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浙江大学学报(农业与生命科学版)  2022, Vol. 48 Issue (2): 172-181    DOI: 10.3785/j.issn.1008-9209.2021.03.181
食品科学     
白茶花青素苷的结构鉴定与分析
胡金祥1(),叶钰珊1,蔡梅生2,张青碧3,李博1,吴媛媛1,屠幼英1,何普明1()
1.浙江大学农业与生物技术学院茶学系, 杭州 310058
2.福鼎市茶业发展领导小组办公室, 福建 宁德 355200
3.福鼎市茶业管理局, 福建 宁德 355200
Structural identification and analysis of white tea anthocyanins
Jinxiang HU1(),Yushan YE1,Meisheng CAI2,Qingbi ZHANG3,Bo LI1,Yuanyuan WU1,Youying TU1,Puming HE1()
1.Department of Tea Science, College of Agriculture and Biotechnology, Zhejiang University, Hangzhou 310058, China
2.Organization Group Office of Fuding Tea Industry Development, Ningde 355200, Fujian, China
3.Fuding Tea Industry Bureau, Ningde 355200, Fujian, China
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摘要:

通过高效液相色谱-质谱联用技术初步鉴定白茶(白毫银针、白牡丹、贡眉和寿眉)中主要的花青素苷组分,并分析白茶花青素苷的组成特点与含量。结果表明:白茶花青素苷主要组分有飞燕草素-3-O-半乳糖苷、矢车菊素-3-O-半乳糖苷、天竺葵素-3-O-半乳糖苷、矢车菊素、飞燕草素-3-O-[6-(Z)对香豆酰]吡喃半乳糖苷、飞燕草素-3-O-[6-(E)对香豆酰]吡喃半乳糖苷、飞燕草素-3-O-芸香糖苷、矢车菊素-3-O-[6-(E)对香豆酰]吡喃半乳糖苷和天竺葵素-3-O-芸香糖苷9种;白毫银针、白牡丹、贡眉和寿眉中的花青素苷组成差异较大。白毫银针特级、白毫银针一级、白牡丹特级、白牡丹一级、贡眉一级、寿眉一级和寿眉二级的花青素苷总量分别为83.80、88.70、90.59、70.67、122.75、126.04和122.28 μg/g,贡眉和寿眉的花青素苷含量显著高于白毫银针和白牡丹。上述研究结果为白茶花青素苷组分分析提供了科学依据。

关键词: 白茶花青素苷结构鉴定    
Abstract:

The main anthocyanin components in white tea (Baihaoyinzhen, Baimudan, Gongmei and Shoumei) were preliminarily identified by high performance liquid chromatography-mass spectrometry, and then the composition characteristics and contents of anthocyanins were analyzed. The results showed that the main components of anthocyanins were delphinidin-3-O-galactoside, cyanidin-3-O-galactoside, pelargonidin-3-O-galactoside, cyanidin, delphinidin-3-O-[6-(Z)-p-coumarin] galactopyranoside, delphinidin-3-O-[6-(E)-p-coumarin] galactopyranoside, delphinidin-3-O-rutinoside, cyanidin-3-O-[6-(E)-p-coumarin] galactopyranoside and pelargonidin-3-O-rutinoside. The anthocyanin composition of Baihaoyinzhen, Baimudan, Gongmei and Shoumei was quite different. The anthocyanin contents of top grade and first grade of Baihaoyinzhen, top grade and first grade of Baimudan, first grade of Gongmei, and first grade and second grade of Shoumei were 83.80, 88.70, 90.59, 70.67, 122.75, 126.04 and 122.28 μg/g, respectively. The anthocyanin contents of Gongmei and Shoumei were significantly higher than those of Baihaoyinzhen and Baimudan. The above research results provide a scientific basis for the analysis of white tea anthocyanin components.

Key words: white tea    anthocyanin    structural identification
收稿日期: 2021-03-18 出版日期: 2022-04-29
CLC:  S 571.1  
基金资助: 校企横向项目“白茶储藏年份判别的研究”(2020-KYY-516107-0015)
通讯作者: 何普明     E-mail: 21716167@zju.edu.cn;pmhe@zju.edu.cn
作者简介: 胡金祥(https://orcid.org/0000-0002-2257-4107),E-mail:21716167@zju.edu.cn
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引用本文:

胡金祥,叶钰珊,蔡梅生,张青碧,李博,吴媛媛,屠幼英,何普明. 白茶花青素苷的结构鉴定与分析[J]. 浙江大学学报(农业与生命科学版), 2022, 48(2): 172-181.

Jinxiang HU,Yushan YE,Meisheng CAI,Qingbi ZHANG,Bo LI,Yuanyuan WU,Youying TU,Puming HE. Structural identification and analysis of white tea anthocyanins. Journal of Zhejiang University (Agriculture and Life Sciences), 2022, 48(2): 172-181.

