不同花色福鼎白茶中挥发性萜类化合物的对映异构体分布研究

摘要/Abstract

摘要： 大部分挥发性萜类化合物的分子结构中存在手性碳原子，往往以不同比例的对映异构体混合形式存在于茶叶香气中，其比例及含量与茶树品种、产地及加工工艺等密切相关。然而，目前白茶中挥发性萜类化合物的对映异构体分布特征尚未被系统研究。本研究采用顶空固相微萃取法（Headspace Solid Phase Microextraction, HS-SPME）-手性气相色谱质谱联用技术（Gas chromatography-mass spectrometry，GC-MS）对不同花色福鼎白茶的香气成分进行分析，查明了白毫银针、白牡丹及寿眉样品中14种挥发性萜类化合物的对映异构体分布情况。相对定量分析结果表明，S-芳樟醇、S-Z-橙花叔醇及(2S, 5R)-芳樟醇氧化物B在大部分白茶样品中具有较高的相对含量，而茶螺烷的4个对映异构体的相对含量普遍较低。对映异构体比例（Enantiomeric ratio, ER）分析结果表明，S-柠檬烯、(2S, 5S)-芳樟醇氧化物A、(2S, 5R)-芳樟醇氧化物B、S-芳樟醇、(2R, 5R)-茶螺烷A、(2R, 5S)-茶螺烷B、R-4-萜品醇、S-α-松油醇、S-香茅醇、S-α-紫罗兰酮、S-Z-橙花叔醇、S-E-橙花叔醇、(1R, 2R)-茉莉酸甲酯及(1R, 2S)-茉莉酸甲酯是大部分福鼎白茶中相应萜类化合物的主导立体构型，其中芳樟醇、茶螺烷B、4-萜品醇、香茅醇、α-紫罗兰酮、芳樟醇氧化物A及Z-橙花叔醇的ER值与福鼎白茶的采摘嫩度呈现一定的相关性。多元统计分析结果表明，12种萜类化合物对映异构体的含量在不同花色的福鼎白茶中存在显著性差异，其中R-芳樟醇、(2R, 5S)-茶螺烷B、S-α-松油醇、R-E-橙花叔醇、R-Z-橙花叔醇、S-柠檬烯及S-E-橙花叔醇在白毫银针样本中含量最高，(2R, 5R)-芳樟醇氧化物A及(2S, 5R)-茶螺烷B的含量与白毫银针样本呈负相关；S-Z-橙花叔醇及(1S, 2S)-茉莉酸甲酯在白牡丹样本中含量普遍较高；而R-α-紫罗兰酮的含量在寿眉样本中有较高的含量分布。本研究为后续白茶香气品质形成机理研究、白茶花色等级判别及指纹图谱构建等奠定了良好的理论基础。

关键词: 福鼎白茶, 挥发性萜类化合物, 对映异构体, 多元统计分析, 手性气相色谱-质谱联用技术

Abstract: Volatile terpenoids tend to exist as mixtures with various stereo distributions in tea aroma for existing of chiral carbons in their structures, and their enantiomeric distribution were closely related to tea cultivar, origin and processing technology. However, enantiomeric distribution of volatile terpenoids in white teas has never been systematically. In this work, the enantiomeric distribution of 14 volatile terpenoids in different types of Fuding white teas were analyzed by headspace solid-phase microextraction (HS-SPME) and enantioselective gas chromatography–mass spectrometry (GC–MS). The relative quantitative analysis results showed that S-linalool, S-Z-nerolidol and (2S, 5R)-linalool oxide B presented high relative contents in most white teas; and conversely, the four enantiomers of theaspirane presented extreme low content levels. The enantiomeric analysis results indicated that S-limonene, (2S, 5S)-linalool oxide A, (2S, 5R)-linalool oxide B, S-linalool, (2R, 5R)-theaspirane A, (2R, 5S)-theaspirane B, R-terpinen-4-ol, S-α-terpineol, S-citronellol, S-α-Ionone, S-Z-nerolidol, S-E-nerolidol, (1R, 2R)-methyl jasmonate and (1R, 2S)-methyl epijasmonate were the major absolute configurations of most white teas, and the enantiomeric ratios (ERs) of linalool, linalool oxide B, terpinen-4-ol, citronellol, α-Ionone, linalool oxide A and Z-nerolidol were related to the plucking standard of white teas. Moreover, multivariate statistical analysis results exhibited that significant content differences of 12 volatile terpenoid enantiomers existed among the three different types of Fuding white teas. R-Linalool, (2R, 5S)-theaspirane B, S-α-terpineol, R-E-nerolidol, R-Z-nerolidol, S-limonene and S-E-nerolidol presented highest content levels in Silver Needle tea samples, while (2R, 5R)-linalool oxide A and (2S, 5R)-theaspirane B presented the opposite trends. S-Z-Nerolidol and (1S, 2S)-methyl epijasmonate showed higher content levels in White Peony tea samples, and the contents of R-α-ionone were higher in Shou Mei tea samples than other types of white teas. The above studies lay the theoretical foundation for further researches about formation mechanism of aroma quality of white teas, discrimination of type and grade of white teas and establishment of fingerprints of white teas.

Key words: Fuding white tea, Volatile terpenoids, Enantiomer, Multivariate statistical analysis, Enantioselective gas chromatography-mass spectrometry

中图分类号:

S571.1

严寒朱荫穆兵吕海鹏 Kang Suyoung 张悦林智. 不同花色福鼎白茶中挥发性萜类化合物的对映异构体分布研究[J]. 食品科学, 0, (): 0-0.

Hai-Peng LV Suyoung KANG Yue Zhang. Enantiomeric Distribution of Volatile Terpenoids in Different Types of Fuding White Teas[J]. FOOD SCIENCE, 0, (): 0-0.

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