Abstract
Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under stan-dard 70eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam-steering voltage of the ion source, the relative abundances of molecular ions at 70eV EI were increased up to ten-fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2-fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high-mass tuning. Thirty-three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([MRH]+, [M-CH3]+ for CI and [M]+., [M-CH3]+. for EI). On average, CI yielded 8-fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8±1.6mm/z units and isotope ratio errors of 2.3±2.0% (A+1/A ratio) and 1.7±1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top-3 hits in 80% of the cases.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 1172-1180 |
| Number of pages | 9 |
| Journal | Rapid Communications in Mass Spectrometry |
| Volume | 24 |
| Issue number | 8 |
| DOIs | |
| State | Published - Apr 30 2010 |
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ASJC Scopus subject areas
- Spectroscopy
- Analytical Chemistry
- Organic Chemistry
Cite this
Determination of elemental compositions by gas chromatography/time-of-flight mass spectrometry using chemical and electron ionization. / Abate, Salvatore; Ahn, Yun Gyong; Kind, Tobias; Cataldi, Tommaso R I; Fiehn, Oliver.
In: Rapid Communications in Mass Spectrometry, Vol. 24, No. 8, 30.04.2010, p. 1172-1180.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Determination of elemental compositions by gas chromatography/time-of-flight mass spectrometry using chemical and electron ionization
AU - Abate, Salvatore
AU - Ahn, Yun Gyong
AU - Kind, Tobias
AU - Cataldi, Tommaso R I
AU - Fiehn, Oliver
PY - 2010/4/30
Y1 - 2010/4/30
N2 - Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under stan-dard 70eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam-steering voltage of the ion source, the relative abundances of molecular ions at 70eV EI were increased up to ten-fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2-fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high-mass tuning. Thirty-three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([MRH]+, [M-CH3]+ for CI and [M]+., [M-CH3]+. for EI). On average, CI yielded 8-fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8±1.6mm/z units and isotope ratio errors of 2.3±2.0% (A+1/A ratio) and 1.7±1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top-3 hits in 80% of the cases.
AB - Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under stan-dard 70eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam-steering voltage of the ion source, the relative abundances of molecular ions at 70eV EI were increased up to ten-fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2-fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high-mass tuning. Thirty-three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([MRH]+, [M-CH3]+ for CI and [M]+., [M-CH3]+. for EI). On average, CI yielded 8-fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8±1.6mm/z units and isotope ratio errors of 2.3±2.0% (A+1/A ratio) and 1.7±1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top-3 hits in 80% of the cases.
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U2 - 10.1002/rcm.4482
DO - 10.1002/rcm.4482
M3 - Article
VL - 24
SP - 1172
EP - 1180
JO - Rapid Communications in Mass Spectrometry
JF - Rapid Communications in Mass Spectrometry
SN - 0951-4198
IS - 8
ER -