Analysis of derivatised steroids by matrix-assisted laser desorption/ionisation and post-source decay mass spectrometry
Analysis of derivatised steroids by matrix-assisted laser desorption/ionisation and post-source decay mass spectrometry
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DOI：
10.1016/j.steroids.2005.08.002
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发表时间：
2006-01-01
期刊：
影响因子：
2.7
通讯作者：
Griffiths, WJ
中科院分区：
文献类型：
--
作者：
Khan, MA;Wang, YQ;Griffiths, WJ
中性类固醇很难使用解吸电离方法结合质谱法（MS）进行分析。然而，具有不受阻碍的酮基的类固醇可以容易地用吉拉德P（GP）试剂衍生化以得到GP腙。类固醇GP腙含有季氮原子，并且在基质辅助激光解吸/电离（MALDI）过程中容易解吸，从而使灵敏度提高两个数量级。不含酮基但具有3 β-羟基-δ（5）官能团的类固醇可容易地转化为3-OXO-δ（4）类固醇，随后衍生为GP腙用于MALDI分析。除了在MALDI时产生强[M]（+）离子外，类固醇GP腙还提供信息性的源后衰减（PSD）光谱。通过使用由MALDI-MS测量的准确质量的类固醇离子，结合其PSD谱中编码的结构信息，可以容易地确定类固醇结构。(c)2005年爱思唯尔公司All rights reserved.
Neutral steroids are difficult to analyse using desorption ionisation methods coupled with mass spectrometry (MS). However, steroids with an unhindered ketone group can readily be derivatised with the Girard P (GP) reagent to give GP hydrazones. Steroid GP hydrazones contain a quaternary nitrogen atom and are readily desorbed in the matrix-assisted laser desorption/ionisation (MALDI) process, giving an improvement in sensitivity of two orders of magnitude. Steroids without a ketone group, but with a 3 beta-hydroxy-Delta(5) function, can be readily converted to 3-OXO-Delta(4) steroids and subsequently derivatised to GP hydrazones for MALDI analysis. In addition to giving strong [M](+) ions upon MALDI, steroid GP hydrazones give informative post-source decay (PSD) spectra. By using the accurate mass of the precursor-ion measured by MALDI-MS, in combination with the structural information encoded in its PSD spectrum, steroid structures can readily be determined. (c) 2005 Elsevier Inc. All rights reserved.