链接本文:

https://www.zjujournals.com/agr/CN/10.3785/j.issn.1008-9209.2021.03.181        https://www.zjujournals.com/agr/CN/Y2022/V48/I2/172

图1  白茶(寿眉)花青素苷的HPLC分析

峰号

Code

保留时间

Retention time/min

分子离子

M (m/z)

分子碎片

MS2 (m/z)

丢失碎片

Loss fragment (m/z)

鉴定的化合物

Identified compound

17.8465303162飞燕草素-3-O-半乳糖苷 Delphinidin-3-O-galactoside (D3Ga)
210.0449287162矢车菊素-3-O-半乳糖苷 Cyanidin-3-O-galactoside (C3Ga)
312.1433271162天竺葵素-3-O-半乳糖苷 Pelargonidin-3-O-galactoside (P3Ga)
415.32872870矢车菊素 Cyanidin (Cy)
519.2611303308飞燕草素-3-O-[6-(Z)对香豆酰]吡喃半乳糖苷 Delphinidin-3-O-[6-(Z)-p-coumarin]galactopyranoside (DCZGa)
620.7611303308飞燕草素-3-O-[6-(E)对香豆酰]吡喃半乳糖苷 Delphinidin-3-O-[6-(E)-p-coumarin]galactopyranoside (DCGa)
723.0611303308飞燕草素-3-O-芸香糖苷 Delphinidin-3-O-rutinoside (D3Ru)
824.1595287308矢车菊素-3-O-[6-(Z)对香豆酰]吡喃半乳糖苷 Cyanidin-3-O-[6-(Z)-p-coumarin]galactopyranoside (CCZGa)
925.6595287308矢车菊素-3-O-[6-(E)对香豆酰]吡喃半乳糖苷 Cyanidin-3-O-[6-(E)-p-coumarin]galactopyranoside (CCGa)
1028.1579271308天竺葵素-3-O-芸香糖苷 Pelargonidin-3-O-rutinoside (P3Ru)
表1  白茶(寿眉)花青素苷组分的质谱数据
图2  4种花青素苷苷元的结构式R1=R2=H:天竺葵素,m/z 271;R1=OH,R2=R3=H:矢车菊素,m/z 287;R1=R2=OH,R3=H:飞燕草素,m/z 303;R1=R3=OH,R2=H:翘摇紫苷元,m/z 303。
图3  白茶花青素苷峰1~10(A~J)的质谱图及结构式

种类

Type

D3GaC3GaP3GaCyDCZGaDCGaD3Ru

白毫银针特级

Baihaoyinzhen top grade

1.78±0.31c1.77±0.39b1.54±0.2645.61±13.96b10.29±3.17b2.32±0.53a8.06±4.63a

白毫银针一级

Baihaoyinzhen first grade

2.99±0.27bNDND61.04±5.30ab16.02±1.87a2.75±0.28a2.82±0.92a

白牡丹特级

Baimudan top grade

2.06±0.36cNDND57.34±5.85ab10.10±0.61b2.04±0.11a5.97±0.65a

白牡丹一级

Baimudan first grade

NDNDND44.38±1.20b6.67±0.79b1.68±0.16a4.30±0.89a

贡眉一级

Gongmei first grade

3.03±0.17b3.13±0.23aND69.15±1.63a8.93±0.17b1.76±0.01a8.79±0.20a

寿眉一级

Shoumei first grade

2.54±0.43bc1.57±0.34bND67.38±2.19a8.65±1.09b1.84±0.49a11.60±0.48a

寿眉二级

Shoumei second grade

3.99±0.41a1.53±0.17bND66.56±2.66a9.32±0.33b1.51±0.23a10.66±0.47a

种类

Type

CCGaP3Ru

未知1

Unknown

compound 1

未知2

Unknown

compound 2

未知3

Unknown

compound 3

总计

Total

白毫银针特级

Baihaoyinzhen top grade

7.26±0.41a2.88±0.25aNDND2.29±0.73a83.80±3.64b

白毫银针一级

Baihaoyinzhen first grade

NDND1.28±0.02bND1.80±0.09a88.70±8.62b

白牡丹特级

Baimudan top grade

2.96±1.38c1.86±0.50b3.76±0.48b1.70±0.46a2.80±0.61a90.59±9.59b

白牡丹一级

Baimudan first grade

2.05±0.32c3.10±0.13a3.97±0.20b1.74±0.42a2.78±0.94a70.67±4.88b

贡眉一级

Gongmei first grade

3.96±0.34bc1.95±0.21b10.80±0.02a5.14±0.17a6.11±0.04a122.75±1.35a

寿眉一级

Shoumei first grade

5.25±0.72b3.17±0.27a11.49±4.42a5.38±3.12a7.17±4.38a126.04±16.41a

寿眉二级

Shoumei second grade

4.74±0.38bc1.67±0.06b10.60±0.50a5.16±0.18a6.54±0.06a122.28±2.18a
表2  白茶花青素苷组成及含量 (μg/g)
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