{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T02:24:19Z","timestamp":1789525459859,"version":"build-2803163510"},"reference-count":25,"publisher":"MDPI AG","issue":"23","license":[{"start":{"date-parts":[[2022,12,6]],"date-time":"2022-12-06T00:00:00Z","timestamp":1670284800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["21-73-20032"],"award-info":[{"award-number":["21-73-20032"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>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, \u201csoft\u201d 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 = CH3 or C2H5) in the presence of triflic acid (CF3SO3H) 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.<\/jats:p>","DOI":"10.3390\/molecules27238600","type":"journal-article","created":{"date-parts":[[2022,12,7]],"date-time":"2022-12-07T04:00:37Z","timestamp":1670385637000},"page":"8600","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["The Use of Polydialkylsiloxanes\/Triflic Acid as Derivatization Agents in the Analysis of Sulfur-Containing Aromatics by \u201cSoft\u201d-Ionization Mass Spectrometry"],"prefix":"10.3390","volume":"27","author":[{"given":"Zhanna","family":"Starkova","sequence":"first","affiliation":[{"name":"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7359-3308","authenticated-orcid":false,"given":"Valentina","family":"Ilyushenkova","sequence":"additional","affiliation":[{"name":"N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nikolay","family":"Polovkov","sequence":"additional","affiliation":[{"name":"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daria","family":"Voskressenskaya","sequence":"additional","affiliation":[{"name":"Institute of Medicine, Peoples\u2019 Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6149-6770","authenticated-orcid":false,"given":"Ilya","family":"Pikovskoi","sequence":"additional","affiliation":[{"name":"Core Facility Center \u2018Arktika\u2019, Northern (Arctic) Federal University, 17 nab.Severnoy Dviny, 163002 Arkhangelsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mikhail","family":"Tebenikhin","sequence":"additional","affiliation":[{"name":"Institute of Medicine, Peoples\u2019 Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ella","family":"Vtorushina","sequence":"additional","affiliation":[{"name":"V.I. Shpilman Research and Analytical Center for the Rational Use of the Subsoil, 2 Studencheskaya Str., 628007 Khanty-Mansiysk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1633-0197","authenticated-orcid":false,"given":"Anastasiia","family":"Kanateva","sequence":"additional","affiliation":[{"name":"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roman","family":"Borisov","sequence":"additional","affiliation":[{"name":"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia"},{"name":"Core Facility Center \u2018Arktika\u2019, Northern (Arctic) Federal University, 17 nab.Severnoy Dviny, 163002 Arkhangelsk, Russia"},{"name":"Department of Plastics, D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Pl., 125047 Moscow, Russia"},{"name":"Organic Chemistry Department, Peoples\u2019 Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vladimir","family":"Zaikin","sequence":"additional","affiliation":[{"name":"A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,12,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2246","DOI":"10.1039\/C9TA12555H","article-title":"A comprehensive review on oxidative desulfurization catalysts targeting clean energy and environment","volume":"8","author":"Rajendran","year":"2020","journal-title":"J. Mater. Chem. A"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"35302","DOI":"10.1039\/C4RA03478C","article-title":"A Review of extractive desulfurization of fuel oils using ionic liquids","volume":"4","author":"Abro","year":"2014","journal-title":"RSC Adv."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"777","DOI":"10.1134\/S1061934806080107","article-title":"X-Ray fluorescence determination of sulfur and jther elements in customs control of oil and liquid oil Products","volume":"61","author":"Drobyshev","year":"2006","journal-title":"J. Anal. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"800","DOI":"10.1016\/j.sab.2008.04.020","article-title":"Total sulfur determination in gasoline, kerosene and diesel fuel using inductively coupled plasma optical emission spectrometry after direct sample introduction as detergent emulsions","volume":"63","author":"Santelli","year":"2008","journal-title":"Spectrochimica Acta Part B At. Spectrosc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"202","DOI":"10.1016\/j.trac.2018.05.007","article-title":"The Impact of Comprehensive Two-Dimensional Gas Chromatography on Oil Gas Analysis: Recent Advances and Applications in Petroleum Industry","volume":"105","author":"Pollo","year":"2018","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3849","DOI":"10.1021\/ac011190e","article-title":"Analysis of Aromatic Sulfur Compounds in Gas Oils Using GC with Sulfur Chemiluminescence Detection and High-Resolution MS","volume":"74","author":"Becchi","year":"2002","journal-title":"Anal. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1039\/b9ay00143c","article-title":"Observations on Comprehensive Two Dimensional Gas Chromatography Coupled with Flame Photometric Detection for Sulfur- and Phosphorus-Containing Compounds","volume":"2","author":"Chin","year":"2010","journal-title":"Anal. Methods"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1055","DOI":"10.1134\/S0965544119100025","article-title":"Mass Spectrometry in petroleum chemistry (petroleomics) (review)","volume":"59","author":"Borisov","year":"2019","journal-title":"Pet. