Liquid chromatography/electron capture atmospheric pressure chemical ionization/mass spectrometry: Analysis of pentafluorobenzyl derivatives of biomolecules and drugs in the attomole range
Liquid chromatography/electron capture atmospheric pressure chemical ionization/mass spectrometry: Analysis of pentafluorobenzyl derivatives of biomolecules and drugs in the attomole range
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DOI：
10.1021/ac000374a
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发表时间：
2000-07-15
影响因子：
7.4
通讯作者：
Blair, IA
中科院分区：
文献类型：
--
作者：
Singh, G;Gutierrez, A;Blair, IA
用于在常规大气压化学电离条件下产生正离子和负离子的电晕放电也提供了气相电子源。这被认为是通过电子从氮鞘气中的位移而发生的。因此，合适的分析物可以以与气相色谱法/电子捕获负化学电离/质谱法所观察到的方式类似的方式在气相中经历电子捕获。这种技术，它已被命名为电子捕获大气压化学电离/质谱，提供了2个数量级的灵敏度增加时，与传统的大气压化学电离方法相比，这是一个简单的程序，标记许多生物分子和药物与电子捕获基团，如五氟苄基部分分析前。五氟苄基衍生物先前已被用作电子捕获衍生物，因为它们在气相中经历解离电子捕获以通过五氟苄基自由基的损失产生负离子。在电子俘获大气压化学电离条件下，发现发生类似的过程。通过监测所形成的负离子，可以获得对代表性类固醇、类固醇代谢物、前列腺素、血栓烷、氨基酸和DNA加合物的五氟苄基衍生物的阿托摩尔灵敏度。
The corona discharge used to generate positive and negative ions under conventional atmospheric pressure chemical ionization conditions also provides a source of gas-phase electrons. This is thought to occur by displacement of electrons from the nitrogen sheath gas. Therefore, suitable analytes can undergo electron capture in the gas phase in a manner similar to that observed for gas chromatography/electron capture negative chemical ionization/mass spectrometry. This technique, which has been named electron capture atmospheric pressure chemical ionization/mass spectrometry, provided an increase in sensitivity of 2 orders of magnitude when compared with conventional atmospheric pressure chemical ionization methodology, It is a simple procedure to tag many biomolecules and drugs with an electron-capturing group such as the pentafluorobenzyl moiety before analysis. Pentafluorobenzyl derivatives have previously been used as electron capturing derivatives because they undergo dissociative electron capture in the gas phase to generate negative ions through the loss of a pentafluorobenzyl radical. A similar process was found to occur under electron capture atmospheric pressure chemical ionization conditions. By monitoring the negative ions that were formed, it was possible to obtain attomole sensitivity for pentafluorobenzyl derivatives of a representative steroid, steroid metabolite, prostaglandin, thromboxane, amino acid, and DNA-adduct.