5种雌激素类化合物的电喷雾四级杆飞行时间质谱裂解规律研究  

Fragmentation pathways of five estrogens using electrospray ionization quadrupole time-of-flight mass spectrometry

作　　者：张婷岚[1,2] 史美云[2] 邸欣[1] 顾景凯[2] 

机构地区：[1]沈阳药科大学药学院,辽宁沈阳110016 [2]吉林大学药物代谢研究中心,吉林长春130012

出　　处：《药学学报》2014年第4期507-512,共6页Acta Pharmaceutica Sinica

基　　金：国家自然科学基金资助项目(81102383);"十二五"重大新药创制专项课题资助项目(2012ZX09303-015)

摘　　要：利用电喷雾-四级杆-飞行时间质谱(ESI-Q-TOF/MS)的高分辨率及高质量准确度特点,在电喷雾负离子模式下,对5种雌激素类化合物的质谱裂解规律进行研究并用其稳定同位素内标进行确证。通过ESI-MS产生的[M-H]-获得相应化合物的相对分子质量信息。结果表明,结构类似的5种雌激素类化合物具有相似的电喷雾质谱行为,在碰撞诱导解离(collisional-induced dissociation,CID)过程中,首先失去C-17位上的氧原子,然后连续断裂D环和C环,开环后重新排列,进而形成稳定的共轭结构,最终得到高丰度的特征碎片离子m/z 183(m/z 181),m/z 169,m/z 145(m/z 143),这些特征有助于甾体激素类化合物的结构解析。The fragmentation pathways of five estrogens （estradiol, estrone, equilin sulfate, 17α-dihydroequilin sulfate and equilenin sulfate） have been studied with high resolution and high mass accuracy using electrospray ionization quadrupole time-of-flight mass spectrometry （ESI-Q-TOF/MS） in the negative ion mode. Molecular weights were obtained from [M-H]- ions in the product ion spectra. The results indicate that the five structurally similar estrogens have similar fragmentation pathways. Using their stable isotope forms as internal reference compounds, the accurate mass and composition of the fragment ions were determined. During collision- induced dissociation （CID）, cleavage is initiated by loss of oxygen atoms from carbon-17, after which D and C rings cleave sequentially and rearrange to finally form stable conjugate structures with highly abundant characteristic fragment ions at m/z 183 （accompanied by m/z 181）, m/z 169 and m/z 145 （accompanied by m/z 143）. Understanding these characteristic fragmentation pathways of estrogens will be helpful in identifying the structures of steroid hormones in general.

关 键 词：雌激素 电喷雾-四级杆-飞行时间质谱 裂解规律 

分 类 号：R917[医药卫生—药物分析学]