不同产地野生黑果枸杞资源果实多酚组成分析

【目的】黑果枸杞（Lycium ruthenicum Murr.）主要分布于中国西北地区。其果实在传统中药中被用来治疗心脏病、月经异常及停经等疾病。近年来，发现多酚特别是花色苷类物质是其主要的功效成分。测定并评价不同产地野生黑果枸杞果实中花色苷等多酚的组成情况，为黑果枸杞的品种选育及开发利用提供依据。【方法】采用分光光度计测定其总酚、总黄酮、总花色苷含量；采用HPLC-MS 方法分析鉴定黑果枸杞酚类物质组成及结构；并根据总多酚含量、总黄酮含量、总花色苷含量及多酚共有峰峰面积分别对26个不同产地黑果枸杞的多酚检测结果进行聚类分析。【结果】26个不同产地的黑果枸杞资源果实的总酚含量、总黄酮含量、总花色苷含量的变化幅度分别为8.25-87.77 mg GAE·g^-1、18.03-60.44 mg RE·g^-1、8.21-31.46 mg·g^-1。不同产地的材料间差异较大，其中青海格尔木乌图美仁、新疆甘河子、新疆巴仑台镇、宁夏贺兰12-01黑果枸杞总酚、总黄酮及总花色苷含量较高；通过HPLC-MS分析鉴定，19个多酚类化合物被鉴定出。其中7个为酰化类花色苷，主要花色苷为Petunidin-3-O-rutinoside (cis-p-coumaroyl)-5-O-glucoside。在所有供试黑果枸杞不同产地的材料中共检测到12种共有酚类化合物，其中Petunidin-3-O-rutinoside (cis-p-coumaroyl)-5-O-glucoside在所有供试黑果枸杞中的含量均最高，是黑果枸杞花色苷类多酚的主要成分。各产地样品HPLC特征图谱相似，有个别质量较差的情况存在；聚类参数不同，聚类结果略有差异。根据总酚含量、总黄酮含量、总花色苷含量聚类，聚为7类，甘肃民勤中渠、新疆喀什、宁夏贺兰12-1聚为第六类，新疆甘河子单独聚为第七类，该两类总酚、总黄酮及总花色苷含量均含量分别介于57.74-87.77 mg·g^-1、41.52-55.46 mg·g^-1和12.25-28.54 mg·g^-1。总酚、总黄酮及总花色苷含量都很高，特别是新疆甘河子产地，可作为以多酚和花色苷含量为指标的优质良种材料。根据共有峰面积共聚为5类，其中宁夏贺兰12-1、青海格尔木乌图美仁、新疆甘河子为一类，该类峰面积很高，其中主成分峰面积介于2 350.84-3 092.94。新疆巴轮台镇单独一类，其主成分峰面积高达为3 579.96。【结论】26个不同产地的黑果枸杞中多数富含多酚类物质，特别是酰化矮牵牛素花色苷含量丰富，是较好的开发富含花色苷类多酚的功能性食品资源。

The Polyphenols Composition of Lycium ruthenicum Murr. from Different Places

【Objective】 Lycium ruthenicum 【Method】The contents of total polyphenols, total flavones and total anthocyanins were analyzed using spectrophotometer and the composition of the polyphenol extracts was analyzed using HPLC and HPLC-MS. Hierarchical cluster analysis (HCA) was also used to classify the tested results. 【Result】 Total contents of polyphenols, flavones and anthocyanins of the L. ruthenicum Murr.s were 8.25-87.77 mg GAE·g^-1 dry fruit, 18.03-60.44 mg RE·g^-1 dry fruit, and 8.21-31.46 mg·g^-1 dry fruit, respectively. The samples from Wutumeiren Gomud of Qinghai, Ganhezi of Xinjiang, Baluntai town of Xinjiang, and Helan12-1 of Ningxia had the higher value of total polyphenols, total flavones and total anthocyanins. Through HPLC-ESI-MS analysis, a total of 19 polyphenols were identified in the tested L. ruthenicum Murr, including 7 acylated anthocyanins, and petunidin-3-O-rutinoside (cis-p-coumaroyl)-5-O-glucoside was found to be the main anthocyanin in L. ruthenicum Murr. Twenty polyphenols were found in all kinds of L. ruthenicum Murr, while Petunidin-3-O-rutinoside (cis-p-coumaroyl)-5-O-glucoside was the main composition of the polyphenols in fruits of L. ruthenicum Murr. The polyphenols fingerprints of L. ruthenicum Murr. from 26 different places were similar, excluding a few of samples. The results of HCA according to the contents of polyphenols, flavones and anthocyanins in L. ruthenicum Murr. were clustered into7 kinds. In the sixth and seventh kinds, all the contents of polyphenols, flavones and anthocyanins were higher(57.74-87.77 mg·g^-1, 41.52-55.46 mg·g^-1, 12.25-28.54 mg·g^-1, respectively) in the L. ruthenicum Murr. samples from Zhongqu Mingqin of Gansu, Kashi of Xinjiang, and 12-01 Helan of Ningxia. Especially, the sample from the Ganhezi of Xinjiang would be the good elite material using the index of the contents of polyphenols and anthocyanins. The result of clustering analysis according to HPLC shared peaks’ area of L. ruthenicum Murr. was clustered into five kinds according to the 12 shared peaks’ area, among which the fourth kinds Helan 12-1, Wutumeiren Gomud of Qinghai, Ganhezi of Xinjiang samples’ relative peak area was high, and as the main component, peak 22 relative peak area was between 2 350.84 and 3 092.94 . The samples from Baluntai town of Xinjiang as a separate kinds, its main component peak 22 relative peak area reached up to 3 579.96. 【Conclusion】 The compositons and total polyphenols contents in fruits of L. ruthenicum Murr. from different places are different, but most of the samples are good resources for development of healthy food which are rich in polyphenols, exceptionally, acylation- petunidin. Murr. is grown in the northwest of China, and its fruits is used in medicinal foods for treatments of heart disease, abnormal menstruation and menopause. In the past few years, the polyphenols (especially anthocyanins) are proved to be the main effective components in Lycium ruthenicum Murr. Composition determination and evaluation of anthocyanin and other polyphenols of wild L. ruthenicum fruit in different origin, so as to provide the basis for the breeding and utilization of it.