不同等级白牡丹茶游离氨基酸构成分析

陈思肜; 赵峰; 王淑燕; 金珊; 周鹏; 危赛明; 叶乃兴

doi:10.19303/j.issn.1008-0384.2019.08.015

不同等级白牡丹茶游离氨基酸构成分析

doi: 10.19303/j.issn.1008-0384.2019.08.015

陈思肜^1,,
赵峰^{1, 2, ,},
王淑燕¹,
金珊¹,
周鹏³,
危赛明⁴,
叶乃兴^1, ,

1.
福建农林大学园艺学院, 福建福州 350002
2.
福建中医药大学药学院, 福建福州 350122
3.
福建省产品质量检验研究院, 福建福州 350002
4.
福建茶叶进出口有限责任公司, 福建福州 350014

基金项目:

国家自然科学基金项目 31270735

福建农林大学科技创新专项 CXZX2016117

茶学福建省高校重点实验室开放课题 KLTS2018001

国家茶叶质量安全工程技术研究中心开放课题 2018NTQS030

详细信息

作者简介:
陈思肜(1995-), 女, 硕士研究生, 研究方向:茶叶品质化学(E-mail:602081987@qq.com)

通讯作者:
赵峰(1983-), 男, 博士, 高级工程师, 研究方向:茶叶品质化学(E-mail:zhaofeng0591@qq.com)

叶乃兴(1963-), 男, 教授, 研究方向:茶树栽培育种和品质化学(E-mail:ynxtea@126.com)

中图分类号: TS272
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- 被引次数: 0
出版历程
- 收稿日期: 2019-06-03
- 修回日期: 2019-07-10
- 刊出日期: 2019-08-01

Amino Acids in White Peony Teas of Different Grades

CHEN Si-rong^1
,,
ZHAO Feng^{1, 2
, ,},
WANG Shu-yan¹,
JIN Shan¹,
ZHOU Peng³,
WEI Sai-ming⁴,
YE Nai-xing^{1
, ,}

1.
College of Horticulture, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002, China
2.
College of Pharmacy, Fujian University of Traditional Chinese Medicine, Fuzhou, Fujian 350122, China
3.
Fujian Inspection and Research Institute for Product Quality, Fuzhou, Fujian 350002, China
4.
Fujian Tea Import & Export Company Limited, Fuzhou, Fujian 350014, China

摘要

摘要: 目的通过对不同等级白牡丹茶游离氨基酸的分析，探究氨基酸种类与白牡丹茶品质等级的关系。方法采用AQC柱前衍生结合超高效液相色谱-串联质谱法（UHPLC-MS/MS）测定游离氨基酸后，通过结合偏最小二乘法判别分析法（Partial least squares discrimination analysis，PLS-DA）和聚类分析法，对9批次不同等级白牡丹茶的35种游离氨基酸进行分析。结果白牡丹茶中除β-氨基丁酸、同型半胱氨酸、半胱氨酸、胱氨酸、酪氨酸5种氨基酸外，其余30种氨基酸均高于定量限。相关分析结果显示，游离氨基酸与白牡丹品质等级间存在密切相关性；其中，γ-氨基丁酸、丝氨酸、脯氨酸、色氨酸、甘氨酸对于白牡丹茶滋味品质的影响最大；味觉分析结果显示，γ-氨基丁酸对白牡丹茶滋味的收敛性有重要贡献，而其余氨基酸主要通过交互作用对白牡丹茶滋味品质产生贡献。结论白牡丹茶的游离氨基酸构成与其品质等级间存在密切相关性，不同氨基酸组分通过交互作用对白牡丹茶的滋味等级形成产生整体性的贡献作用。
- 白茶 /
- 白牡丹 /
- 游离氨基酸组分 /
- 滋味 /
- 品质等级
Abstract: Objective The amino acids in white peony teas of various quality grades were compared. Method Free amino acid compositions of 9 white peony tea specimens were determined using AQC pre-column derivatization combined with the ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The analytical results on 35 amino acids were compared for the study by the partial least squares discrimination analysis (PLS-DA) and cluster analysis. Result Aside from β-aminobutyric acid, homocysteine, cysteine, cystine, and tyrosine, the remaining 30 amino acids in the tea samples showed higher contents than the limit of quantitation. The correlation analysis on the data indicated a significant correlation between the amino acid composition and the quality of the teas. For instance, γ-aminobutyric acid, serine, proline, tryptophan, and glycine significantly affected the taste, while γ-aminobutyric acid was crucial on the astringency, of the brewed tea as shown in a taste test. The other amino acids appeared to interactively contribute to the sensory quality. Conclusion Either individually or interactively, free amino acids had a significant effect on the taste, therefore, the grading of the white peony teas.
- white tea /
- white peony /
- free amino acid composition /
- taste /
- quality grade

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图 1 不同等级白牡丹30种游离氨基酸组分含量热图(n=3)

注：红框内为常量氨基酸，蓝框内为微量氨基酸。

Figure 1. Heat map of 30 amino acids from white peony teas (n=3)

Note:The red box is a constant amino acid, and the blue box is a trace amino acid.

