{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,14]],"date-time":"2026-05-14T11:51:34Z","timestamp":1778759494102,"version":"3.51.4"},"reference-count":48,"publisher":"MDPI AG","issue":"17","license":[{"start":{"date-parts":[[2019,8,26]],"date-time":"2019-08-26T00:00:00Z","timestamp":1566777600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-1057942"],"award-info":[{"award-number":["CHE-1057942"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Faculty Research Investment Program","award":["na"],"award-info":[{"award-number":["na"]}]}],"content-domain":{"domain":["www.mdpi.com"],"crossmark-restriction":true},"short-container-title":["Molecules"],"abstract":"<jats:p>Glutathione-based products, GSnX, of the reaction of hydrogen sulfide, H2S, S-nitroso glutathione, and GSNO, at varied stoichiometries have been analyzed by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and chemical trapping experiments. A wide variety of glutathione-based species with catenated sulfur chains have been identified including sulfanes (GSSnG), sulfides (GSSnH), and sulfenic acids (GSnOH); sulfinic (GSnO2H) and sulfonic (GSnO3H) acids are also seen in reactions exposed to air. The presence of each species of GSnX within the original reaction mixtures was confirmed using Single Ion Chromatograms (SICs), to demonstrate the separation on the LC column, and given approximate quantification by the peak area of the SIC. Further, confirmation for different GSnX families was obtained by trapping with species-specific reagents. Several unique GSnX families have been characterized, including bridging mixed di- and tetra-valent polysulfanes and internal trithionitrates (GSNHSnH) with polysulfane branches. Competitive trapping experiments suggest that the polysulfane chains are formed via the intermediacy of sulfenic acid species, GSSnOH. In the presence of radical trap vinylcyclopropane (VCP) the relative distributions of polysulfane speciation are relatively unaffected, suggesting that radical coupling is not a dominant pathway. Therefore, we suggest polysulfane catenation occurs via reaction of sulfides with sulfenic acids.<\/jats:p>","DOI":"10.3390\/molecules24173090","type":"journal-article","created":{"date-parts":[[2019,8,26]],"date-time":"2019-08-26T04:38:23Z","timestamp":1566794303000},"page":"3090","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H2S"],"prefix":"10.3390","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8570-129X","authenticated-orcid":false,"given":"Murugaeson R","family":"Kumar","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9911-999X","authenticated-orcid":false,"given":"Patrick J","family":"Farmer","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2019,8,26]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"493","DOI":"10.1089\/152308603768295249","article-title":"The Gasotransmitter Role of Hydrogen Sulfide","volume":"5","author":"Wang","year":"2003","journal-title":"Antioxid. Redox Signal."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"769","DOI":"10.1021\/tx2005234","article-title":"Small Molecule Signaling Agents: The Integrated Chemistry and Biochemistry of Nitrogen Oxides, Oxides of Carbon, Dioxygen, Hydrogen Sulfide, and Their Derived Species","volume":"25","author":"Fukuto","year":"2012","journal-title":"Chem. Res. Toxicol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"313","DOI":"10.1016\/j.redox.2013.05.001","article-title":"A Tale of Two Gases: NO and H2S, Foes or Friends for Life?","volume":"1","author":"Kolluru","year":"2013","journal-title":"Redox Biol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"527","DOI":"10.1006\/bbrc.1997.6878","article-title":"The Possible Role of Hydrogen Sulfide as an Endogenous Smooth Muscle Relaxant in Synergy with Nitric Oxide","volume":"237","author":"Hosoki","year":"1997","journal-title":"Biochem. Biophys. Res. Commun."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.freeradbiomed.2012.11.005","article-title":"Potential Biological Chemistry of Hydrogen Sulfide (H2S) with the Nitrogen Oxides","volume":"55","year":"2013","journal-title":"Free Radic. Biol. Med."