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Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione
Phosphorus species are potent modulators of physicochemical and bioactive properties of peptide compounds. O,O-diorganyl dithiophoshoric acids (DTP) form bioactive salts with nitrogen-containing biomolecules; however, their potential as a peptide modifier is poorly known. We synthesized amphiphilic...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8157023/ https://www.ncbi.nlm.nih.gov/pubmed/34067789 http://dx.doi.org/10.3390/molecules26102973 |
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author | Ishkaeva, Rezeda A. Nizamov, Ilyas S. Blokhin, Dmitriy S. Urakova, Elizaveta A. Klochkov, Vladimir V. Nizamov, Ilnar D. Gareev, Bulat I. Salakhieva, Diana V. Abdullin, Timur I. |
author_facet | Ishkaeva, Rezeda A. Nizamov, Ilyas S. Blokhin, Dmitriy S. Urakova, Elizaveta A. Klochkov, Vladimir V. Nizamov, Ilnar D. Gareev, Bulat I. Salakhieva, Diana V. Abdullin, Timur I. |
author_sort | Ishkaeva, Rezeda A. |
collection | PubMed |
description | Phosphorus species are potent modulators of physicochemical and bioactive properties of peptide compounds. O,O-diorganyl dithiophoshoric acids (DTP) form bioactive salts with nitrogen-containing biomolecules; however, their potential as a peptide modifier is poorly known. We synthesized amphiphilic ammonium salts of O,O-dimenthyl DTP with glutathione, a vital tripeptide with antioxidant, protective and regulatory functions. DTP moiety imparted radical scavenging activity to oxidized glutathione (GSSG), modulated the activity of reduced glutathione (GSH) and profoundly improved adsorption and electrooxidation of both glutathione salts on graphene oxide modified electrode. According to NMR spectroscopy and GC–MS, the dithiophosphates persisted against immediate dissociation in an aqueous solution accompanied by hydrolysis of DTP moiety into phosphoric acid, menthol and hydrogen sulfide as well as in situ thiol-disulfide conversions in peptide moieties due to the oxidation of GSH and reduction of GSSG. The thiol content available in dissolved GSH dithiophosphate was more stable during air oxidation compared with free GSH. GSH and the dithiophosphates, unlike DTP, caused a thiol-dependent reduction of MTS tetrazolium salt. The results for the first time suggest O,O-dimenthyl DTP as a redox modifier for glutathione, which releases hydrogen sulfide and induces biorelevant redox conversions of thiol/disulfide groups. |
format | Online Article Text |
id | pubmed-8157023 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-81570232021-05-28 Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione Ishkaeva, Rezeda A. Nizamov, Ilyas S. Blokhin, Dmitriy S. Urakova, Elizaveta A. Klochkov, Vladimir V. Nizamov, Ilnar D. Gareev, Bulat I. Salakhieva, Diana V. Abdullin, Timur I. Molecules Article Phosphorus species are potent modulators of physicochemical and bioactive properties of peptide compounds. O,O-diorganyl dithiophoshoric acids (DTP) form bioactive salts with nitrogen-containing biomolecules; however, their potential as a peptide modifier is poorly known. We synthesized amphiphilic ammonium salts of O,O-dimenthyl DTP with glutathione, a vital tripeptide with antioxidant, protective and regulatory functions. DTP moiety imparted radical scavenging activity to oxidized glutathione (GSSG), modulated the activity of reduced glutathione (GSH) and profoundly improved adsorption and electrooxidation of both glutathione salts on graphene oxide modified electrode. According to NMR spectroscopy and GC–MS, the dithiophosphates persisted against immediate dissociation in an aqueous solution accompanied by hydrolysis of DTP moiety into phosphoric acid, menthol and hydrogen sulfide as well as in situ thiol-disulfide conversions in peptide moieties due to the oxidation of GSH and reduction of GSSG. The thiol content available in dissolved GSH dithiophosphate was more stable during air oxidation compared with free GSH. GSH and the dithiophosphates, unlike DTP, caused a thiol-dependent reduction of MTS tetrazolium salt. The results for the first time suggest O,O-dimenthyl DTP as a redox modifier for glutathione, which releases hydrogen sulfide and induces biorelevant redox conversions of thiol/disulfide groups. MDPI 2021-05-17 /pmc/articles/PMC8157023/ /pubmed/34067789 http://dx.doi.org/10.3390/molecules26102973 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Ishkaeva, Rezeda A. Nizamov, Ilyas S. Blokhin, Dmitriy S. Urakova, Elizaveta A. Klochkov, Vladimir V. Nizamov, Ilnar D. Gareev, Bulat I. Salakhieva, Diana V. Abdullin, Timur I. Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title | Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title_full | Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title_fullStr | Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title_full_unstemmed | Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title_short | Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione |
title_sort | dithiophosphate-induced redox conversions of reduced and oxidized glutathione |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8157023/ https://www.ncbi.nlm.nih.gov/pubmed/34067789 http://dx.doi.org/10.3390/molecules26102973 |
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