亮菌甲素琥珀酸单酯的正离子电喷雾离子阱质谱裂解途径的研究

Study of fragmentation pathways of armillarisin amber acid ester by electron spray ionization-ion trap mass spectrometry in positive mode

目的采用电喷雾离子阱质谱(ESI-MS)技术对亮菌甲素琥珀酸单酯(ArAAE)的结构和裂解途径进行研究,归属其主要特征碎片离子,分析和讨论该化合物的结构和质谱特征。方法 ArAAE采用注射泵直接进样,ESI-MS检测,流速为300μL·h-1,分别获得ESI-MS1-3各个主要碎片离子。结果 ESI-MS获得了m/z 335[M1+H]+,采用ESI-MS2获得了m/z 217碎片离子,而采用ESI-MS3主要获得了m/z 189、175和161等碎片离子。ESI-MS和ESI-MS2主要有1种裂解途径,而ESI-MS3主要有3种裂解途径,主要是酯键的裂解,并对m/z 189、175和161特征碎片离子进行ESI-MS4质谱研究,推断出ArAAE有3种主要的裂解途径。结论采用ESI-MS技术对进一步研究ArAAE的体内代谢过程与结构修饰提供了实验依据。

Objective The structure and fragmentation pathway of armillarisin amber acid ester（ArAAE） were elucidated by electron spray ionization-ion trap mass spectrometry（ESI-MS）,and the structure and mass characteristics of the compound were analyzed and discussed. Methods The ArAAE standard solution was directly infused into ESI-MS by syringe pump and the flow rate was 300 μL·h-1.The main fragment ions were obtained by ESI-MS1-3. Results Quasi-molecular ion peak m/z 335＋ was detected by ESI-MS,the fragment ion of m/z 217 was detected by ESI-MS2 and the main fragment ions of m/z 189,175 and 161 were found by ESI-MS3.There was one main fragment pathway for m/z 335＋ and ESI-MS2 and three were there main fragment pathway for ESI-MS3 and the fragment broken in ester bond.The full scan ESI-MS4 spectra of fragment m/z 189,175 and 161 were obtained by ion trap mass spectrometry.There were three possible main fragment ions cleavage pathway. Conclusion It can provide the experimental data for studying pharmacokinetics in vivo and modifying structure for ArAAE.