A Fast and Selective Approach for Profiling Vicinal Diols Using Liquid Chromatography-Post Column Derivatization-Double Precursor Ion Scanning Mass Spectrometry

• Published in: Molecules (Basel, Switzerland) Vol. 27; no. 1; p. 283
• Main Authors: Wan, Debin, Morisseau, Christophe, Hammock, Bruce D, Yang, Jun
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 03.01.2022; MDPI
• Subjects: Biomarkers; Bromine isotopes; Chromatography; Chromatography, Liquid; Column chromatography; Diols; double precursor ion scan; Epoxide hydrolase; Epoxy Compounds - analysis; Esters; Fatty acids; Fatty Acids - analysis; Humans; Inflammatory diseases; Ions; Liquid chromatography; Mass spectrometry; Mass spectroscopy; Metabolism; Metabolites; online post-column derivatization; Precursors; Reagents; Scientific imaging; Selectivity; Spectroscopy; Tandem Mass Spectrometry; vicinal diols; online post-column derivatization; vicinal diols; double precursor ion scan; epoxide hydrolase
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27010283

Vicinal diols are important signaling metabolites of various inflammatory diseases, and some of them are potential biomarkers for some diseases. Utilizing the rapid reaction between diol and 6-bromo-3-pyridinylboronic acid (BPBA), a selective and sensitive approach was established to profile these vicinal diols using liquid chromatography-post column derivatization coupled with double precursor ion scan-mass spectrometry (LC-PCD-DPIS-MS). After derivatization, all BPBA-vicinal-diol esters gave a pair of characteristic isotope ions resulting from Br and Br. The unique isotope pattern generated two characteristic fragment ions of 200 and 202. Compared to a traditional offline derivatization technique, the new LC-PCD-DPIS-MS method retained the capacity of LC separation. In addition, it is more sensitive and selective than a full scan MS method. As an application, an in vitro study of the metabolism of epoxy fatty acids by human soluble epoxide hydrolase was tested. These vicinal-diol metabolites of individual regioisomers from different types of polyunsaturated fatty acids were easily identified. The limit of detection (LOD) reached as low as 25 nM. The newly developed LC-PCD-DPIS-MS method shows significant advantages in improving the selectivity and therefore can be employed as a powerful tool for profiling vicinal-diol compounds from biological matrices.