Comprehensive 2-dimensional gas chromatography fast quadrupole mass spectrometry (GC × GC-qMS) for urinary steroid profiling: mass spectral characteristics with chemical ionization.
Comprehensive 2-dimensional gas chromatography fast quadrupole mass spectrometry (GC × GC-qMS) for urinary steroid profiling: mass spectral characteristics with chemical ionization.
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DOI：
10.1002/dta.380
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发表时间：
2011-11
影响因子：
2.9
通讯作者：
Brenna, J. Thomas
中科院分区：
文献类型：
--
作者：
Zhang, Ying;Tobias, Herbert J.;Auchus, Richard J.;Brenna, J. Thomas
关键词：
与传统的GC-MS相比，结合飞行时间质谱（TOF-MS）或快速扫描四极杆质谱（qMS）的综合二维气相色谱（GC×GC）大大增加了峰容量和分离空间。然而，商业GC×GC-TOFMS系统不配备化学电离（CI），也不提供主要分子离子或使单离子监测达到最大灵敏度。以CH_4和NH_3为反应气体，采用EI和正CI（PCI）技术，研究了GC×GC-qMS的质量扫描模式。与EI相比，PCI-NH3产生了更丰富的分子离子和更高质量的结构特异性离子。色谱在两个维度上进行了优化，与12个内源性和3个标准乙酰化类固醇（SM 15-AC）的混合物有关的兴奋剂控制。根据其两个保留时间，EI和PCI-NH3质谱，在正常尿液中鉴定了11种内源性目标类固醇乙酸酯;其中9种内源性目标类固醇乙酸酯在先天性肾上腺增生（CAH）患者中鉴定。通过GC×GC-qMS色谱图可以很容易地区分正常人和CAH患者尿类固醇谱之间的差异。在这里，我们专注于目标内源性类固醇的各种质谱的比较和解释。PCI-NH3质谱是最有用的明确的分子量测定和建立1个或多个乙酸酯基团的损失的-OH的数量。我们得出结论，PCI-NH3与GC×GC-qMS提供了改进的峰容量和具有结构特异性的准分子离子。
Comprehensive two dimensional GC (GC×GC), coupled to either a time of flight MS (TOF-MS) or a fast scanning quadrupole MS (qMS) has greatly increased the peak capacity and separation space compared to conventional GC-MS. However, commercial GC×GC-TOFMS systems are not equipped with chemical ionization (CI) and do not provide dominant molecular ions or enable single ion monitoring for maximal sensitivity. A GC×GC-qMS in mass scanning mode was investigated with EI and positive CI (PCI), using CH4 and NH3 as reagent gases. Compared to EI, PCI-NH3 produced more abundant molecular ions and high mass structure specific ions for steroid acetates. Chromatography in two dimensions was optimized with a mixture of 12 endogenous and 3 standard acetylated steroids (SM15-AC) relevant to doping control. Eleven endogenous target steroid acetates were identified in normal urine based on their two retention times, and EI and PCI-NH3 mass spectra; nine of these endogenous target steroid acetates were identified in congenital adrenal hyperplasia (CAH) patients. The difference between the urinary steroids profiles of normal individuals and from a CAH patient can easily be visually distinguished by their GC×GC-qMS chromatograms. We focus here on the comparison and interpretation of the various mass spectra of the targeted endogenous steroids. PCI-NH3 mass spectra were most useful for unambiguous molecular weight determination and for establishing the number of -OH by the losses of 1 or more acetate groups. We conclude that PCI-NH3 with GC×GC-qMS provides improved peak capacity and pseudomolecular ions with structural specificity.
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影响因子：
3.6
作者：
HOMOKI, J;SOLYOM, J;TELLER, WM
通讯作者：
TELLER, WM
影响因子：
2.7
作者：
Dehennin, L;Ferry, M;Lafarge, JP
通讯作者：
Lafarge, JP
影响因子：
2
作者：
Piper, Thomas;Mareck, Ute;Schaenzer, Wilhelm
通讯作者：
Schaenzer, Wilhelm
影响因子：
9.3
作者：
Robinson, Neil;Saugy, Martial;Sottas, Pierre-Edouard
通讯作者：
Sottas, Pierre-Edouard
影响因子：
2.7
作者：
Christakoudi, Sofia;Cowan, David A.;Taylor, Norman F.
通讯作者：
Taylor, Norman F.