14个欧亚种红色酿酒葡萄品种(品系)的花色苷组成和含量分析

The compositions and contents of anthocyanins of 14 red wine grape varieties or clones(Vitis vinifera)

【目的】对14个欧亚种红色酿酒葡萄品种(品系)的花色苷组成和含量进行分析,以探究利用花色苷作为化学指纹来区分品种。【方法】以北京市海淀区中国农业大学上庄实验站的14个欧亚种红色酿酒葡萄品种(品系)为材料,利用高效液相色谱-质谱联用(HPLC-MS)方法检测其果皮中的花色苷组成和含量,对不同葡萄品种中各种花色苷类型进行比较,并基于各单体花色苷含量进行聚类分析和主成分分析。【结果】共检测到21种花色苷,‘西拉’花色苷含量最高;‘黑比诺115’的二甲花翠素-3-葡萄糖苷相对含量最高,且不含酰化类花色苷;‘丹魄’是花翠素-3-葡萄糖苷、甲基花翠素-3-葡萄糖苷相对含量较高的品种。从酰化花色苷的相对含量可以看出,乙酰化和香豆酰化花色苷相对含量高于咖啡酰化类,‘马贝克’‘西拉’酰化花色苷相对含量高于其他品种;‘品丽珠’和‘内比奥罗’的乙酰化花色苷相对含量最高;‘马贝克’的香豆酰化花色苷含量最高;‘蒙特布查诺’的咖啡酰化类花色苷含量最高。聚类分析表明,供试的14个品种(品系)可以被分为2大类,第1大类是‘黑比诺115’,第2大类包括‘马贝克’和其他品种。主成分分析将‘黑比诺115’和‘多塞托’分在第1象限,‘蒙特布查诺’和‘丹魄’分在第2象限,第3象限是‘比诺塔吉’‘内比奥罗’‘西拉’和‘马贝克’,‘品丽珠’和‘美乐’的各个品系都在第4象限。【结论】不同品种单体花色苷所占比例有明显差异,供试的14个葡萄品种(品系)主成分分析结果与聚类分类结果基本一致,花色苷可以作为化学指纹区分14个欧亚种红色酿酒葡萄品种(品系)。

[Objective] The content of anthocyanins in grape is influenced by many factors such as vari- ety, climate, soil property and training system, but the composition and relative content of anthocyanins of different cultivars are mainly determined by genetic factors. Therefore, anthocyanins can be used as chem- ical fingerprints for distinguishing grape varieties. [Methods] In this study, 14 red wine grape varieties （clones） （V. vinifera） were used, including ‘Cabernet Franc 409＇ ‘Cabernet Franc 327＇ ‘Dolcetto＇, ‘Merlot 343＇ ＇Merlot 181＇ ‘Malbec＇ ‘Marselan＇ ‘Montepulciano＇ ‘Nebbiolo＇‘Pinot Noir 115＇ ‘Pinotage＇ ‘Syrah 100＇ ‘Syrah 525＇ and ‘Tempranillo＇ grown in the Shangzhuang Experimental Station of China Agricultural University, Haidian district, Beijing, China. Samples were collected in September 10, Septem- ber 15, September 25, and October 16, 2016, respectively. Three biological repeats were made for each va-rieties （clones）. The soluble solids in grape juice were measured by hand sugar meter, the pH was mea- sured by pH meter. The titratable acid concentration of juice was determined by potentiometric titration. The compositions and contents of anthocyanins of the grape skins were determined by high performance liquid chromatography-mass spectrometry （HPLC-MS）. The contents of anthocyanins of different grape varieties （clones） were compared and analyzed by principal component analysis. The classification of the varieties was made by cluster analysis. [Results] A total of 21 anthocyanins were detected. The trend of the relative contents was malvidin-3-glucoside （Mv）〉 petunidin-3-glucoside （Pt）〉 deiphinidin-3-gluco- side （Dp）, and the relative content of cyanidin-3-glucoside （Cy） was low. The content of anthocyanins of ＇Syrah＇ was the highest. ＇Pinot Noir 115＇ had the highest relative content of malvidin-3-glucoside while it did not have acylated anthocyanins. ‘Tempranillo＇ had higher relative content of delphinidin-3-gluco- side and petunidin-3-glucoside and ‘Cabernet Franc＇ had the lowest value. The relative contents of acet- ylated and coumarylated anthocyanins were higher than that of caffeylated anthocyanins. The relative con- tent of acylated anthocyanins of ＇Malbec＇ and ＇Syrah＇ was higher than that of other varieties （clones）. The acetylated anthocyanins of ‘Cabernet Franc＇ and ‘Nebbiolo＇ were the highest while the values of ‘Dolcetto＇, ‘Malbec＇ and ‘Tempranillo＇ were less than 20%. The coumarylated anthocyanins in differ- ent varieties were quite different. ‘ Malbec＇ had the highest coumarylated anthocyanin＇ s proportion while the ＇Montepulciano＇ had the highest caffeylated anthocyanins. The relative content of delphinidin-3-cou- maryl glucoside was relatively low, and it was only found in ＇Malbec＇ ＇Syrah＇ and ＇Tempranillo＇ （〈 0.4%）. Cyanidin- 3- coumaryl glucoside was relatively high in ‘ Merlot＇ ‘ Syrah＇ and ‘ Tempranillo＇, and it was not detected in other varieties. 14 varieties （clones） could be divided into two categories by the cluster diagram of the relative content of anthocyanins. The first category included ‘Pinot Noir 115＇ and‘Dol- cetto＇, the second category includes ＇Malbec＇ and other varieties. ‘Syrah＇ ‘Montepulciano＇ ‘ Nebbiolo＇ ‘ Merlot＇ ‘ Dolcetto＇‘Cabernet Franc＇ ‘Pinotage＇ ‘Marselan＇ were classified to the same class. Among them, the distance between ‘Cabernet Franc＇ and ‘Merlot＇ was near, and ‘Marselan＇ ‘Pinotage＇ and ‘Nebbiolo＇ were relatively close. ‘Pinot Noir 115＇ and ‘Dolcetto＇ were located in the first quadrant, while ＇Montepulciano＇ and ‘Tempranillo＇ in the second quadrant, ＇Nebbiolo＇‘Pinotage＇‘ Malbec＇ and ‘Syrah＇ in the third quadrant includes according to the results of the principal component analysis. The different clones of ＇Merlot＇ and ‘Cabernet Franc＇ were all located in the fourth quadrant. [Conclusion] Different varieties （clones） of grape differ significantly in anthocyanin contents and compositions of fruit skins. The classification of 14 wine grape varieties by principal component analysis was basieally the same as that by clustering analysis. Anthocyanins can be used as chemical fingerprints for distinguishing red wine grape varieties （clones）.