Tolonen Ari, Uusitalo Jouko
Novamass Analytical Ltd, P.O. Box 3000, 90014 Oulu, Finland.
Rapid Commun Mass Spectrom. 2004;18(24):3113-22. doi: 10.1002/rcm.1736.
A liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) method based on time-of-flight (TOF) MS with polarity switching and continuous exact mass measurement using a LockSpray ion source was developed for fast evaluation of the total flavonoid content in plants and foodstuffs. No complicated sample preparation was needed, but only a dilution of the extracts. A fast generic gradient elution and wide mass range acquisition was used with good sensitivity. The total analysis time was only 23 min. The ion chromatograms for flavonoid compounds were automatically extracted, and the fragmentation patterns obtained using positive ion mode and exact mass data for both polarities were used for the tentative identification of compounds. Software-based automated searching of molecular ions for flavonoids and their glycosides (xylosides/arabinosides, rhamnosides, glucosides/galactosides) from total ion chromatograms was used. The compounds were quantified using quercetin, quercitrin, rutin and kuromanine as external standards and dextromethorphan as an internal standard. The detection limits ranged from 0.01-0.04 microg/mL, while the quantitation ranges obtained were 0.2-10 microg/mL for anthocyanins and 0.2-4 microg/mL for the other flavonoids. The accuracies within these ranges varied between 80-120% and precision was in the range 0-14% (relative standard deviation). Flavonoid contents of two medicinal plants (Hypericum perforatum and Rhodiola rosea), two grape red wines, two orange juices and two green teas were evaluated using the method, and the results obtained were in good agreement with those published previously.
建立了一种基于飞行时间(TOF)质谱的液相色谱/电喷雾电离质谱(LC/ESI-MS)方法,该方法采用极性切换,并使用LockSpray离子源进行连续精确质量测量,用于快速评估植物和食品中的总黄酮含量。无需复杂的样品制备,只需对提取物进行稀释。采用快速通用梯度洗脱和宽质量范围采集,灵敏度良好。总分析时间仅为23分钟。自动提取黄酮类化合物的离子色谱图,并使用正离子模式获得的碎片模式以及两种极性的精确质量数据对化合物进行初步鉴定。使用基于软件的自动搜索总离子色谱图中黄酮类化合物及其糖苷(木糖苷/阿拉伯糖苷、鼠李糖苷、葡萄糖苷/半乳糖苷)的分子离子。使用槲皮素、槲皮苷、芦丁和花青素作为外标,右美沙芬作为内标对化合物进行定量。检测限范围为0.01 - 0.04μg/mL,而获得的定量范围对于花青素为0.2 - 10μg/mL,对于其他黄酮类化合物为0.2 - 4μg/mL。这些范围内的准确度在80 - 120%之间变化,精密度在0 - 14%范围内(相对标准偏差)。使用该方法评估了两种药用植物(贯叶连翘和红景天)、两种红葡萄酒、两种橙汁和两种绿茶中的黄酮类化合物含量,所得结果与先前发表的结果高度一致。