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图 2 主成分分析

注：Ⅰ为PLS-DA得分图，R² = 96.21%，Q² =73.25%；A为特级，B为一级，C为二级; Ⅱ为PLS-DA载荷矩阵图，不同等级白牡丹PCA-DA得分图均值点(●)，氨基酸组分(▼)。

Figure 2. Principal component analysis chart

Note:Ⅰ PLS-DA score plot, R² = 96.21%, Q² = 73.25%; A:special-class, B:first-class, C:second-class; Ⅱ PLS-DA Loading scatter plot, PCA-DA score plot mean point (●), amino acid composition (▼).

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表 1 35种游离氨基酸检测的质谱条件

Table 1. Conditions applied for mass spectrometry on 35 amino acids in tea specimens

氨基酸组分 Amino acid	分子量 Molecular weight	母离子 Precurser ion m/z	子离子 Product ion m/z
茶氨酸(Thea)	174.2	345.1	171*/145.1
羟赖氨酸 (Hy-Lys)	162.2	333	171*/265
胱氨酸 (Cys)	240.3	581.1	171*/411.1
1-甲基-L-组氨酸 (1-M-His)	169.2	340.1	171*/196
3-甲基-L-组氨酸 (3-M-His)	169.2	340.1	171*/196
豆叶氨酸 (Pip)	129.16	300.1	171*/130.1
半胱氨酸 (Cysteine)	121.16	292.1	171.1*/116
β-氨基丁酸 (β-ABA)	103.1	274.1	171*/116
精氨酸 (Arg)	174.2	345.1	171*/175.1
α-氨基丁酸 (α-ABA)	103.1	274.1	171*/116
蛋氨酸 (Met)	149.2	320.1	171*/150.1
谷氨酰胺 (Gln)	146.15	318.1	171*/116
瓜氨酸 (Cit)	175.2	346.1	171.1*/329.1
L-2-氨基己二酸 (α-AAA)	161.2	322.1	171*/279
同型半胱氨酸 (Homocystine)	268.4	609.2	171.1*/306.1
羟脯氨酸 (Hy-Pro)	131.1	302.1	171.1*/132.1
组氨酸 (His)	155.2	326.1	171*/156.1
色氨酸 (Trp)	204.2	375.1	171*/188.1
丙氨酸 (Ala)	89.09	260.1	171*/116
γ-氨基丁酸 (GABA)	103.1	274.1	171*/116
脯氨酸 (Pro)	115.1	286.1	171*/116
苏氨酸 (Thr)	119.1	290.1	171*/116
赖氨酸 (Lys)	146.2	487.1	171*/145
天冬氨酸 (Asp)	133.1	304.1	171*/116
鸟氨酸 (Orn)	132.2	473.1	171.1*/145
酪氨酸 (Tyr)	181.2	352.1	171*/116
谷氨酸 (Glu)	147.1	318.1	171*/116
异亮氨酸 (Ile)	131.2	302.1	171*/116
天冬酰胺 (Asn)	132.12	303.1	171.1*/116
亮氨酸 (Leu)	131.2	302.1	171*/116
苯丙氨酸 (Phe)	165.2	335.1	171*/116
缬氨酸 (Val)	117.2	288.1	171*/116
肌氨酸 (Sar)	89.09	260	171*/116
丝氨酸 (Ser)	105.1	276.1	171*/116
甘氨酸 (Gly)	75.07	246.1	171*/116
注：定量离子。 Note： Quantitative ion.

