Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry
Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry
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DOI：
10.1002/rcm.1989
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发表时间：
2005-01-01
影响因子：
2
通讯作者：
Guo, DA
中科院分区：
文献类型：
--
作者：
Ye, M;Guo, DA
采用高效液相色谱-大气压化学电离串联质谱法（APCI-MS/MS）对中药蟾酥中的蟾蜍二烯内酯类成分进行定性分析。蟾毒二烯内酯是蟾毒素的主要活性成分，在传统中医药中用于治疗心力衰竭和癌症。研究了蟾蜍二烯内酯的APCI-MS裂解行为。对于蟾蜍二烯内酯，只有羟基取代基，碎片的特点是通过连续消除H2O和CO分子，和MS/MS产物离子的配置文件与羟基的数量。如果存在：C-16乙酰氧基，则[M+H]（+）离子的断裂由60 Da（HOAc）的初始损失触发。具有19-甲酰基的蟾蜍二烯内酯的CO消除是显著的，并且19-羟基可以通过30 Da（HCHO）的损失来表征。将这些裂解规律应用于蟾酥甲醇提取物中蟾蜍二烯内酯的鉴定，该提取物在C-18柱上采用梯度洗脱进行分离。共鉴定出35个蟾蜍二烯内酯类化合物，其中包括4个新化合物。该方法简便、快速，可用于蟾酥药材及其制剂的质量控制。版权所有（c）2005年约翰威利父子有限公司。
The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H2O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a: C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C-18 column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations. Copyright (c) 2005 John Wiley & Sons, Ltd.