Pyrrolizidine alkaloid profile in a traditional Chinese herbal medicine Chuan Zi Wan (Ligulariae Radix et Rhizoma) by liquid chromatography/electrospray ionization ion trap mass spectrometry
Pyrrolizidine alkaloid profile in a traditional Chinese herbal medicine Chuan Zi Wan (Ligulariae Radix et Rhizoma) by liquid chromatography/electrospray ionization ion trap mass spectrometry
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DOI：
10.1039/c2ay25300c
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发表时间：
2012-08
影响因子：
3.1
通讯作者：
Jun Tang;Min Cheng;M. Hattori
中科院分区：
文献类型：
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作者：
Jun Tang;Min Cheng;M. Hattori
川子丸是一种来源于橐吾属植物的传统中草药，用于民间止咳化痰。最近在大鼠中证实了其毒性，其中检测到肝毒性吡咯里西啶生物碱（PA），但未充分研究。为了进一步评估其安全性，使用高效液相色谱法（HPLC）结合电喷雾电离离子阱质谱法研究了CZW的整个PA特征。根据诊断离子、质量裂解模式、色谱行为和生物合成考虑，检测和/或表征了26种有毒PA（25种otonecine型和1种retronecine型PA）和1种Platynecine型无毒PA。除了clivorine，ligularine，hodgsonine和ligularizine，所有其他的PAs都是第一次被描述，而且，大多数otonecine型PAs被发现含有乙酰基，一个重要的子结构密切相关的，他们在体内的毒性作用。在提取物中明确鉴定出Clivorine为主要PA，通过HPLC/UV测定法测定其含量为3.94 mg g−1干燥提取物。有毒多胺的总含量估计约为7.92 mg g-1干提取物。这些结果表明，这种草药产品可能对人类的健康构成潜在威胁。
Chuan Zi Wan (CZW) is a traditional Chinese herbal medicine derived from Ligularia species and used as an antitussive and expectorant folk remedy. Its toxicity was recently demonstrated in rats, for which the hepatotoxic pyrrolizidine alkaloids (PAs) were detected but not fully examined. In order to further assess its safety, the entire PA profile of CZW was investigated using high-performance liquid chromatography (HPLC) coupled to electrospray ionization ion trap mass spectrometry. Twenty-six toxic PAs (25 otonecine-type and one retronecine-type PAs) and one non-toxic PA of platynecine-type were detected and/or characterized based on diagnostic ions, mass fragmentation patterns, chromatographic behaviors and biosynthetic consideration. Except clivorine, ligularine, hodgsonine and ligularizine, all other PAs were described for the first time; moreover, most otonecine-type PAs were found to contain the acetyl group, an important substructure closely linked to their toxic effects in vivo. Clivorine was unequivocally identified as a major PA in the extract, with a content of 3.94 mg g−1 dried extractant determined by a HPLC/UV assay. The total content of the toxic PAs was estimated to be about 7.92 mg g−1 dried extract. These results indicated that this herbal product may have a potential health threat to humans in its Chinese medical practice.