Article (Scientific journals)
Fragment Formula Calculator (FFC): Determination of chemical formulas for fragment ions in mass spectrometric data
Wegner, André; Weindl, Daniel; Jäger, Christian et al.
2014In Analytical Chemistry, 86 (4), p. 2221–2228
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Abstract :
[en] The accurate determination of mass isotopomer distributions (MID) is of great significance for stable isotope-labeling experiments. Most commonly, MIDs are derived from gas chromatography/electron ionization mass spectrometry (GC/EI-MS) measurements. The analysis of fragment ions formed during EI, which contain only specific parts of the original molecule can provide valuable information on the positional distribution of the label. The chemical formula of a fragment ion is usually applied to derive the correction matrix for accurate MID calculation. Hence, the correct assignment of chemical formulas to fragment ions is of crucial importance for correct MIDs. Moreover, the positional distribution of stable isotopes within a fragment ion is of high interest for stable isotope-assisted metabolomics techniques. For example, 13C-metabolic flux analyses (13C-MFA) are dependent on the exact knowledge of the number and position of retained carbon atoms of the unfragmented molecule. Fragment ions containing different carbon atoms are of special interest, since they can carry different flux information. However, the process of mass spectral fragmentation is complex, and identifying the substructures and chemical formulas for these fragment ions is nontrivial. For that reason, we developed an algorithm, based on a systematic bond cleavage, to determine chemical formulas and retained atoms for EI derived fragment ions. Here, we present the fragment formula calculator (FFC) algorithm that can calculate chemical formulas for fragment ions where the chemical bonding (e.g., Lewis structures) of the intact molecule is known. The proposed algorithm is able to cope with general molecular rearrangement reactions occurring during EI in GC/MS measurements. The FFC algorithm is able to integrate stable isotope labeling experiments into the analysis and can automatically exclude candidate formulas that do not fit the observed labeling patterns.1 We applied the FFC algorithm to create a fragment ion repository that contains the chemical formulas and retained carbon atoms of a wide range of trimethylsilyl and tert-butyldimethylsilyl derivatized compounds. In total, we report the chemical formulas and backbone carbon compositions for 160 fragment ions of 43 alkylsilyl-derivatives of primary metabolites. Finally, we implemented the FFC algorithm in an easy-to-use graphical user interface and made it publicly available at http://www.ffc.lu.
Research center :
Luxembourg Centre for Systems Biomedicine (LCSB): Metabolomics (Hiller Group)
Disciplines :
Life sciences: Multidisciplinary, general & others
Author, co-author :
Wegner, André ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
Weindl, Daniel ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
Jäger, Christian  ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
Sapcariu, Sean ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
Dong, Xiangyi  ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
Stephanopoulos, Greg
Hiller, Karsten ;  University of Luxembourg > Luxembourg Centre for Systems Biomedicine (LCSB)
External co-authors :
yes
Language :
English
Title :
Fragment Formula Calculator (FFC): Determination of chemical formulas for fragment ions in mass spectrometric data
Publication date :
January 2014
Journal title :
Analytical Chemistry
ISSN :
1520-6882
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
86
Issue :
4
Pages :
2221–2228
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
FNR - Fonds National de la Recherche [LU]
Available on ORBilu :
since 07 April 2014

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