Outils chimiques pour l'étude et la compréhension du rôle du sulfure d'hydrogène en biologie

Après avoir été considéré pendant des années comme un polluant environnemental, il a récemment été mis en évidence que le sulfure d hydrogène est le troisième transmetteur gazeux, aux côtés des monoxydes d azote et de carbone. Dans ce travail de thèse, deux types d outils moléculairesont été visés : a) Des sondes fluorescentes pour détecter H2S, basées sur une utilisation originale de la chimie de coordination cherchant à favoriser l attaque du sulfure d hydrogène sur le ligand plutôt que sur le métal. Malgré leur forte réponse à H2S en solution tampon, celles-ci ne se sont malheureusement pas révélées sélectives vis-à-vis d autres thiols biologiques. b) Des donneurs lents de sulfure d hydrogène. Les premiers composés développés, basée sur la chimie de coordination, se comportent malheureusement comme des donneurs rapides. Par contre, la seconde famille, constituée de molécules organiques, s est révélée être un excellent substitut des sels d H2S couramment utilisés dans les études biologiques malgré leurs effets indésirables. De plus, nous avons aussi répondu à un défi synthétique en obtenant le premier complexe Fe SH comportant un ligand hydrosulfure impliqué dans une liaison hydrogène, telle que celle trouvée dans les hémoglobines des bactéries Bacillus subtilis et Thermobifida fusca.Pas de résumé en anglaisPARIS5-Bibliotheque electronique (751069902) / SudocPARIS-BIUM-Bib. électronique (751069903) / SudocSudocFranceF

Supplementary material for the article: Wedmann, R.; Onderka, C.; Wei, S.; Szijártó, I. A.; Miljkovic, J. L.; Mitrovic, A.; Lange, M.; Savitsky, S.; Yadav, P. K.; Torregrossa, R.; et al. Improved Tag-Switch Method Reveals That Thioredoxin Acts as Depersulfidase and Controls the Intracellular Levels of Protein Persulfidation. Chemical Science 2016, 7 (5), 3414–3426. https://doi.org/10.1039/c5sc04818d

Supplementary material for: [https://doi.org/10.1039/c5sc04818d]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1925

Efficient C3-alkylsulfenylation of indoles under mild conditions using Lewis acid-activated 8-quinolinethiosulfonates.

The importance of sulfur-containing compounds in various fields, ranging from material science1-2 to medicinal chemistry, 3 has called for the development of synthetic strategies to form carbon-sulfur (C-S) bonds. Thus, numerous approaches based on the nucleophilicity of thiols have been designed over the years, which mostly use air-sensitive noble metal catalysts.4- 9 At the opposite, the use of electrophilic sulfur reagents is also a powerful, more eco-friendly approach, in particular for the sulfenylation of C-H bonds into C-S bonds.10-11 In this context, the sulfenylation of indoles (Equation 1) has become a benchmark reaction to develop and test new sulfenyl transfer reagents, because indoles are good nucleophiles and their occurrence in many natural products or biological active compounds makes them attractive synthetic targets.12-14 For instance, metal-catalyzed or metal-free protocols have been proposed, in which disulfides, sulfinic acid and their salts, sulfonyl chlorides, sulfonylhydrazine, or Nthiophtalimides are used as source of electrophilic sulfur.10,15-16 Thiosulfonates (RSO2SR’) are another class of emerging17 reagents, which were also studied for C-S bond formation18-20 and for indole sulfenylation.21 However, despite the large pool of sulfenylation agents listed above, the difficult activation of the chalcogen centre essentially limits these reagents to the formation of C-S(aryl) bonds. On the other hand, the transfer of alkylsulfenyl groups requires harsher activating conditions and is so far still limited<br /

Reversible Detection and Quantification of Hydrogen Sulfide by Fluorescence Using the Hemoglobin I from Lucina pectinata

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Reactivity of Persulfides Toward Strained Bicyclo[6.1.0]nonyne Derivatives: Relevance to Chemical Tagging of Proteins

Persulfides are an emerging class of cysteine oxidative post-translational modification. They react with the bioconjugation reagents bicyclo[6.1.0]­nonynes (BCNs) to engender thioethers and/or disulfides. This new reactivity of BCNs with a biologically important redox-signaling species efficiently interferes with the recent usage of strained cycloalkynes to specifically trap protein sulfenic acids

Synthesis, Stability, and Reactivity of [(TPA)Zn(SH)]+ in Aqueous and Organic Solutions

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New fluorescent zinc complexes: towards specific sensors for hydrogen sulfide in solution

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Synthesis, Characterization, and Reactivity of Alkyldisulfanido Zinc Complexes

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An Alternate Route to Disulfanido Complexes by Nucleophilic Attack of Thiolates on Ruthenium-Bound Thiosulfonato Ligands

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Synthesis and characterization of mononuclear hydroxamato and hydroximato complexes of iron(iii) based on the tris-(2-pyridylmethyl)amine ligand

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