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Gallium- and Iron-Pyoverdine Coordination Compounds Investigated by X-ray Photoelectron Spectroscopy and X-ray Absorption Spectroscopy

dc.contributor.authorNICOLAFRANCESCO, Chiara
hal.structure.identifierCentre d'Etudes Nucléaires de Bordeaux Gradignan [CENBG]
dc.contributor.authorPORCARO, Francesco
dc.contributor.authorPIS, Igor
dc.contributor.authorNAPPINI, Silvia
dc.contributor.authorSIMONELLI, Laura
dc.contributor.authorMARINI, Carlo
dc.contributor.authorFRANGIPANI, Emanuela
dc.contributor.authorVISAGGIO, Daniela
dc.contributor.authorVISCA, Paolo
dc.contributor.authorMOBILIO, Settimio
dc.contributor.authorMENEGHINI, Carlo
dc.contributor.authorFRATODDI, Ilaria
dc.contributor.authorIUCCI, Giovanna
dc.contributor.authorBATTOCCHIO, Chiara
dc.date.issued2019
dc.identifier.issn0020-1669
dc.description.abstractEnIron is an essential nutrient for nearly all forms of life, although scarcely available due to its poor solubility in nature and complex formation in higher eukaryotes. Microorganisms have evolved a vast array of strategies to acquire iron, the most common being the production of high-affinity iron chelators, termed siderophores. The opportunistic bacterial pathogen Pseudomonas aeruginosa synthesizes and secretes two siderophores, pyoverdine (PVD) and pyochelin (PCH), characterized by very different structural and functional properties. Due to its chemical similarity with Fe(III), Ga(III) interferes with several iron-dependent biological pathways. Both PVD and PCH bind Fe(III) and Ga(III). However, while the Ga-PCH complex is more effective than Ga(III) in inhibiting P. aeruginosa growth, PVD acts as a Ga(III) scavenger and protects bacteria from Ga(III) toxicity. To gain more insight into the different outcomes of the biological paths observed for the Fe(III) and Ga(III)-siderophore complexes, better knowledge is needed of their coordination geometries that directly influence the metal complexes chemical stability. The valence state and coordination geometry of the Ga-PCH and Fe-PCH complexes has recently been investigated in detail; as for PVD complexes, several NMR structural studies of Ga(III)-PVD are reported in the literature, using Ga(III) as a diamagnetic isosteric substitute for Fe(III). In this work, we applied up-to-date spectroscopic techniques as synchrotron-radiation-induced X-ray photoelectron spectroscopy (SR-XPS) and X-ray absorption fine structure (XAFS) spectroscopy coupled with molecular modeling to describe the electronic structure and coordination chemistry of Fe and Ga coordinative sites in PVD metal complexes. These techniques allowed us to unambiguously determine the oxidation state of the coordinative ions and to gather interesting information about the similarities and differences between the two coordination compounds as induced by the different metal.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enGallium- and Iron-Pyoverdine Coordination Compounds Investigated by X-ray Photoelectron Spectroscopy and X-ray Absorption Spectroscopy
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.inorgchem.8b03574
dc.subject.halPhysique [physics]
bordeaux.journalInorganic Chemistry
bordeaux.page4935-4944
bordeaux.volume58
bordeaux.issue8
bordeaux.peerReviewedoui
hal.identifierhal-02116475
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-02116475v1
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