Infrared ion spectroscopy: New opportunities for small-molecule identification in mass spectrometry - A tutorial perspective

• Published in: Analytica chimica acta Vol. 1093; pp. 1 - 15
• Main Authors: Martens, Jonathan, van Outersterp, Rianne E., Vreeken, Rob J., Cuyckens, Filip, Coene, Karlien L.M., Engelke, Udo F., Kluijtmans, Leo A.J., Wevers, Ron A., Buydens, Lutgarde M.C., Redlich, Britta, Berden, Giel, Oomens, Jos
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 06-01-2020
• Subjects: Biomarker discovery; Inborn errors of metabolism; Infrared ion spectroscopy; Liquid chromatography; Molecular structure identification; Untargeted metabolomics; Biomarker discovery; Liquid chromatography; Inborn errors of metabolism; Molecular structure identification; Infrared ion spectroscopy; Untargeted metabolomics
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2019.10.043

Combining the individual analytical strengths of mass spectrometry and infrared spectroscopy, infrared ion spectroscopy is increasingly recognized as a powerful tool for small-molecule identification in a wide range of analytical applications. Mass spectrometry is itself a leading analytical technique for small-molecule identification on the merit of its outstanding sensitivity, selectivity and versatility. The foremost shortcoming of the technique, however, is its limited ability to directly probe molecular structure, especially when contrasted against spectroscopic techniques. In infrared ion spectroscopy, infrared vibrational spectra are recorded for mass-isolated ions and provide a signature that can be matched to reference spectra, either measured from standards or predicted using quantum-chemical calculations. Here we present an overview of the potential for this technique to develop into a versatile analytical method for identifying molecular structures in mass spectrometry-based analytical workflows. In this tutorial perspective, we introduce the reader to the technique of infrared ion spectroscopy and highlight a selection of recent experimental advances and applications in current analytical challenges, in particular in the field of untargeted metabolomics. We report on the coupling of infrared ion spectroscopy with liquid chromatography and present experiments that serve as proof-of-principle examples of strategies to address outstanding challenges.
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•IR ion spectroscopy (IRIS) provides a fingerprint for peaks in a mass spectrum.•The IR fingerprint is a sensitive diagnostic for the molecular structure.•Identification through reference spectra from standards or from computation.•IRIS can be integrated in analytical MS workflows including MSn and LC-MS.•A tutorial on IRIS and selected applications in untargeted metabolomics is presented.