title: Highly sensitive and selective analysis of urinary steroids by comprehensive two-dimensional gas chromatography combined with positive chemical ionization quadrupole mass spectrometry.
abstract: Comprehensive two dimensional gas chromatography (GC × GC) provides greater separation space than conventional GC. Because of fast peak elution, a time of flight mass spectrometer (TOFMS) is the usual structure-specific detector of choice. The quantitative capabilities of a novel GC × GC fast quadrupole MS were investigated with electron ionization (EI), and CH(4) or NH(3) positive chemical ionization (PCI) for analysis of endogenous urinary steroids targeted in anti-doping tests. Average precisions for steroid quantitative analysis from replicate urine extractions were 6% (RSD) for EI and 8% for PCI-NH(3). The average limits of detection (LODs) calculated by quantification ions for 12 target steroids spiked into steroid-free urine matrix (SFUM) were 2.6 ng mL(-1) for EI, 1.3 ng mL(-1) for PCI-CH(4), and 0.3 ng mL(-1) for PCI-NH(3), all in mass scanning mode. The measured limits of quantification (LOQs) with full mass scan GC × GC-qMS were comparable with the LOQ values measured by one-dimensional GC-MS in selected ion monitoring (SIM) mode. PCI-NH(3) yields fewer fragments and greater (pseudo)molecular ion abundances than EI or PCI-CH(4). These data show that a benchtop GC × GC-qMS system has the sensitivity, specificity, and resolution to analyze urinary steroids at normal urine concentrations, and that PCI-NH(3), not currently available on most GC × GC-TOFMS instruments, is of particular value for generation of structure-specific ions.
authors.affiliation: Cornell University, Division of Nutritional Sciences, Ithaca, NY 14853, USA. yz92@cornell.edu
authors.forename: Ying
authors.initials: Y
authors.lastname: Zhang
authors.forename: Herbert J
authors.initials: HJ
authors.lastname: Tobias
authors.forename: J Thomas
authors.initials: JT
authors.lastname: Brenna
mesh_terms: D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006801:Humans; D057230:Limit of Detection; D015203:Reproducibility of Results; D013256:Steroids / Q000652:urine*
chemical_list: D013256:Steroids