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Molecules

Title:		The Use of Polydialkylsiloxanes/Triflic Acid as Derivatization Agents in the Analysis of Sulfur-Containing Aromatics by 'Soft'-Ionization Mass Spectrometry
Author(s):		Starkova Z; Ilyushenkova V; Polovkov N; Voskressenskaya D; Pikovskoi I; Tebenikhin M; Vtorushina E; Kanateva A; Borisov R; Zaikin V;
Address:		"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, Russia. Institute of Medicine, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia. Core Facility Center 'Arktika', Northern (Arctic) Federal University, 17 nab.Severnoy Dviny, 163002 Arkhangelsk, Russia. V.I. Shpilman Research and Analytical Center for the Rational Use of the Subsoil, 2 Studencheskaya Str., 628007 Khanty-Mansiysk, Russia. Department of Plastics, D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Pl., 125047 Moscow, Russia. Organic Chemistry Department, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia"
Journal Title:		Molecules
Year:		2022
Volume:		20221206
Issue:		23
Page Number:		-
DOI:		10.3390/molecules27238600
ISSN/ISBN:		1420-3049 (Electronic) 1420-3049 (Linking)
Abstract:		"Polycyclic aromatic sulfur-containing compounds are widely distributed in oil, especially in its low-volatile and heavy fractions (resins, asphaltenes), and this dictates the need for their determination when reliable methods for sulfur removing, cleaning and processing oil are developed. In these cases, 'soft' ionization mass spectrometry methods, based on electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI), are particularly effective. However, aromatic sulfur-containing compounds have low polarity and cannot be readily ionized by these methods. To overcome the problem, their preliminary conversion into sulfonium salts by the action of alkyl iodides and a silver-containing agent is widely used. In the process of developing more economical derivatization methods, we found a rather unexpected possibility of implementing S-alkylation of organic sulfides with commercial polydialkylsiloxanes (alkyl = CH(3) or C(2)H(5)) in the presence of triflic acid (CF(3)SO(3)H) as a superacid co-alkylating agent. For homologous dibenzothiophenes as a typical model representative of petroleum sulfur-containing aromatic compounds, ESI and MALDI mass spectra exhibited the signals of corresponding S-alkylsulfonium salts with a high signal-to-noise ratio. A rational mechanism for the described chemical transformation is proposed, including the indispensable activation by triflic acid and the cleavage of the Si-C bond. Specific collision-induced dissociation of corresponding S-alkylated sulfonium cations is considered. The applicability of the derivatization approach to the analysis of petroleum products by high-resolution mass spectrometry is demonstrated"
Keywords:		"*Spectrometry, Mass, Electrospray Ionization/methods Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/methods Mesylates Sulfur Organic Chemicals *Petroleum Cid Esi Maldi derivatization dibenzothiophenes high resolution mass spectrometry pol;"
Notes:		"MedlineStarkova, Zhanna Ilyushenkova, Valentina Polovkov, Nikolay Voskressenskaya, Daria Pikovskoi, Ilya Tebenikhin, Mikhail Vtorushina, Ella Kanateva, Anastasiia Borisov, Roman Zaikin, Vladimir eng 21-73-20032/Russian Science Foundation/ Switzerland 2022/12/12 Molecules. 2022 Dec 6; 27(23):8600. doi: 10.3390/molecules27238600"