Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds

• Published in: Journal of the American Society for Mass Spectrometry Vol. 28; no. 8; pp. 1687 - 1695
• Main Authors: Acter, Thamina, Kim, Donghwi, Ahmed, Arif, Ha, Ji-Hyoung, Kim, Sunghwan
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.08.2017; Springer Nature B.V
• Subjects: Analytical Chemistry; Atmospheric pressure; Bioinformatics; Biotechnology; Chemistry; Chemistry and Materials Science; CORROSION; DEUTERIUM; Exchanging; HYDROGEN; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Ionization; Mass spectrometry; MASS SPECTROSCOPY; Organic Chemistry; PHOTOIONIZATION; Proteomics; Research Article; Scientific imaging; Speciation; Spectroscopy; Sulfur; SULFUR COMPOUNDS; THIOLS; Thiophenes; Hydrogen/deuterium exchange; Mass spectrometry; Atmospheric-pressure photoionization
• ISSN: 1044-0305; 1879-1123
• DOI: 10.1007/s13361-017-1678-z

Herein we report the observation of atmospheric pressure in-source hydrogen–deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