基于HPLC-Q-TOF/MS的白屈菜生物碱化学组成快速辨识研究

Rapid identification of the alkaloids of Chelidonium majus L.by HPLC-Q-TOF/MS

利用HPLC-Q-TOF/MS技术快速准确、系统全面的定性鉴定白屈菜中生物碱。采用XCharge C18色谱柱(5μm,4.6 mm×250 mm);以乙腈-0.1%甲酸为流动相梯度洗脱;流速0.7 mL·min^-1。根据一级质谱分子离子和二级质谱碎片离子,归纳白屈菜生物碱的质谱裂解规律,结合相关文献,对白屈菜中生物碱进行系统的结构鉴定。为验证结果的准确性,纯化制备其中3个生物碱并通过核磁技术鉴定化学结构。从白屈菜中鉴定出21个生物碱,包含1个阿朴菲类生物碱、3个普罗托品类生物碱、11个苯并菲啶类生物碱以及6个原小檗碱类生物碱。其中N-甲基金罂粟碱(8)为白屈菜中首次报道,二氢黄连碱(11)和去甲基白屈菜碱(12)为白屈菜中首次用该技术鉴定。制备化合物的化学结构鉴定结果与质谱定性结果一致。经验证,该方法快速准确,可为白屈菜化学成分的分析鉴定和提取分离提供依据。

A method was developed for the rapid and systematic identification of alkaloids in Chelidonium majus L.by HPLC-Q-TOF/MS.The separation was performed on an XCharge C18 column(5μm,4.6 mm×250 mm)with acetonitrile-0.1%formic acid in water by gradient elution.The flow rate was 0.7 mL·min^-1.The primary mass spectrometer molecular ion and the secondary mass spectrometry fragment ion were determined.The mass spectro‐metric cleavage of alkaloids was determined and the structures were used to systematically identify the alkaloids in Chelidonium majus L.To verify the accuracy of the qualitative results,three alkaloids were purified and identified by NMR.Twenty-one alkaloids were identified from Chelidonium majus L.,including one aporphine-type alkaloid three protopine-type alkaloids,11 benzophenanthrine-type alkaloids and six protoberberine-type alkaloids.(S)-N-methylstylopine(8)was first reported in Chelidonium majus L.and dihydrocoptisine(11)and norchelidonine(12)were identified for the first time in Chelidonium majus L.using this technique.The chemical structures of the purified compounds are consistent with the qualitative results of the mass spectrometric analysis.The method is fast and accurate and can provide a basis for the identification and extraction of the chemical constituents of Chelidonium majus L.