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表 2 不同等级白牡丹离氨基酸含量

Table 2. Amino acid compositions of white peony teas of various grades

[单位/(mg·g^-1)]
氨基酸组分 Amino acid	特级 Super			一级 First level			二级 Second level
氨基酸组分 Amino acid	A1	A2	A3	B1	B2	B3	C1	C2	C3
茶氨酸(Thea)	18.87	19.23	20.55	17.42	17.24	16.14	12.04	8.32	10.77
谷氨酰胺(Gln)	3.14	4.35	5.49	2.77	3.77	3.84	2.74	1.75	2.85
天冬酰胺(Asn)	3.36	2.55	2.59	2.60	2.73	2.35	1.92	1.56	0.85
精氨酸(Arg)	2.63	2.55	2.20	1.69	1.90	1.99	1.27	0.64	1.44
谷氨酸(Glu)	1.76	1.70	2.07	1.43	1.42	1.94	1.61	1.32	1.59
天冬氨酸(Asp)	1.80	1.60	1.77	1.21	1.49	1.38	1.51	1.28	1.04
丝氨酸(Ser)	1.83	1.68	1.86	1.71	1.45	1.37	1.00	0.99	0.82
苯丙氨酸(Phe)	1.36	1.27	1.34	1.10	1.10	1.13	1.38	0.99	1.38
丙氨酸(Ala)	1.18	1.09	1.24	1.21	1.08	1.00	1.03	0.74	0.89
γ-氨基丁酸(GABA)	1.32	1.36	1.42	0.87	1.25	0.99	0.88	0.78	0.46
赖氨酸(Lys)	0.98	0.90	0.95	0.78	0.85	0.76	0.81	0.71	0.47
脯氨酸(Pro)	0.97	0.85	0.94	0.71	0.83	0.75	0.83	0.71	0.50
缬氨酸(Val)	1.00	0.94	0.98	0.66	0.84	0.71	0.67	0.57	0.35
亮氨酸(Leu)	0.86	0.82	0.86	0.72	0.76	0.65	0.61	0.51	0.35
色氨酸(Trp)	0.75	0.71	0.88	0.52	0.64	0.65	0.65	0.50	0.54
异亮氨酸(Ile)	0.80	0.71	0.82	0.57	0.70	0.64	0.65	0.51	0.39
苏氨酸(Thr)	0.69	0.62	0.66	0.55	0.54	0.56	0.51	0.42	0.37
组氨酸(His)	0.45	0.39	0.34	0.31	0.31	0.28	0.28	0.31	0.10
甘氨酸(Gly)	0.05	0.05	0.07	0.03	0.09	0.08	0.08	0.06	0.05
α-氨基丁酸(α-ABA)	0.07	0.06	0.05	0.05	0.04	0.04	0.09	0.09	0.04
豆叶氨酸(Pip)	0.07	0.06	0.05	0.05	0.05	0.03	0.05	0.05	0.04
肌氨酸(Sar)	0.05	0.03	0.04	0.03	0.03	0.04	0.05	0.05	0.04
羟赖氨酸(Hy-Lys)	0.05	0.03	0.04	0.03	0.03	0.04	0.05	0.04	0.03
L-2-氨基己二酸(α-AAA)	0.04	0.04	0.04	0.03	0.03	0.03	0.03	0.03	0.03
蛋氨酸(Met)	0.03	0.02	0.02	0.01	0.02	0.01	0.02	0.02	0.02
鸟氨酸(Orn)	0.01	0.01	0.01	0.01	0.01	0.01	0.02	0.01	0.03
瓜氨酸(Cit)	0.02	0.01	0.02	0.01	0.02	0.01	0.01	0.01	0.01
1-甲基-L-组氨酸(1-M-His)	0.003	0.003	0.003	0.002	0.003	0.004	0.003	0.003	0.002
羟脯氨酸(Hy-Pro)	0.004	0.004	0.003	0.001	0.003	0.002	0.003	0.004	0.002
3-甲基-L-组氨酸(3-M-His)	0.003	0.004	0.003	0.003	0.002	0.003	0.003	0.004	0.001
氨基酸总量	44.16	43.67	47.31	37.10	39.23	37.43	30.82	23.00	25.42

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表 3 不同等级白牡丹离氨基酸含量统计结果

Table 3. Statistics on amino acid compositions of white peony teas of various grades