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"82","DOI":"10.1016\/j.freeradbiomed.2014.09.007","article-title":"Redox Chemistry and Chemical Biology of H2S, Hydropersulfides, and Derived Species: Implications of Their Possible Biological Activity and Utility","volume":"77","author":"Ono","year":"2014","journal-title":"Free Radic. Biol. Med."},{"key":"ref_7","first-page":"2451","article-title":"Polysulfides Are Possible H2S-Derived Signaling Molecules in Rat Brain","volume":"27","author":"Kimura","year":"2013","journal-title":"FASEB J. Off. Publ. Fed. Am. Soc. Exp. Biol."},{"key":"ref_8","first-page":"E4651","article-title":"Key Bioactive Reaction Products of the NO\/H2S Interaction Are S\/N-Hybrid Species, Polysulfides, and Nitroxyl","volume":"112","author":"Kuhnle","year":"2015","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Eberhardt, M., Dux, M., Namer, B., Miljkovic, J., Cordasic, N., Will, C., Kichko, T.I., De La Roche, J., Fischer, M., and Su\u00e1rez, S.A. (2014). H2S and NO Cooperatively Regulate Vascular Tone by Activating a Neuroendocrine HNO-TRPA1-CGRP Signalling Pathway. Nat. Commun., 5.","DOI":"10.1038\/ncomms5381"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"498","DOI":"10.1016\/j.cbpa.2012.10.016","article-title":"Mechanisms of S-Nitrosothiol Formation and Selectivity in Nitric Oxide Signaling","volume":"16","author":"Smith","year":"2012","journal-title":"Curr. Opin. Chem. Biol."},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Grman, M., Nasim, M.J., Leontiev, R., Misak, A., Jakusova, V., Ondrias, K., and Jacob, C. (2017). Inorganic Reactive Sulfur-Nitrogen Species: Intricate Release Mechanisms or Cacophony in Yellow, Blue and Red?. Antioxidants, 6.","DOI":"10.3390\/antiox6010014"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"362","DOI":"10.1089\/ars.2014.5869","article-title":"Signaling Molecules: Hydrogen Sulfide and Polysulfide","volume":"22","author":"Kimura","year":"2015","journal-title":"Antioxid. Redox Signal."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"10459","DOI":"10.1038\/s41598-017-11004-7","article-title":"3-Mercaptopyruvate Sulfurtransferase Produces Potential Redox Regulators Cysteine- and Glutathione-Persulfide (Cys-SSH and GSSH) Together with Signaling Molecules H2S2, H2S3 and H2S","volume":"7","author":"Kimura","year":"2017","journal-title":"Sci. Rep."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/s41467-017-01311-y","article-title":"Cysteinyl-TRNA Synthetase Governs Cysteine Polysulfidation and Mitochondrial Bioenergetics","volume":"8","author":"Akaike","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Nishimura, A., Nasuno, R., Yoshikawa, Y., Jung, M., Ida, T., Matsunaga, T., Morita, M., Takagi, H., Motohashi, H., and Akaike, T. (2019). Mitochondrial Cysteinyl-TRNA Synthetase Is Expressed via Alternative Transcriptional Initiation Regulated by Energy Metabolism in Yeast Cells. J. Biol. Chem.","DOI":"10.1074\/jbc.RA119.009203"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"217","DOI":"10.1021\/acschemneuro.7b00363","article-title":"8-Nitro-CGMP Attenuates the Interaction between SNARE Complex and Complexin through S-Guanylation of SNAP-25","volume":"9","author":"Kishimoto","year":"2018","journal-title":"ACS Chem. Neurosci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1715","DOI":"10.1021\/acschemneuro.5b00196","article-title":"8-Nitro-CGMP Enhances SNARE Complex Formation through S-Guanylation of Cys90 in SNAP25","volume":"6","author":"Kunieda","year":"2015","journal-title":"ACS Chem. Neurosci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"C3","DOI":"10.1152\/ajpcell.00282.2016","article-title":"Hydrogen Sulfide, an Enhancer of Vascular Nitric Oxide Signaling: Mechanisms and Implications","volume":"312","author":"Szabo","year":"2017","journal-title":"Am. J. Physiol. Cell Physiol."},{"key":"ref_19","unstructured":"Atwood, D.A., and Zaman, M.K. (2011). Sulfur: Organic Polysulfanes Based in Part on the Article Sulfur: Organic Polysulfanes by Ralf Steudel & Monika Kustos Which Appeared in the Encyclopedia of Inorganic Chemistry, First Edition. Encyclopedia Inorg. Bioinorg. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"457","DOI":"10.1038\/nchembio.1834","article-title":"Biogenesis of Reactive Sulfur Species for Signaling by Hydrogen Sulfide Oxidation Pathways","volume":"11","author":"Mishanina","year":"2015","journal-title":"Nat. Chem. Biol."