Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S
Glutathione-based products, GS<sub>n</sub>X, of the reaction of hydrogen sulfide, H<sub>2</sub>S, S-nitroso glutathione, and GSNO, at varied stoichiometries have been analyzed by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and chemical trapping experimen...
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| Format: | Article |
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MDPI AG
2019-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/17/3090 |
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| author | Murugaeson R Kumar Patrick J Farmer |
| author_facet | Murugaeson R Kumar Patrick J Farmer |
| author_sort | Murugaeson R Kumar |
| collection | DOAJ |
| description | Glutathione-based products, GS<sub>n</sub>X, of the reaction of hydrogen sulfide, H<sub>2</sub>S, 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 (GSS<sub>n</sub>G), sulfides (GSS<sub>n</sub>H), and sulfenic acids (GS<sub>n</sub>OH); sulfinic (GS<sub>n</sub>O<sub>2</sub>H) and sulfonic (GS<sub>n</sub>O<sub>3</sub>H) acids are also seen in reactions exposed to air. The presence of each species of GS<sub>n</sub>X 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 GS<sub>n</sub>X families was obtained by trapping with species-specific reagents. Several unique GS<sub>n</sub>X families have been characterized, including bridging mixed di- and tetra-valent polysulfanes and internal trithionitrates (GSNHS<sub>n</sub>H) with polysulfane branches. Competitive trapping experiments suggest that the polysulfane chains are formed via the intermediacy of sulfenic acid species, GSS<sub>n</sub>OH. 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. |
| first_indexed | 2024-12-11T10:57:08Z |
| format | Article |
| id | doaj.art-3b66e34df55f4ef8b96f4b45ec62906f |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-11T10:57:08Z |
| publishDate | 2019-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-3b66e34df55f4ef8b96f4b45ec62906f2022-12-22T01:10:00ZengMDPI AGMolecules1420-30492019-08-012417309010.3390/molecules24173090molecules24173090Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>SMurugaeson R Kumar0Patrick J Farmer1Department of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, USADepartment of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, USAGlutathione-based products, GS<sub>n</sub>X, of the reaction of hydrogen sulfide, H<sub>2</sub>S, 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 (GSS<sub>n</sub>G), sulfides (GSS<sub>n</sub>H), and sulfenic acids (GS<sub>n</sub>OH); sulfinic (GS<sub>n</sub>O<sub>2</sub>H) and sulfonic (GS<sub>n</sub>O<sub>3</sub>H) acids are also seen in reactions exposed to air. The presence of each species of GS<sub>n</sub>X 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 GS<sub>n</sub>X families was obtained by trapping with species-specific reagents. Several unique GS<sub>n</sub>X families have been characterized, including bridging mixed di- and tetra-valent polysulfanes and internal trithionitrates (GSNHS<sub>n</sub>H) with polysulfane branches. Competitive trapping experiments suggest that the polysulfane chains are formed via the intermediacy of sulfenic acid species, GSS<sub>n</sub>OH. 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.https://www.mdpi.com/1420-3049/24/17/3090hydrogen sulfideS-nitroso glutathionepolysulfanessulfidessulfenic acidshigh-resolution mass spectrometrydimedoneiodoacetamidevinylcyclopropane |
| spellingShingle | Murugaeson R Kumar Patrick J Farmer Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S Molecules hydrogen sulfide S-nitroso glutathione polysulfanes sulfides sulfenic acids high-resolution mass spectrometry dimedone iodoacetamide vinylcyclopropane |
| title | Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S |
| title_full | Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S |
| title_fullStr | Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S |
| title_full_unstemmed | Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S |
| title_short | Characterization of Polysulfides, Polysulfanes, and Other Unique Species in the Reaction between GSNO and H<sub>2</sub>S |
| title_sort | characterization of polysulfides polysulfanes and other unique species in the reaction between gsno and h sub 2 sub s |
| topic | hydrogen sulfide S-nitroso glutathione polysulfanes sulfides sulfenic acids high-resolution mass spectrometry dimedone iodoacetamide vinylcyclopropane |
| url | https://www.mdpi.com/1420-3049/24/17/3090 |
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