu—Glutamic acid；G—Grade.

图4 不同花色白茶标准样主要化学物质的多元统计分析A：PLS-DA分析；B：S-plot分析；C：VIP值柱形图。C—儿茶素；EC—表儿茶素；EGC—表没食子儿茶素；EGCG—表没食子儿茶素没食子酸酯；ECG—表儿茶素没食子酸酯；CAF—咖啡因；Ala—丙氨酸；Pro—脯氨酸；Asn—天冬酰胺；Val—缬氨酸；Met—蛋氨酸；L-Thea—茶氨酸；Phe—苯丙氨酸；Tyr—酪氨酸；Gln—谷氨酰胺；Ser—丝氨酸；Trp—色氨酸；Lys—赖氨酸；GABA—氨基丁酸；His—组氨酸；Arg—精氨酸；Asp—天冬氨酸；Ile—异亮氨酸；Leu—亮氨酸；Thr—苏氨酸；Glu—谷氨酸

Fig. 4 Multivariate statistical analysis of main chemical compounds in standard samples of different types of white teaA： PLS-DA analysis； B： S-plot analysis； C：VIP value bar chart. C—Catechin hydrate；EC—Epicatechin；EGC—Epigallocatechin；EGCG—Epigallocatechin gallate；ECG—Epicatechin gallate；CAF—Caffeine；Ala—Alpha linolenic acid；Pro—Proline；Asn—Asparagine；Val—Valine；Met—Methionine；L-Thea—L-Theanine；Phe—Phenylalanine；Tyr—Tyrosine；Gln—Glutamine；Ser—Serine；Trp—Tryptophan；Lys—Lysine；GABA—Aminobutyric acid；His—Histidine；Arg—Arginine；Asp—Aspartic acid；Ile—Isoleucine；Leu—Leucine；Thr—Threonine；Glu—Glutamic acid

图5 同一花色内不同等级白茶标准样主要化学物质的多元统计分析A、D、G、J：白毫银针、白牡丹、贡眉、寿眉的PLS-DA分析；B、E、H、K：白毫银针、白牡丹、贡眉、寿眉的S-plot分析；C、F、I、L：白毫银针、白牡丹、贡眉、寿眉的VIP值柱形图。C—儿茶素；EC—表儿茶素；EGC—表没食子儿茶素；EGCG—表没食子儿茶素没食子酸酯；ECG—表儿茶素没食子酸酯；CAF—咖啡因；Ala—丙氨酸；Pro—脯氨酸；Asn—天冬酰胺；Val—缬氨酸；Met—蛋氨酸；L-Thea—茶氨酸；Phe—苯丙氨酸；Tyr—酪氨酸；Gln—谷氨酰胺；Ser—丝氨酸；Trp—色氨酸；Lys—赖氨酸；GABA—氨基丁酸；His—组氨酸；Arg—精氨酸；Asp—天冬氨酸；Ile—异亮氨酸；Leu—亮氨酸；Thr—苏氨酸；Glu—谷氨酸

Fig. 5 Multivariate statistical analysis of main chemical compounds in standard samples of white tea of the same type and different gradesA， D， G， J： PLS-DA analysis of Baihaoyinzhen， Baimudan， Gongmei， Shoumei； B， E， H， K： S-plot analysis of Baihaoyinzhen， Baimudan， Gongmei， Shoumei； C， F， I， L： VIP value bar chart analysis of Baihaoyinzhen， Baimudan， Gongmei， Shoumei. C—Catechin hydrate；EC—Epicatechin；EGC—Epigallocatechin；EGCG—Epigallocatechin gallate；ECG—Epicatechin gallate；CAF—Caffeine；Ala—Alpha linolenic acid；Pro—Proline；Asn—Asparagine；Val—Valine；Met—Methionine；L-Thea—L-Theanine；Phe—Phenylalanine；Tyr—Tyrosine；Gln—Glutamine；Ser—Serine；Trp—Tryptophan；Lys—Lysine；GABA—Aminobutyric acid；His—Histidine；Arg—Arginine；Asp—Aspartic acid；Ile—Isoleucine；Leu—Leucine；Thr—Threonine；Glu—Glutamic acid

图6 同一花色不同等级白茶标准样中特征性主要化学物质的韦恩图

Fig. 6 Venn diagram of characteristic main chemical compounds in standard samples of white tea with the same type but different grades

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基于UPLC-MS/MS技术的9个白茶实物标准样主要化学成分分析

Main Chemical Compounds Analysis of 9 White Tea Standard Samples Based on UPLC-MS/MS Technology

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