黑果枸杞中花色苷的提取与结构鉴定  

Extraction and Identification of Anthocyanins in Lycium ruthenicum Murr.

作　　者：谭亮[1] 董琦[1] 曹静亚[1] 耿丹丹[1] 胡风祖[1] 

机构地区：[1]中国科学院西北高原生物研究所,西宁810008

出　　处：《天然产物研究与开发》2014年第11期1797-1802,1760,共7页Natural Product Research and Development

基　　金：中国科学院知识创新工程重要方向项目(KSCX2-EW-J-26)

摘　　要：采用紫外-可见光谱法并结合高效液相色谱-电喷雾串联质谱对黑果枸杞中花色苷的组成及结构进行了鉴定。结果显示:(1)黑果枸杞花色苷在0.1%盐酸-甲醇溶液中呈紫红色表明花色苷中的主要成分可能是飞燕草色素、牵牛花色素、锦葵色素及其衍生物中的一种或几种;向提取溶液中加入5%Al Cl3甲醇溶液后无红移现象表明花色苷结构B环上无邻位酚羟基;A440nm/Aλmax比值小于20%表明该色素是3,5位均带有糖苷键的双取代花色苷;在304 nm处有一最大吸收峰表明该色素分子内含有酰基;色素水解后主要生成葡萄糖。由上述可初步推测出黑果枸杞色素中主要为酰基化的锦葵色素-3,5-二葡萄糖苷;(2)经紫外分光光度法、质谱和文献报道综合分析鉴定出黑果枸杞中含有8种花色苷,分别是:飞燕草素-3-O-葡萄糖苷、芍药素-3-O-葡萄糖苷、矮牵牛素-5-O-葡萄糖苷、矮牵牛素-3-O-(6-O-对香豆酰)芸香糖苷-5-O-葡萄糖苷、锦葵色素-3-O-(6-O-对香豆酰-3-O-乙酰)-5-O-二葡萄糖苷、飞燕草素-3-O-(6-O-乙酰)葡萄糖苷、锦葵色素-3-O-(6-O-对香豆酰)葡萄糖苷和锦葵色素-3,5-二葡萄糖苷,其含量依次为0.86%、1.17%、2.38%、11.79%、68.35%、0.63%、5.24%、9.58%。花色苷是黑果枸杞中重要的组成成分,该试验可为黑果枸杞的质量控制提供依据。The compositions of anthocyanins in Lycium ruthenicum Murr. were characterized and identified by UV-visible spectrophotometry and HPLC-ESI-MS/MS. The results indicated that （ 1 ） One or more of delphinidiu, petunidin, maid- din and their derivatives might be the main components due to the antbecyanins from L. ruthen/cum in 0. I% hydrocldo- rlc acid-methanol showing a mulberry solution ;no redshift after 5% AICI3 -methanol solution was added in extract proved that there was no ortho phenolic hydroxyl in the B ring of anthocyanin structure; the ratio of A,0m/A^E was less than 20% indicated that the pigment was a disubstituted anthocyanins of 3,5-O-diglycoside;thcre was a maximum absorption at 304 ran indicated that acyl was contained within the pigment molecules;the main monosaccharide in hudrulyzate of pigment was glucose. The above results may initially speculated that the main pigment was a acylated malvidin-3,5-O- diglucoside. （2） Eight anthoeyanins in L. ruthenicum were separated and identified through comprehensive analysis of UV absorption spectra,MS spectra and literature data. The pigments （ contents, % ） were finally determined to be del- phinidin-3-O-glucoside （0.86%） ,peonidin-3-O-glucoside （1.17%） ,petunidin-5-O-glucoside （2.38%） ,petunidin-3- O- （ 6-O-p-coumaryl ） -mtinoside-5 -O-glucoside （ 11. 79% ）, malvidin-3 -0- （ 6-O-p-coumaryl, 3-O-acetyl ） -5 -O-diglu- coside （ 68.35% ）, delphinidin-3-O-（6-O-acetyl） -glucoside （ 0.63 % ）, malvidin-3-O-（6-O-p-coumaryl） -glucoside （ 5. 24% ） and maividin-3,5-O-diglucoside （9.58%）. Anthocyanlns were important components of L. ruthenicum,thls stud- y provided additional evidence for the quality evaluation of L ruthen/cum.

关 键 词：黑果枸杞 花色苷 紫外-可见光谱法 高效液相色谱-电喷雾串联质谱 结构鉴定 

分 类 号：Q946.83[生物学—植物学] R284.1[医药卫生—中药学]