采用ACQUITY UPLC HSS T3色谱柱,以含0?1%( v/v)甲酸的乙腈?水为流动相,梯度洗脱,建立了超高效液相色谱?二极管阵列检测?串联质谱( UPLC?PDA?MS/MS)联用技术测定茶叶中黄酮醇糖苷类化合物的方法。结合色谱保留时间、紫外光谱、一级和二级质谱参数等信息,在绿茶和红茶中共识别了15种黄酮醇糖苷类化合物,包括3种杨梅素糖苷、6种槲皮素糖苷和6种山柰素糖苷类化合物。定量分析中采用串联四极杆质谱检测,以槲皮素?3?葡萄糖?鼠李糖二糖糖苷( Q?GRh)为标准品,其他黄酮醇糖苷进行相对定量。结果表明,绿茶和红茶中黄酮醇糖苷类化合物的含量和分布差异显著,绿茶中的黄酮醇糖苷总量是红茶的1?7倍,绿茶中的黄酮醇糖苷主要以杨梅素?3?半乳糖糖苷( M?Ga)、杨梅素?3?葡萄糖糖苷( M?G)、槲皮素?3?葡萄糖?鼠李糖?葡萄糖三糖糖苷( Q?GaRhG)、槲皮素?3?半乳糖?鼠李糖?葡萄糖三糖糖苷( Q?GRhG)、山柰素?3?半乳糖?鼠李糖?葡萄糖三糖糖苷( K?GaRhG)和山柰素?3?葡萄糖?鼠李糖?葡萄糖三糖糖苷( K?GRhG)为主,而红茶中主要以Q?GRh、槲皮素?3?葡萄糖糖苷( Q?G)、山柰素?3?葡萄糖?鼠李糖二糖糖苷( K?GRh)和山柰素?3?半乳糖糖苷( K?Ga)为主。本方法简单快速,准确性好,可用于茶叶中黄酮醇糖苷类化合物的分析。
An ultra?high performance liquid chromatography?photodiode array detection?tandem mass spectrometry ( UPLC?PDA?MS/MS) method was developed for the determination of flavo?nol glycosides in tea samples. The chromatographic separation was performed on an UPLC HSS T3 column by gradient elution with the mobile phases of acetonitrile and water both containing 0?1%( v/v) formic acid. A total of 15 flavonol glycosides which include 3 myricetin glycosides, 6 quercetin glycosides and 6 kaempferol glycosides were positively identified in green and black tea samples by comparing the retention times and mass spectra of the samples with standards and publications. The quantities of flavonol glycosides were relatively calculated with the stand?ard quercetin?3?rhamnosylglucoside ( Q?GRh) which was calibrated with external quantification method using multi?reaction monitoring ( MRM ) mode. The results showed that there were different flavonol glycoside distributions in green tea and black tea. The total amount of flavonol glycosides in green tea was 1?7 times of that in black tea. The major flavonol glycosides in green tea were myricetin?3?galactoside ( M?Ga) , myricetin?3?glucoside ( M?G) , quercetin?3?glucosyl?rhamnosyl?galactoside ( Q?GaRhG ) , quercetin?3?glucosyl?rhamnosyl?glucoside ( Q?GRhG) , kaempferol?3?glucosyl?rhamnosyl?galactoside ( K?GaRhG ) and kaempferol?3?glucosyl?rhamnosyl?glucoside ( K?GRhG) , but for black tea, the major flavonol glycosides were querce?tin?3?rhamnosylglucoside ( Q?GRh) , quercetin?3?glucoside ( Q?G) , kaempferol?3?rhamnosylglu?coside (K?GRh) and kaempferol?3?galactoside (K?Ga). The present method is accurate, con?venient for the rapid identification of flavonol glycosides and analysis of constituent distribution for green and black teas.
参考文献
[1] | Peterson J;Dwyer J;Bhagwat S;Haytowitz D;Holden J;Eldridge A L;Beecher G;Aladesanmi J.Major flavonoids in dry tea.[J].Journal of Food Composition and Analysis,20056(6):487-501. |
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