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"197","DOI":"10.1016\/S1387-3806(99)00186-4","article-title":"Electrospray Mass Spectrometry of Fossil Fuels","volume":"194","author":"Zhan","year":"2000","journal-title":"Int. J. Mass Spectrom."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"337","DOI":"10.1002\/jms.1893","article-title":"Petroleomics: Advanced Molecular Probe for Petroleum Heavy Ends","volume":"46","author":"Hsu","year":"2011","journal-title":"J. Mass Spectrom."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"405","DOI":"10.1146\/annurev-anchem-091619-091824","article-title":"Petroleomics: Tools, challenges, and developments","volume":"13","author":"Thomas","year":"2020","journal-title":"Annu. Rev. Anal. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1021\/ac302789c","article-title":"Unraveling the mechanism of electrospray ionization","volume":"85","author":"Konermann","year":"2012","journal-title":"Anal. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.aca.2006.08.062","article-title":"Matrix-Assisted Laser Desorption\/Ionization (MALDI) Mechanism Revisited","volume":"582","author":"Chang","year":"2007","journal-title":"Anal. Chim. Acta"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1287","DOI":"10.1080\/10408347.2021.1873100","article-title":"Options of the main derivatization approaches for analytical ESI and MALDI mass spectrometry","volume":"52","author":"Zaikin","year":"2021","journal-title":"Crit. Rev. Anal. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1016\/j.trac.2014.03.013","article-title":"Derivatization for liquid chromatography-mass spectrometry","volume":"59","author":"Qi","year":"2014","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"108","DOI":"10.1177\/1469066717723909","article-title":"Regio-isomeric effects in tandem mass spectra of sulfonium cations generated from thiacyclane based sulfonium salts under soft ionization conditions","volume":"24","author":"Zaikin","year":"2018","journal-title":"Eur. J. Mass Spectrom."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1396","DOI":"10.1134\/S1061934819140065","article-title":"Permanent-charge generation derivatization for the analysis of thiols by \u201csoft\u201d ionization mass spectrometry methods","volume":"74","author":"Kozlov","year":"2019","journal-title":"J. Anal. Chem."},{"key":"ref_18","first-page":"101","article-title":"Effects of isomerism in the mass spectra of stimulated dissociation of sulfonium cations desorbed from S-alkylated thiacyclanes under MALDI conditions. A convenient way to derivatize sulfides under the influence of alkyl formats","volume":"18","author":"Starkova","year":"2021","journal-title":"Mass-spektrometriya"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2536","DOI":"10.1021\/ac0483522","article-title":"Characterization of high-molecular-weight sulfur-containing aromatics in vacuum residues using Fourier transform ion cyclotron resonance mass spectrometry","volume":"77","author":"Andersson","year":"2005","journal-title":"Anal. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1797","DOI":"10.1021\/acs.energyfuels.8b02756","article-title":"Selective methylation of sulfides in petroleum for electrospray ionization mass spectrometry analysis","volume":"33","author":"Li","year":"2019","journal-title":"Energy Fuels"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"10842","DOI":"10.1021\/acs.energyfuels.0c01987","article-title":"Characterization of sulfur-containing compounds in petroleum using AgSbF6 as a methylation reagent","volume":"34","author":"Ge","year":"2020","journal-title":"Energy Fuels"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1039\/P29840000267","article-title":"Cleavage of silicon\u2013carbon bonds in tris(trimethylsilyl)methylsilicon compounds by trifluoroacetic acid. Rearrangements and anchimeric assistance","volume":"2","author":"Eaborn","year":"1984","journal-title":"J. Chem. Soc. Perkin Trans."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1016\/0022-328X(94)87166-3","article-title":"Selective intramolecular cleavage of the carbon-silicon bond by palladium salts","volume":"483","author":"Valk","year":"1994","journal-title":"J. Organomet. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"8659","DOI":"10.1016\/S0040-4039(00)78464-4","article-title":"Synthesis of sulfonium salts by sulfide alkylation; an alternative approach","volume":"35","author":"Aggarwal","year":"1994","journal-title":"Tetrahedron Lett."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1483","DOI":"10.1021\/jasms.0c00109","article-title":"DropMS: Petroleomics data treatment based in Web server for high-resolution mass spectrometry","volume":"31","author":"Rosa","year":"2020","journal-title":"J. Am. Soc. Mass Spectrom."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/23\/8600\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:34:52Z","timestamp":1760146492000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/23\/8600"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,12,6]]},"references-count":25,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2022,12]]}},"alternative-id":["molecules27238600"],"URL":"https:\/\/doi.org\/10.3390\/molecules27238600","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,12,6]]}}}