利用DAD-HPLC和LC-MS法检测金丝小枣中黄酮类化合物

采用二极管阵列高效液相色谱分离技术和液相色谱-质谱联用技术对金丝小枣中黄酮类物质进行分析和鉴别。液相色谱条件为：色谱柱为Hypersil BDS-C18（250 mm×4.6 mm，5 μm），柱温30 ℃，甲醇-0.1%甲酸溶液为流动相，梯度洗脱，流速0.8 mL/min，进样量10 μL，采用270 nm和370 nm双波长检测。结果表明：金丝小枣中含有杨梅素、芦丁、槲皮素、异鼠李素4 种黄酮类物质，含量分别为40.90、8.40、32.60 μg/g和12.56 μg/g。并且在5～125 μg/mL范围内，该方法显示良好的线性关系和重复性，当信噪比为3时，检出限为1.23～1.73 ng/L。精密度实验的相对标准偏差为1.10%～4.31%，加标回收率为93.50%～106.70%（相对标准偏差为0.68%～2.90%）。由此可以看出：该方法样品前处理简单、回收率较高、精密度良好，是一种便捷且精确的分析方法，适用于金丝小枣中黄酮类化合物的检测。

Determination of Flavonoid in Ziziphus jujuba Mill. cv. Jinsixiaozao Fruits by DAD-HPLC and LC-MS

In this study, the flavonoids in Ziziphus jujuba Mill. cv. Jinsixiaozao fruits were analyzed by using high
performance liquid chromatography with diode array detector (DAD-HPLC) and liquid chromatography-mass spectrometry
(LC-MS). The chromatographic separation was achieved on a Hypersil BDS-C18 column (250 mm × 4.6 mm, 5 μm) using a
mobile phase consisting of methanol and 0.1% formic acid aqueous solution at 0.8 mL/min flow rate by gradient elution. The
column temperature was set at 30 ℃, and the injection volume was 10 μL. Dual-wavelength detection was carried out at 270
and 370 nm. Then LC-MS was employed to determine the flavonoids. Results demonstrated that Jinsixiaozao jujube contained
four flavonoids, myricetin, rutin, quercetin, and isorhamnetin and their contents were 40.90, 8.40, 32.60 and 12.56 μg/g,
respectively. In the range of 5–125 μg/mL, the method exhibited a good linear relationship and repeatability. The limits of
detection (LODs) were in the range of 1.23–1.73 ng/L at a signal-to-noise ratio of 3. The relative standard deviation (RSD)
values for precision were 1.10%–4.31%. The recoveries from spiked samples were 93.50%–106.70% (RSD = 0.68%–2.90%).
Conclusively, this method had the advantages of simple pretreatment, high recovery rate and good precision, and it could
provide a convenient and precise method for the analysis of flavonoids in Ziziphus jujuba Mill. cv. Jinsixiaoza fruits.