},{"key":"ref_21","first-page":"62","article-title":"Chemical Trapping and Characterization of Small Oxoacids of Sulfur (SOS) Generated in Aqueous Oxidations of H2S","volume":"112","author":"Kumar","year":"2017","journal-title":"Redox Biol."},{"key":"ref_22","doi-asserted-by":"crossref","unstructured":"Makarov, S.V., Horv\u00e1th, A.K., and Makarova, A.S. (2019). Reactivity of Small Oxoacids of Sulfur. Mol. Basel Switz., 24.","DOI":"10.3390\/molecules24152768"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3173","DOI":"10.1016\/j.bbagen.2013.02.004","article-title":"S-NITROSOGLUTATHIONE","volume":"1830","author":"Broniowska","year":"2013","journal-title":"Biochim. Biophys. Acta"},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Corpas, F.J., Alch\u00e9, J.D., and Barroso, J.B. (2013). Current Overview of S-Nitrosoglutathione (GSNO) in Higher Plants. Front. Plant Sci., 4.","DOI":"10.3389\/fpls.2013.00126"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"786","DOI":"10.1105\/tpc.107.052647","article-title":"Modulation of Nitrosative Stress by S-Nitrosoglutathione Reductase Is Critical for Thermotolerance and Plant Growth in Arabidopsis","volume":"20","author":"Lee","year":"2008","journal-title":"Plant Cell"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"429","DOI":"10.4149\/gpb_2013026","article-title":"Low Molecular Thiols, PH and O2 Modulate H2S-Induced S-Nitrosoglutathione Decomposition\u2013\u2022NO Release","volume":"32","author":"Grman","year":"2013","journal-title":"Gen. Physiol. Biophys."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1016\/0014-5793(96)00086-5","article-title":"The Role of Glutathione in the Transport and Catabolism of Nitric Oxide","volume":"382","author":"Hogg","year":"1996","journal-title":"FEBS Lett."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"234","DOI":"10.1016\/j.redox.2013.12.031","article-title":"Nitrosopersulfide (SSNO\u2212) Accounts for Sustained NO Bioactivity of S-Nitrosothiols Following Reaction with Sulfide","volume":"2","author":"Fernandez","year":"2014","journal-title":"Redox Biol."},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Wedmann, R., Ivanovic-Burmazovic, I., and Filipovic, M.R. (2017). Nitrosopersulfide (SSNO\u2212) Decomposes in the Presence of Sulfide, Cyanide or Glutathione to Give HSNO\/SNO\u2212: Consequences for the Assumed Role in Cell Signalling. Interface Focus, 7.","DOI":"10.1098\/rsfs.2016.0139"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"9367","DOI":"10.1021\/acs.inorgchem.5b00831","article-title":"Does Perthionitrite (SSNO-) Account for Sustained Bioactivity of NO? A (Bio)Chemical Characterization","volume":"54","author":"Wedmann","year":"2015","journal-title":"Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/j.niox.2014.12.009","article-title":"On the Chemical Biology of the Nitrite\/Sulfide Interaction","volume":"46","author":"Fernandez","year":"2015","journal-title":"Nitric Oxide-Biol. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.niox.2018.04.012","article-title":"The Reaction between GSNO and H2S: On the Generation of NO, HNO and N2O","volume":"77","author":"Kumar","year":"2018","journal-title":"Nitric Oxide"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1342","DOI":"10.1002\/anie.201007175","article-title":"Quantification of Protein Sulfenic Acid Modifications Using Isotope-Coded Dimedone and Iododimedone","volume":"50","author":"Seo","year":"2011","journal-title":"Angew. Chem. Int. Ed Engl."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1473","DOI":"10.1074\/mcp.M700065-MCP200","article-title":"Protein Sulfenation as a Redox Sensor: Proteomics Studies Using a Novel Biotinylated Dimedone Analogue","volume":"6","author":"Charles","year":"2007","journal-title":"Mol. Cell. Proteomics"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4633","DOI":"10.1021\/cr300163e","article-title":"Cysteine-Mediated Redox Signaling: Chemistry, Biology, and Tools for Discovery","volume":"113","author":"Paulsen","year":"2013","journal-title":"Chem. Rev."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"783","DOI":"10.1021\/cb900105q","article-title":"Mining the Thiol Proteome for Sulfenic Acid Modifications Reveals New Targets for Oxidation in Cells","volume":"4","author":"Leonard","year":"2009","journal-title":"ACS Chem. Biol."