Systematic identification and quantification of tetracyclic monoterpenoid oxindole alkaloids in Uncaria rhynchophylla and their fragmentations in Q-TOF-MS spectra
Systematic identification and quantification of tetracyclic monoterpenoid oxindole alkaloids in Uncaria rhynchophylla and their fragmentations in Q-TOF-MS spectra
复制标题
钩藤中四环单萜羟吲哚生物碱的系统鉴定和定量及其 Q-TOF-MS 谱图碎片
DOI：
10.1016/j.jpba.2013.03.017
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发表时间：
2013-07-01
影响因子：
3.4
通讯作者：
Xie, Ning
中科院分区：
文献类型：
--
作者：
Xie, Shuanglu;Shi, Yuanyuan;Xie, Ning
钩藤（Uncaria rhynchophylla，UR）是钩藤属植物，主要分布于中国和日本。在这项研究中，化学成分，包括生物碱，黄酮类化合物，奎尼酸，在UR已被系统地确定和定量的高效液相色谱法结合二极管阵列检测器和四极杆飞行时间质谱（Q-TOF-MS）的方法。四环单萜类氧化吲哚生物碱（TMOAs）是该植物的特征化合物，其质谱裂解进行了研究。诊断碎片离子（DFI）首先划定为isorhynchophylline型（7S，C-20-乙基）和corynoxeine型（7 R，C-20-乙烯基）TMOAs，这些被用于鉴定这些生物碱在UR。在这项研究中，共有29个化合物，包括18个生物碱，6个黄酮类化合物，和5个奎尼酸，被确定。其中，有4个新的TMOAs，命名为22-O-β-吡喃葡萄糖基异钩藤酸（10），22-O-β-吡喃葡萄糖基钩藤酸（11），9-羟基异紫堇氧素（16）和9-羟基紫堇氧素（20），以前没有报道。此外，8种标记化合物，即绿原酸（3）、儿茶素（8）、表儿茶素（9）、异corynoxeine（24）、钩藤碱（25）、异钩藤碱（27）、长春苷内酰胺（28）和corynoxeine（29），已同时定量。该方法已成功应用于江西省3个尿嘧啶样品的分析。并对各指标化合物的含量进行了测定和比较。(C)2013 Elsevier B. V.保留所有权利。
Uncaria rhynchophylla (UR) is a species of Uncaria that is distributed mainly in China and Japan. In this study, the Chemical constituents, including alkaloids, flavonoids, and quinic acids, in UR have been systematically identified and quantified by a developed method of high-performance liquid chromatography coupled with diode-array detection and quadrupole time-of-flight mass spectrometry(Q-TOF-MS). Tetracyclic monoterpenoid oxindole alkaloids (TMOAs) are characteristic compounds in this herb, and their fragmentations in Q-TOF-MS have been investigated. Diagnostic fragmentation ions (DFIs) were first delineated for isorhynchophylline-type (7S, C-20-ethyl) and corynoxeine-type (7R, C-20-vinyl) TMOAs, and these were used for identification of these alkaloids in UR. In this study, a total of 29 compounds, comprising 18 alkaloids, six flavonoids, and five quinic acids, were identified. Among them, there are four novel TMOAs, named as 22-O-beta-glucopyranosyl isorhynchophyllic acid (10), 22-O-beta-glucopyranosyl rhynchophyllic acid (11), 9-hydroxy isocorynoxeine (16), and 9-hydroxy corynoxeine (20), which have not been reported previously. Furthermore, eight marker compounds, namely chlorogenic acid (3), catechin (8), epicatechin (9), isocorynoxeine (24), rhynchophylline (25), isorhynchophylline (27), vincoside lactam (28), and corynoxeine (29), have been simultaneously quantified. The developed method has been validated and successfully applied to analyze three samples of UR from Jiangxi Province. The contents of the marker compounds have been detected and compared. (C) 2013 Elsevier B.V. All rights reserved.