Analysis of aristolochic acids, aristololactams and their analogues using liquid chromatography tandem mass spectrometry

详细信息    查看全文

• 作者：Jie YU^a ; ^c ; Chao-Mei MA^b ; ^d ; Xuan WANG^a ; Ming-Ying SHANG^a ; Masao Hattori^b ; ^{mhattori@po4.canet.ne.jp" class="auth_mail" title="E-mail the corresponding author} ; Feng XU^a ; Yu JING^a ; Shi-Wen DONG^a ; Yu-Qiong XU^a ; Cui-Ying ZHANG^a ; Shao-Qing CAI^a ; ^{sqcai@hsc.pku.edu.cn" class="auth_mail" title="E-mail the corresponding author}
• 关键词：LC/MSn ; Aristolochic acids ; Aristololactams ; Fragmentation rules ; Aristolochia genus
• 刊名：Chinese Journal of Natural Medicines
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：14
• 期：8
• 页码：626-640
• 全文大小：1848 K

文摘

More than 80 aristolochic acids (AAs) and aristololactams (ALs) have been found in plants of the Aristolochiaceae family, but relatively few have been fully studied. The present study aimed at developing and validating a liquid chromatography tandem mass spectrometry (LC/MSⁿ) for the analysis of these compounds. We characterized the fragmentation behaviors of 31 AAs, ALs, and their analogues via high performance liquid chromatography coupled with electrospray ionization mass spectrometry. We summarized their fragmentation rules and used these rules to identify the constituents contained in Aristolochia contorta, Ar. debilis, Ar. manshurensis, Ar. fangchi, Ar. cinnabarina, and Ar. mollissima. The AAs and ALs showed very different MS behaviors. In MS¹ of AAs, the characteristic pseudomolecular ions were [M + NH₄]⁺, [M + H]⁺, and [M + H − H₂O]⁺. However, only [M + H]⁺ was found in the MS¹ of ALs, which was simpler than that of AAs. Distinct MSⁿfragmentation patterns were found for AAs and ALs, showing the same skeleton among the different substituent groups. The distribution of the 31 constituents in the 6 species of Aristolochia genus was reported for the first time. 25 Analogues of AAs and ALs were detected in this genus. A hierarchical schemes and a calculating formula of the molecular formula of these nitrophenanthrene carboxylic acids and their lactams were proposed. In conclusion, this method could be applied to identification of similar unknown constituents in other plants.