Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids
Thiyl radicals are important reactive sulfur species and can cause cis to trans isomerization on unsaturated fatty acids. However, biocompatible strategies for the controlled generation of thiyl radicals are still lacking. In this work, we report the study of a series of naphthacyl-derived thioether...
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| Format: | Article |
| Language: | English |
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Elsevier
2025-02-01
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| Series: | Redox Biology |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2213231724004531 |
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| author | Biswajit Roy Ryota Kojima Obaed Shah Meg Shieh Eshani Das Shahrzad Ezzatpour Emiko Sato Yusuke Hirata Stephen Lindahl Atsushi Matsuzawa Hector C. Aguilar Ming Xian |
| author_facet | Biswajit Roy Ryota Kojima Obaed Shah Meg Shieh Eshani Das Shahrzad Ezzatpour Emiko Sato Yusuke Hirata Stephen Lindahl Atsushi Matsuzawa Hector C. Aguilar Ming Xian |
| author_sort | Biswajit Roy |
| collection | DOAJ |
| description | Thiyl radicals are important reactive sulfur species and can cause cis to trans isomerization on unsaturated fatty acids. However, biocompatible strategies for the controlled generation of thiyl radicals are still lacking. In this work, we report the study of a series of naphthacyl-derived thioethers as photo-triggered thiyl radical precursors. Tertiary naphthacyl thioether was identified to be a suitable template that could be used to produce both aryl and alkyl thiyl radicals under ultraviolet (UV) light or sunlight. The effective cis-to trans-isomerization of unsaturated fatty acid models (methyl oleate, methyl linoleate) and a natural phospholipid (cardiolipin) using these photo-triggered substrates was demonstrated. This reaction was also proved to proceed effectively in cells to produce thiyl radicals and subsequent fatty acid isomerization. Additionally, the most promising thiyl radical precursor showed antiviral activity in a pseudotyped virus model, likely due to disrupting viral lipid membranes upon UV activation. These findings highlight the potential of thiyl radicals for both biochemical and antiviral applications. |
| format | Article |
| id | doaj-art-56a759b9eff34c6bb116b555a49edcd7 |
| institution | Kabale University |
| issn | 2213-2317 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Redox Biology |
| spelling | doaj-art-56a759b9eff34c6bb116b555a49edcd72025-01-14T04:12:12ZengElsevierRedox Biology2213-23172025-02-0179103475Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipidsBiswajit Roy0Ryota Kojima1Obaed Shah2Meg Shieh3Eshani Das4Shahrzad Ezzatpour5Emiko Sato6Yusuke Hirata7Stephen Lindahl8Atsushi Matsuzawa9Hector C. Aguilar10Ming Xian11Department of Chemistry, Brown University, Providence, RI, 02912, USALaboratory of Health Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, JapanDepartment of Microbiology and Immunology, Cornell University, Ithaca, NY, 14853, USADepartment of Chemistry, Brown University, Providence, RI, 02912, USADepartment of Chemistry, Brown University, Providence, RI, 02912, USADepartment of Microbiology and Immunology, Cornell University, Ithaca, NY, 14853, USADivision of Clinical Pharmacology and Therapeutics, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, JapanLaboratory of Health Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, JapanDepartment of Chemistry, Brown University, Providence, RI, 02912, USALaboratory of Health Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, JapanDepartment of Microbiology and Immunology, Cornell University, Ithaca, NY, 14853, USADepartment of Chemistry, Brown University, Providence, RI, 02912, USA; Corresponding author.Thiyl radicals are important reactive sulfur species and can cause cis to trans isomerization on unsaturated fatty acids. However, biocompatible strategies for the controlled generation of thiyl radicals are still lacking. In this work, we report the study of a series of naphthacyl-derived thioethers as photo-triggered thiyl radical precursors. Tertiary naphthacyl thioether was identified to be a suitable template that could be used to produce both aryl and alkyl thiyl radicals under ultraviolet (UV) light or sunlight. The effective cis-to trans-isomerization of unsaturated fatty acid models (methyl oleate, methyl linoleate) and a natural phospholipid (cardiolipin) using these photo-triggered substrates was demonstrated. This reaction was also proved to proceed effectively in cells to produce thiyl radicals and subsequent fatty acid isomerization. Additionally, the most promising thiyl radical precursor showed antiviral activity in a pseudotyped virus model, likely due to disrupting viral lipid membranes upon UV activation. These findings highlight the potential of thiyl radicals for both biochemical and antiviral applications.http://www.sciencedirect.com/science/article/pii/S2213231724004531Unsaturated fatty acidThiyl radicalsThioetherCis to trans isomerizationPhotoreaction |
| spellingShingle | Biswajit Roy Ryota Kojima Obaed Shah Meg Shieh Eshani Das Shahrzad Ezzatpour Emiko Sato Yusuke Hirata Stephen Lindahl Atsushi Matsuzawa Hector C. Aguilar Ming Xian Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids Redox Biology Unsaturated fatty acid Thiyl radicals Thioether Cis to trans isomerization Photoreaction |
| title | Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids |
| title_full | Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids |
| title_fullStr | Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids |
| title_full_unstemmed | Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids |
| title_short | Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids |
| title_sort | generation of thiyl radicals in a spatiotemporal controlled manner by light applied for the cis to trans isomerization of unsaturated fatty acids phospholipids |
| topic | Unsaturated fatty acid Thiyl radicals Thioether Cis to trans isomerization Photoreaction |
| url | http://www.sciencedirect.com/science/article/pii/S2213231724004531 |
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