Structural characterization and identification of iridoid glycosides, saponins, phenolic acids and flavonoids in Flos Lonicerae Japonicae by a fast liquid chromatography method with diode-array detection and time-of-flight mass spectrometry
Structural characterization and identification of iridoid glycosides, saponins, phenolic acids and flavonoids in Flos Lonicerae Japonicae by a fast liquid chromatography method with diode-array detection and time-of-flight mass spectrometry
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DOI：
10.1002/rcm.4245
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发表时间：
2009-10-01
影响因子：
2
通讯作者：
Li, Ping
中科院分区：
文献类型：
--
作者：
Qi, Lian-Wen;Chen, Chun-Yun;Li, Ping
建立了一种快速液相色谱-二极管阵列检测器（DAD）-飞行时间质谱（TOF-MS）联用技术，用于中药金银花（FLJ）的化学成分分析。色谱分析时间减少到25分钟，而不牺牲分辨率，使用填充有1.8 μ m多孔颗粒（4.6 × 50 mm）的柱，比传统的5.0 μ m柱（4.6 × 150 mm）的性能快三倍。采用DAD-TOF-MS对从FLJ中分离得到的4类主要化合物进行了结构表征：环烯醚萜苷在240 nm处有最大紫外吸收;酚酸在217、242和326 nm处有最大紫外吸收;黄酮类在255和355 nm处有最大紫外吸收;而皂苷类则无吸收。在电喷雾离子化（ESI）-飞行时间质谱（TOF-MS）实验中，环烯醚萜苷类化合物中通常会出现葡萄糖单元（162 Da）的消除，以及H_2O、CH_3OH和CO的连续损失。酚酸类通常通过损失咖啡酸单元（162 Da）和几个标记的奎尼酸部分离子而在[M-H-咖啡酰基]（-）处产生基峰;糖苷键的断裂（162或308 Da的损失）、随后的H2O、CO、RDA的损失和C-环断裂是类黄酮最可能的断裂途径。通过对每个分子离子和随后的碎片离子的精确质量测量（误差在4ppm以内），以及飞行时间质谱的“全质谱”信息，共鉴定出41个化合物，包括13个环烯醚萜苷类化合物、11.在FLJ的甲醇提取物中鉴定了酚酸类、7种皂苷和10种黄酮类化合物。版权所有（C）2009约翰威利父子有限公司
A fast liquid chromatography method with diode-array detection (DAD) and time-of-flight mass spectrometry (TOF-MS) has been developed for analysis of constituents in Flos Lonicerae Japonicae (FLJ), a traditional Chinese medicine derived from the flower bud of Lonicera japonica. The chromatographic analytical time decreased to 25 min without sacrificing resolution using a column packed with 1.8-mu m porous particles (4.6 X 50 mm), three times faster than the performance of conventional 5.0-mu m columns (4.6 X 150 mm). Four major groups of compounds previously isolated from FLJ were structurally characterized by DAD-TOF-MS: iridoid glycosides showed maximum UV absorption at 240nm; phenolic acids at 217, 242, and 326 nm; flavonoids at 255 and 355 nm; while saponins had no absorption. In electrospray ionization (ESI)-TOF-MS experiments, elimination of a glucose unit (162 Da), and successive losses of H2O, CH3OH and CO, were generally observed in iridoid glycosides; saponins were characterized by a series of identical aglycone ions; phenolic acids typically generated a base peak at [M-H-caffeoyl](-) by loss of a caffeic acid unit (162 Da) and several marked quinic acid moiety ions; cleavage of the glycosidic bond (loss of 162 or 308 Da), subsequent losses of H2O, CO, RDA and C-ring fragmentation were the most possible fragmentation pathways for flavonoids. By accurate mass measurements within 4ppm error for each molecular ion and subsequent fragment ions, as well as the 'full mass spectral' information of TOF-MS, a total of 41 compounds including 13 iridoid glycosides, 11. phenolic acids, 7 saponins, and 10 flavonoids were identified in a methanolic extract of FLJ. Copyright (C) 2009 John Wiley & Sons, Ltd.