Inferring the nominal molecular mass of an analyte from its electron ionization mass spectrum

Published

August 23, 2023

Author(s)

Arun Moorthy, Anthony J. Kearsley, William Mallard, William E. Wallace, Stephen E. Stein

Abstract

The performance of three algorithms for predicting nominal molecular mass from an analyte's electron ionization mass spectrum is presented. The Peak Interpretation Method (PIM) attempts to quantify the likelihood that a molecular ion peak is contained in the mass spectrum, whereas the Simple Search Hitlist Method (SS-HM) and iterative Hybrid Search Hitlist Method (iHS-HM) leverage results from mass spectral library searching. These predictions can be employed in combination (recommended) or independently. The methods were tested on two sets of query mass spectra searched against libraries that did not contain the reference mass spectra of the same compounds: 19,074 spectra of various organic molecules searched against the NIST17 mass spectral library and 162 spectra of small molecule drugs searched against SWGDRUG version 3.3. Individually, each molecular mass prediction method had computed precisions (the fraction of positive predictions that were correct) of 91, 89, and 74%, respectively. The methods become more valuable when predictions are taken together. When all three predictions were identical, which occurred in 33% of the test cases, the predicted molecular mass was almost always correct (>99%).

Citation

Analytical Chemistry

Volume

95

Issue

5

Pub Type

Journals

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DOI Link

Keywords

Compound Identification, Electron Ionization Mass Spectrometry, Hybrid Search, Mass Spectral Library Searching, Molecular Mass

Citation

Moorthy, A. , Kearsley, A. , Mallard, W. , Wallace, W. and Stein, S. (2023), Inferring the nominal molecular mass of an analyte from its electron ionization mass spectrum, Analytical Chemistry, [online], https://doi.org/10.1021/acs.analchem.3c01815 (Accessed October 16, 2025)