[单位/(mg·g^-1)]
氨基酸组分 Amino acid	总平均值 Overall average	特级 Super	一级 First level	二级 Second level
茶氨酸(Thea)	15.62	19.55±0.88c	16.93±0.68b	10.37±1.89a
谷氨酰胺(Gln)	3.41	4.32±1.17c	3.45±0.59b	2.44±0.60a
天冬酰胺(Asn)	2.28	2.83±0.45bc	2.56±0.19b	1.44±0.54a
精氨酸(Arg)	1.81	2.45±0.22c	1.85±0.15b	1.11±0.41a
谷氨酸(Glu)	1.65	1.84±0.19a	1.59±0.29a	1.50±0.16a
天冬氨酸(Asp)	1.45	1.78±0.09c	1.51±0.18b	0.93±0.10a
丝氨酸(Ser)	1.41	1.72±0.10b	1.36±0.13a	1.27±0.23a
苯丙氨酸(Phe)	1.05	1.36±0.04b	1.03±0.19ab	0.70±0.21a
丙氨酸(Ala)	1.04	1.32±0.04a	1.10±0.01a	1.25±0.22a
γ-氨基丁酸(GABA)	1.04	1.16±0.07b	1.09±0.10ab	0.88±0.14a
赖氨酸(Lys)	0.8	0.97±0.03c	0.73±0.09b	0.52±0.16a
脯氨酸(Pro)	0.79	0.94±0.04b	0.79±0.04a	0.66±0.17a
缬氨酸(Val)	0.75	0.92±0.06b	0.76±0.06ab	0.68±0.17a
亮氨酸(Leu)	0.68	0.84±0.01bc	0.71±0.05b	0.48±0.13a
色氨酸(Trp)	0.65	0.78±0.08b	0.60±0.07a	0.56±0.07a
异亮氨酸(Ile)	0.64	0.77±0.05b	0.63±0.06ab	0.52±0.13a
苏氨酸(Thr)	0.55	0.65±0.03c	0.55±0.01b	0.43±0.07a
组氨酸(His)	0.31	0.39±0.05b	0.30±0.02ab	0.23±0.11a
甘氨酸(Gly)	0.06	0.06±0.01b	0.04±0.01a	0.04±0.01a
α-氨基丁酸(α-ABA)	0.06	0.06±0.01a	0.07±0.03a	0.06±0.01a
豆叶氨酸(Pip)	0.05	0.06±0.01a	0.05±0.01a	0.07±0.02a
肌氨酸(Sar)	0.04	0.04±0.00a	0.03±0.00a	0.03±0.00a
羟赖氨酸(Hy-Lys)	0.04	0.04±0.01a	0.03±0.01a	0.04±0.01a
L-2-氨基己二酸(α-AAA)	0.03	0.04±0.01a	0.03±0.00a	0.05±0.01a
蛋氨酸(Met)	0.02	0.01±0.00a	0.01±0.00a	0.01±0.00a
鸟氨酸(Orn)	0.02	0.02±0.00a	0.01±0.00a	0.02±0.00a
瓜氨酸(Cit)	0.01	0.02±0.00a	0.01±0.00a	0.01±0.00a
1-甲基-L-组氨酸(1-M-His)	0.004	0.01±0.00a	0.01±0.01a	0.01±0.02a
羟脯氨酸(Hy-Pro)	0.003	0.01±0.00b	0.01±0.00ab	0.02±0.00a
3-甲基-L-组氨酸(3-M-His)	0.003	0.01±0.00a	0.01±0.00a	0.01±0.00a
氨基酸总量	36.46	45.04±0.98c	37.92±0.88b	26.41±1.89a
注：同行数据后不同字母代表氨基酸含量差异显著(P＜0.05)。 Note：Different lowercase letters in the same column represented significant difference (P＜0.05).

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表 4 不同等级白牡丹中氨基酸的味觉活性值

Table 4. DoT of amino acids in white peony teas of various grades

氨基酸组分 Amino acid	滋味特性 Taste characteristics	滋味阈值 Taste threshold /(mg·L^-1)	DoT值 Dose-over-threshold
氨基酸组分 Amino acid	滋味特性 Taste characteristics	滋味阈值 Taste threshold /(mg·L^-1)	特级 Super	一级 First level	二级 Second level
茶氨酸(Thea)	甜味 Sweet taste	4181²	0.13	0.11	0.07
丝氨酸(Ser)		3153¹	0.01	0.01	0.01
丙氨酸(Ala)		713¹	0.05	0.04	0.05
脯氨酸(Pro)		2993¹	0.01	0.01	0.01
苏氨酸(Thr)		4764¹	< 0.01	< 0.01	< 0.01
甘氨酸(Gly)		2252¹	< 0.01	< 0.01	< 0.01
茶氨酸(Thea)	鲜味 Fresh taste	4181²	0.13	0.11	0.07
谷氨酰胺(Gln)		7308¹	0.02	0.01	0.01
天冬酰胺(Asn)		4000¹	0.02	0.02	0.01
谷氨酸(Glu)		441¹	0.11	0.10	0.09
精氨酸(Arg)	苦味 Bitter taste	13065¹	0.01	< 0.01	< 0.01
苯丙氨酸(Phe)		9582¹	< 0.01	< 0.01	< 0.01
缬氨酸(Val)		2461¹	0.01	0.01	0.01
赖氨酸(Lys)		1170¹	0.02	0.02	0.01
亮氨酸(Leu)		1574¹	0.01	0.01	0.01
色氨酸(Trp)		89848¹	< 0.01	< 0.01	< 0.01
异亮氨酸(Ile)		1443¹	0.01	0.01	0.01
组氨酸(His)		6984¹	< 0.01	< 0.01	< 0.01
γ-氨基丁酸(GABA)	引起口腔干燥和柔软收敛性的涩味 Astringency causing dry mouth and soft astringency	2¹	15.43	14.45	11.70
注：。1：阈值来源文献[20]，2：阈值来源文献[7]。 Note：1：Threshold Reference Source[20], 2：Threshold Reference Source[7].

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