title: Matching structures to mass spectra using fragmentation patterns: are the results as good as they look?
abstract: Three programs were assessed for their ability to predict mass spectral fragmentation patterns for all constitutional isomers of an experimental low-resolution electron impact mass spectrum (EI-MS), given the molecular formula, and use this information to identify the "correct structure". MOLGEN 3.5 was used to generate the structures, while all spectra were extracted from the NIST database. The commercial programs Mass Frontier and ACD MS Manager, as well as MOLGEN-MSF (developed by the University of Bayreuth) were used to generate mass spectral fragments. MOLGEN-MSF was used to generate "match values" to compare the different programs and their ability to identify the "correct structure". Although high match values could be achieved with certain settings, the ranking of the correct structure relative to other constitutional isomers was not significantly better than the results published previously and in some cases significantly worse. Furthermore, all programs showed bias toward specific structures, which changed significantly with minor changes to the program settings. Thus, advances in mass spectral fragment prediction have not necessarily improved computer aided structure elucidation (CASE) from EI-MS and indicate that caution must be used when confirming the identity of a compound only based on the match between its predicted fragments and the mass spectrum.
authors.affiliation: Helmholtz Centre for Environmental Research-UFZ, Department of Effect-Directed Analysis, Permoserstrasse 15, D-04318 Leipzig, Germany. emma.schymanski@ufz.de
authors.forename: Emma L
authors.initials: EL
authors.lastname: Schymanski
authors.forename: Markus
authors.initials: M
authors.lastname: Meringer
authors.forename: Werner
authors.initials: W
authors.lastname: Brack