Mechanism of formation of the major estradiol product ions following collisional activation of the molecular anion in a tandem quadrupole mass spectrometer.
Mechanism of formation of the major estradiol product ions following collisional activation of the molecular anion in a tandem quadrupole mass spectrometer.
复制标题
串联四极杆质谱仪中分子阴离子碰撞激活后主要雌二醇产物离子的形成机制。
DOI：
10.1007/s13361-013-0705-y
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发表时间：
2013
影响因子：
3.2
通讯作者：
Murphy,RobertC
中科院分区：
文献类型：
--
作者：
Wooding,KerryM;Barkley,RobertM;Hankin,JosephA;Johnson,ChristopherA;Bradford,AndrewP;Santoro,Nanette;Murphy,RobertC
质谱产物离子结构的重要性在定量分析（通常使用多反应监测 (MRM)）和新代谢物的发现中得到强调。雌二醇是一种重要的性类固醇，使用串联质谱法对其进行定量和代谢物鉴定已广泛应用于众多临床研究中。雌二醇 (E2) 的负电喷雾电离串联质谱可产生多种产物离子，包括丰富的 m/z183 和 169。尽管 m/z183 是许多定量测定中使用的最丰富的产物离子之一，但 m/z183 的结构尚未经过严格检查。我们提出了 /z183 的结构形式和形成机制，其形成与 E2 和几种稳定同位素（[D4]-E2、[13C6]-E2 和 [D1]-E2）的碰撞诱导解离 (CID) 一致。 E2 的另外一个产物离子，即 m/z169，也已得到检验。 MS3实验表明m/z183和m/z169仅源自E2 [M – H]–m/z271。这些离子 m/z183 和 m/z169 也存在于其他主要雌激素雌酮 (E1) 和雌三醇 (E3) 的碰撞诱导分解质谱中，表明这两种产物离子可用于阐明新代谢物的雌激素来源。我们提出了两种碎片方案来解释 CID 数据，并提出了与几种同位素变体和高分辨率质谱测量一致的 m/z183 和 m/z169 结构。
The importance of the mass spectral product ion structure is highlighted in quantitative assays, which typically use multiple reaction monitoring (MRM), and in the discovery of novel metabolites. Estradiol is an important sex steroid whose quantitation and metabolite identification using tandem mass spectrometry has been widely employed in numerous clinical studies. Negative electrospray ionization tandem mass spectrometry of estradiol (E2) results in several product ions, including the abundantm/z183 and 169. Althoughm/z183 is one of the most abundant product ions used in many quantitative assays, the structure ofm/z183 has not been rigorously examined. We suggest a structure form/z183 and a mechanism of formation consistent with collision induced dissociation (CID) of E2 and several stable isotopes ([D4]-E2, [13C6]-E2, and [D1]-E2). An additional product ion from E2, namelym/z169, has also been examined. MS3experiments indicated that bothm/z183 andm/z169 originate from only E2 [M – H]–m/z271. These ions,m/z183 andm/z169, were also present in the collision induced decomposition mass spectra of other prominent estrogens, estrone (E1) and estriol (E3), indicating that these two product ions could be used to elucidate the estrogenic origin of novel metabolites. We propose two fragmentation schemes to explain the CID data and suggest a structure ofm/z183 andm/z169 consistent with several isotopic variants and high resolution mass spectrometric measurements.