中国野生笃斯越橘花青素的初步分离和分析

Preliminary Separation and Analysis of Anthocyanidins in Blueberries of Vaccinium uliginosum of China

采用反相高效液相色谱法和电喷雾质谱法对我国野生笃斯越橘中花青素组分进行了分离和分析.制备野生越橘花青素的粗提物,经大孔树脂柱层析得到花青素样品,其得率为0.72%.用香草醛法测得其总黄烷醇含量为95%.采用Alltima C18反相色谱柱(250 mm×4.6 mm,5μm),以2%甲酸水溶液(A)和2%甲酸/甲醇溶液(B)作为流动相,分2个梯度对花青素组分进行洗脱,将其主要洗脱峰在电喷雾正离子模式下进行分析,根据质谱的准分子离子[M+H](m/z)检测其聚合度.结果表明,我国野生越橘花青素的提取物被展开成8个主要的洗脱峰,以峰面积计算,主要洗脱峰总含量达85%.经质谱分析,判断为2个单体,3个二聚体,1个三聚体,2个四聚体.结果表明,我国野生笃斯越橘中含有较丰富的花青素,低聚体是其中的主要成分.本文首次报道了我国大兴安岭野生笃斯越橘花青素的组成情况,对于开展其后续的结构、功能、质量检测以及生产开发研究都具有一定的参考价值.

A RP-HPLC method and ESI-MS were established to separate and analyze the component of anthocyanidins from blueberries of Vaccinium uliginosum of China. The method was first used to prepare the crude extract of anthocyanidins from blueberries. After the macroporous resin chromatography, the yield of anthocyanidins came up to 0.72 %. The total content of flavanol was measured up to 95 % by vanillin method. Then the RP-HPLC was performed on Alltima C18 column （250 mm × 4.6 mm, 5 μm）, with the mobile phase of solution A （2% formic acid in water ） and solution B （2% formic acid in methanol）, to elute the component of anthocyanidins by two gradient. The main elution peak was collected and then analyzed using ESI-MS in positive ion model. According to the value of m/z, the degree of polymerization was detected. The result showed that the extract of anthocyanidins in blueberries of Vaccinium uliginosum was separated mainly into eight elution peaks, the total content up to 85 % measured by peak areas. Two monomers, three dimers, one trimer and two tetramers were identified by MS. It was showed that blueberries of Vaccinium uliginosum of China contained a wealth of anthocyanidins and the oligomer was the main component. This paper reported the composition of anthocyanidins in blueberries of Vaccinium uliginosum at Daxinganling of China for the first time. These results have some references value in the subsequent study on the structure, the function, the quality inspection, the production research and development in blueberries of Vaccinium uliginosum of China.