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"14428","DOI":"10.1073\/pnas.93.25.14428","article-title":"The Chemistry of the S-Nitrosoglutathione\/Glutathione System","volume":"93","author":"Singh","year":"1996","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2140","DOI":"10.1002\/1873-3468.13090","article-title":"Biological Hydropersulfides and Related Polysulfides\u2014A New Concept and Perspective in Redox Biology","volume":"592","author":"Fukuto","year":"2018","journal-title":"FEBS Lett."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"474","DOI":"10.1021\/acschembio.6b00980","article-title":"Trapping Reactions of the Sulfenyl and Sulfinyl Tautomers of Sulfenic Acids","volume":"12","author":"Kumar","year":"2016","journal-title":"ACS Chem. Biol."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3500","DOI":"10.1021\/acs.jpca.5b00779","article-title":"Mechanisms of Reactions of Sulfur Hydride Hydroxide: Tautomerism, Condensations, and C-Sulfenylation and O-Sulfenylation of 2,4-Pentanedione","volume":"119","author":"Freeman","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"3905","DOI":"10.1021\/cr010127m","article-title":"The Chemistry of Organic Polysulfanes R-Sn-R (n > 2)","volume":"102","author":"Steudel","year":"2002","journal-title":"Chem. Rev."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"66","DOI":"10.1006\/niox.1998.0166","article-title":"The Reaction of Nitroxyl (HNO) with Nitrosobenzene Gives Cupferron (N-Nitrosophenylhydroxylamine)","volume":"2","author":"Shoeman","year":"1998","journal-title":"Nitric Oxide Biol. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"299","DOI":"10.1016\/j.freeradbiomed.2014.07.022","article-title":"Glutathione Sulfinamide Serves as a Selective, Endogenous Biomarker for Nitroxyl after Exposure to Therapeutic Levels of Donors","volume":"76","author":"Johnson","year":"2014","journal-title":"Free Radic. Biol. Med."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"A1205","DOI":"10.1149\/2.045308jes","article-title":"In-Situ Raman Investigation of Polysulfide Formation in Li-S Cells","volume":"160","author":"Hagen","year":"2013","journal-title":"J. Electrochem. Soc."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1016\/j.freeradbiomed.2016.09.020","article-title":"The chemical biology of the persulfide (RSSH)\/perthiyl (RSS\u00b7) redox couple and possible role in biological redox signaling","volume":"101","author":"Bianco","year":"2016","journal-title":"Free Radic. Biol. Med."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"18596","DOI":"10.1074\/jbc.271.31.18596","article-title":"Mechanism of Nitric Oxide Release from S-Nitrosothiols","volume":"271","author":"Singh","year":"1996","journal-title":"J. Biol. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"3415","DOI":"10.1021\/ja00245a037","article-title":"Timing of the Radical Recombination Step in Cytochrome P-450 Catalysis with Ring-Strained Probes","volume":"109","author":"Stearns","year":"1987","journal-title":"J. Am. Chem. Soc."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"671","DOI":"10.1111\/bph.14372","article-title":"The Reaction of Hydrogen Sulfide with Disulfides: Formation of a Stable Trisulfide and Implications for Biological Systems","volume":"176","author":"Bianco","year":"2019","journal-title":"Br. J. Pharmacol."}],"updated-by":[{"DOI":"10.3390\/molecules24244610","type":"correction","label":"Correction","source":"publisher","updated":{"date-parts":[[2019,8,26]],"date-time":"2019-08-26T00:00:00Z","timestamp":1566777600000}}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/17\/3090\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,8,3]],"date-time":"2025-08-03T22:03:00Z","timestamp":1754258580000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/17\/3090"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,8,26]]},"references-count":48,"journal-issue":{"issue":"17","published-online":{"date-parts":[[2019,9]]}},"alternative-id":["molecules24173090"],"URL":"https:\/\/doi.org\/10.3390\/molecules24173090","relation":{"correction":[{"id-type":"doi","id":"10.3390\/molecules24244610","asserted-by":"object"}]},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,8,26]]}}}