FiehnLib: Mass Spectral and Retention Index Libraries for Metabolomics Based on Quadrupole and Time-of-Flight Gas Chromatography/Mass Spectrometry

At least two independent parameters are necessary for compound identification in metabolomics. We have compiled 2 212 electron impact mass spectra and retention indices for quadrupole and time-of-flight gas chromatography/mass spectrometry (GC/MS) for over 1 000 primary metabolites below 550 Da, covering lipids, amino acids, fatty acids, amines, alcohols, sugars, amino-sugars, sugar alcohols, sugar acids, organic phosphates, hydroxyl acids, aromatics, purines, and sterols as methoximated and trimethylsilylated mass spectra under electron impact ionization. Compounds were selected from different metabolic pathway databases. The structural diversity of the libraries was found to be highly overlapping with metabolites represented in the BioMeta/KEGG pathway database using chemical fingerprints and calculations using Instant-JChem. In total, the FiehnLib libraries comprised 68% more compounds and twice as many spectra with higher spectral diversity than the public Golm Metabolite Database. A range of unique compounds are present in the FiehnLib libraries that are not comprised in the 4 345 trimethylsilylated spectra of the commercial NIST05 mass spectral database. The libraries can be used in conjunction with GC/MS software but also support compound identification in the public BinBase metabolomic database that currently comprises 5 598 unique mass spectra generated from 19 032 samples covering 279 studies of 47 species (plants, animals, and microorganisms).