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Total synthesis, isolation, surfactant properties, and biological evaluation of ananatosides and related macrodilactone-containing rhamnolipids

Cloutier Maude, Prévost Marie-Joëlle, Lavoie Serge, Feroldi Thomas, Piochon Marianne, Groleau Marie-Christine, Legault Jean, Villaume Sandra, Crouzet Jérôme, Dorey Stéphan, Dìaz De Rienzo Mayri Alejandra, Déziel Eric et Gauthier Charles. (2021). Total synthesis, isolation, surfactant properties, and biological evaluation of ananatosides and related macrodilactone-containing rhamnolipids. Chemical Science, 12, (21), p. 7533-7546.

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URL officielle: http://dx.doi.org/doi:10.1039/d1sc01146d

Résumé

Rhamnolipids are a specific class of microbial surfactants, which hold great biotechnological and therapeutic potential. However, their exploitation at the industrial level is hampered because they are mainly produced by the opportunistic pathogen Pseudomonas aeruginosa. The non-human pathogenic bacterium Pantoea ananatis is an alternative producer of rhamnolipid-like metabolites containing glucose instead of rhamnose residues. Herein, we present the isolation, structural characterization, and total synthesis of ananatoside A, a 15-membered macrodilactone-containing glucolipid, and ananatoside B, its open-chain congener, from organic extracts of P. ananatis. Ananatoside A was synthesized through three alternative pathways involving either an intramolecular glycosylation, a chemical macrolactonization or a direct enzymatic transformation from ananatoside B. A series of diasteroisomerically pure (1→2), (1→3), and (1→4)-macrolactonized rhamnolipids were also synthesized through intramolecular glycosylation and their anomeric configurations as well as ring conformations were solved using molecular modeling in tandem with NMR studies. We show that ananatoside B is a more potent surfactant than its macrolide counterpart. We present evidence that macrolactonization of rhamnolipids enhances their cytotoxic and hemolytic potential, pointing towards a mechanism involving the formation of pores into the lipidic cell membrane. Lastly, we demonstrate that ananatoside A and ananatoside B as well as synthetic macrolactonized rhamnolipids can be perceived by the plant immune system, and that this sensing is more pronounced for a macrolide featuring a rhamnose moiety in its native 1C4 conformation. Altogether our results suggest that macrolactonization of glycolipids can dramatically interfere with their surfactant properties and biological activity.

Type de document:Article publié dans une revue avec comité d'évaluation
ISSN:2041-6520
Volume:12
Numéro:21
Pages:p. 7533-7546
Version évaluée par les pairs:Oui
Date:2021
Identifiant unique:10.1039/d1sc01146d
Sujets:Sciences naturelles et génie > Sciences naturelles > Biologie et autres sciences connexes
Sciences naturelles et génie > Sciences naturelles > Chimie
Département, module, service et unité de recherche:Départements et modules > Département des sciences fondamentales
Mots-clés:Rhamnolipids, isolation, surfactant properties, cytotoxicity, hemolytic potential
Déposé le:27 oct. 2021 21:02
Dernière modification:27 oct. 2021 21:02
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