Applying In-Silico Retention Index and Mass Spectra Matching for Identification of Unknown Metabolites in Accurate Mass GC-TOF Mass Spectrometry

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• 作者：Sangeeta Kumari ; Doug Stevens ; Tobias Kind ; Carsten Denkert ; Oliver Fiehn
• 刊名：Analytical Chemistry
• 出版年：2011
• 出版时间：August 1, 2011
• 年：2011
• 卷：83
• 期：15
• 页码：5895-5902
• 全文大小：897K
• 年卷期：v.83,no.15(August 1, 2011)
• ISSN：1520-6882

文摘

One of the major obstacles in metabolomics is the identification of unknown metabolites. We tested constraints for reidentifying the correct structures of 29 known metabolite peaks from GCT premier accurate mass chemical ionization GC-TOF mass spectrometry data without any use of mass spectral libraries. Correct elemental formulas were retrieved within the top-3 hits for most molecular ion adducts using the 鈥淪even Golden Rules鈥?algorithm. An average of 514 potential structures per formula was downloaded from the PubChem chemical database and in-silico-derivatized using the ChemAxon software package. After chemical curation, Kovats retention indices (RI) were predicted for up to 747 potential structures per formula using the NIST MS group contribution algorithm and corrected for contribution of trimethylsilyl groups using the Fiehnlib RI library. When matching the range of predicted RI values against the experimentally determined peak retention, all but three incorrect formulas were excluded. For all remaining isomeric structures, accurate mass electron ionization spectra were predicted using the MassFrontier software and scored against experimental spectra. Using a mass error window of 10 ppm for fragment ions, 89% of all isomeric structures were removed and the correct structure was reported in 73% within the top-5 hits of the cases.