Development of algorithms for automated elucidation of spectral feature/substructure relationships in tandem mass spectrometry

A pattern-recognition/artificial-intelligence program, referred to as MAPS (method for analyzing patterns in spectra), is described for the identification of relationships that exist between the presence of substructures in molecules and the characteristic features they produce in mass spectrometry (MS) and MS/MS data. The MAPS algorithm discovers these relationships by intelligent analysis of a data base of MS and MS/MS spectra. The relationships found are expressed as rules, which may then be used to identify characterized substructures in “unknowns”. No prior knowledge of fragmentation pathways or rearrangements is assumed in the rule-generation process. While MAPS currently uses MS and MS/MS data, the approach (and much of the software) is equally suited to multiple-stage mass spectrometric data.