Generation of substructure identification rules using feature-combinations from tandem mass spectra

• Published in: Journal of the American Society for Mass Spectrometry Vol. 3; no. 2; pp. 159 - 168
• Main Authors: Hart, K.J., Palmer, P.T., Diedrich, D.L., Enke, C.G.
• Format: Journal Article
• Language: English
• Published: New York, NY Elsevier Inc 01.02.1992; Elsevier Science
• Subjects: Chemistry; Exact sciences and technology; Mass spectrometry; Organic chemistry; Reactivity and mechanisms; Sulfur nitrogen heterocycle; Computer program; Nitrogen heterocycle; Six membered ring; Mass spectrometry MS/MS; Database; Aromatic compound; Substructure; Tricyclic compound; Computer aid
• ISSN: 1044-0305; 1879-1123
• DOI: 10.1016/1044-0305(92)87049-5

Software to interpret tandem mass spectra, entitled Method for Analyzing Patterns in Spectra (MAPS), has been developed to provide substructure information for an automated compound identification system. This software consists of several program modules which manipulate databases of tandem mass spectra and substructure information, generate substructure identification rules, and apply these rules to the tandem mass spectra of unknown compounds to identify components of their structure. The MAPS rule generation program has been modified to generate rules based on specific combinations of spectral features that occur concertedly. False positives are drastically reduced by searching for “feature-combinations” that have 100% uniqueness with respect to a reference database of compounds. Recall is increased by the determination of multiple feature-combinations indicative of the presence of a given substructure. Strategies were developed in the algorithm for the discovery of feature-combinations that avoid the computation “explosion” that occurs when working with a large number of spectral features. The rules developed have the form: “IF feature-combination a (FC a) or FC b, ⋯, or FCx, THEN substructure SSn is present.”