Unsupervised Reconstruction of Analyte-Specific Mass Spectra Based on Time-Domain Morphology with a Modified Cross-Correlation Approach

Concomitant species that appear at the same or very similar times in a mass-spectral analysis can clutter a spectrum because of the coexistence of many analyte-related ions (e.g., molecular ions, adducts, fragments). One method to extract ions stemming from the same origin is to exploit the chemical...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2021-03, Vol.93 (12), p.5009-5014
Main Authors: You, Yi, Song, Linxia, Young, Montwaun D, van der Wielen, Matthew, Evans-Nguyen, Theresa, Riedel, Jens, Shelley, Jacob T
Format: Article
Language:English
Subjects:
Adducts
Algorithms
Chemistry
Clutter
Coexistence
Correlation coefficient
Correlation coefficients
Cross correlation
Ions
Libraries
Mass spectra
Mass spectroscopy
Molecular ions
Morphology
Spectral analysis
Spectrometry
Spectrum analysis
Time domain analysis
Workflow
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Summary:Concomitant species that appear at the same or very similar times in a mass-spectral analysis can clutter a spectrum because of the coexistence of many analyte-related ions (e.g., molecular ions, adducts, fragments). One method to extract ions stemming from the same origin is to exploit the chemical information encoded in the time domain, where the individual temporal appearances inside the complex structures of chronograms or chromatograms differ with respect to analytes. By grouping ions with very similar or identical time-domain structures, single-component mass spectra can be reconstructed, which are much easier to interpret and are library-searchable. While many other approaches address similar objectives through the Pearson’s correlation coefficient, we explore an alternative method based on a modified cross-correlation algorithm to compute a metric that describes the degree of similarity between features inside any two ion chronograms. Furthermore, an automatic workflow was devised to be capable of categorizing thousands of mass-spectral peaks into different groups within a few seconds. This approach was tested with direct mass-spectrometric analyses as well as with a simple, fast, and poorly resolved LC–MS analysis. Single-component mass spectra were extracted in both cases and were identified based on accurate mass and a mass-spectral library search.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.0c04396