基于UPLC-MS代谢组学技术的枣果皮黄酮类化合物分析

Analysis of Flavonoids in Fruit of Jujube(Ziziphus jujuba)by UPLC-MS-based Metabonomics

采用超高效液相色谱-质谱联用技术,结合代谢组学分析方法,研究黄酮类化合物种类及含量与“三变红”枣果实着色间的关系。结果表明“三变红”枣果发育的S1、S2和S3时期,枣皮总黄酮呈由高到低再到高的变化趋势,其含量分别为4.94、0.95、4.45 mg/g(干质量),而与之对应时期的果实则经历了由紫红到绿白再到深红过程,枣皮着色与总黄酮含量表现为明显相关性。利用主成分分析和偏最小二乘法分析发现,3个不同发育期黄酮类化合物组成及含量的分布上具有明显差异。其中,槲皮素3-O-芸香糖苷、甲基槲皮素O-己糖苷、木犀草素O-芥子酰己糖苷、羟甲基黄酮5-O-己糖苷、柚皮素O-丙二酰己糖苷、3,4,5-三羟黄酮O-芸香糖苷、6-C-己糖基-木犀草素O-己糖苷、异牧荆素在S1中远高于S2和S3,它们被鉴定为S1期特征性黄酮类化合物,而矢车菊素O-己糖基、芹菜素O-己糖基-戊糖苷、槲皮素5-O-己糖苷-O-丙二酰己糖苷、金圣草黄素O-葡萄糖醛酸(水杨醇)醚O-二葡萄糖醛酸、金圣草黄素被认为是S3期标志性黄酮类化合物。本研究阐明了枣果发育过程中果皮颜色与黄酮类化合物的内在关系,对揭示“三变红”枣果着色机理具有重要意义。

Ultra-high performance liquid chromatography-mass spectrometry(UPLC-MS)based metabolomics was used to analyze the relationship between the varieties and contents of flavonoids and color change during the fruit development of jujube(cv.Sanbianhong).Results showed that as fruit development proceeded from S1 to S2 to S3,the color changed from purple red to green white to deep red,and the total flavonoid content of jujube peel showed an increase-decrease-increase trend,which was 4.94,0.95 and 4.45 mg/g dry at mass at the three time points,respectively,indicating that the content of total flavonoids in jujube peel was positively correlated with the color change.Principal component analysis(PCA)and orthogonal partial least square-discriminate analysis(OPLS-DA)showed clear differences in the composition and contents of flavonoids at the three developmental times.The contents of quercetin 3-O-rutinoside,methyl quercetin O-hexoside,luteolin O-sinapoylhexoside,luteolin O-sinyl hexoglucoside,naringenin O-malonylhexoside,3,4,5-trihydroxyflavone O-rutinoside,6-C-hexosyl-luteolin O-hexoside and isovitexin at S1 were much higher than those at S2 and S3,and they were identified as characteristic flavonoids at the S1 stage,while cyanidin O-hexose,apigenin O-hexosyl-pentoside,quercetin 5-O-malonylhexosyl-hexoside,sirolimus O-glucuronoic acid(salicyl alcohol)ether O-dialuronic acid,and chrysoeriol were considered as characteristic flavonoids at the S3 stage.This study is of great significance to reveal the mechanism of fruit coloration in“Sanbianhong”jujube.