title: Redox Reactivity of Cerium Oxide Nanoparticles Induces the Formation of Disulfide Bridges in Thiol-Containing Biomolecules.
abstract: The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine-cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce(4+)/Ce(3+) redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce(3+) disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules.
authors.affiliation: CEA/DSV/iBEB/SBTN, Laboratoire d'Etude des Protéines Cibles, BP17171, F-30207 Bagnols sur Cèze Cedex, France.|Labex Serenade Safe(r) Ecodesign Research and Education applied to NAnomaterial DEvelopment.
authors.forename: Françoise
authors.initials: F
authors.lastname: Rollin-Genetet
authors.affiliation: CEA/DSV/iBEB/SBTN, Laboratoire d'Etude des Protéines Cibles, BP17171, F-30207 Bagnols sur Cèze Cedex, France.
authors.forename: Caroline
authors.initials: C
authors.lastname: Seidel
authors.affiliation: Institut Méditerranéen de Biodiversité et d'Ecologie marine et continentale (IMBE), Technopôle Arbois-Méditerranée, Bât. Villemin - BP 80, F-13545 Aix-en-Provence cedex 04, France.|Labex Serenade Safe(r) Ecodesign Research and Education applied to NAnomaterial DEvelopment.
authors.forename: Ester
authors.initials: E
authors.lastname: Artells
authors.affiliation: Aix-Marseille Université, CNRS, IRD, CEREGE UM34, UMR 7330, F-13545 Aix en Provence, France.|iCEINT International Consortium for the Environmental Implications of Nanotechnology , F-13545 Aix en Provence, France.|Labex Serenade Safe(r) Ecodesign Research and Education applied to NAnomaterial DEvelopment.
authors.forename: Mélanie
authors.initials: M
authors.lastname: Auffan
authors.affiliation: Institut Méditerranéen de Biodiversité et d'Ecologie marine et continentale (IMBE), Technopôle Arbois-Méditerranée, Bât. Villemin - BP 80, F-13545 Aix-en-Provence cedex 04, France.|iCEINT International Consortium for the Environmental Implications of Nanotechnology , F-13545 Aix en Provence, France.|Labex Serenade Safe(r) Ecodesign Research and Education applied to NAnomaterial DEvelopment.
authors.forename: Alain
authors.initials: A
authors.lastname: Thiéry
authors.affiliation: CEA/DSV/iBEB/SBTN, Laboratoire d'Etude des Protéines Cibles, BP17171, F-30207 Bagnols sur Cèze Cedex, France.|iCEINT International Consortium for the Environmental Implications of Nanotechnology , F-13545 Aix en Provence, France.|Labex Serenade Safe(r) Ecodesign Research and Education applied to NAnomaterial DEvelopment.
authors.forename: Claude
authors.initials: C
authors.lastname: Vidaud
mesh_terms: D000818:Animals; D002563:Cerium / Q000737:chemistry*; D002942:Circular Dichroism; D003545:Cysteine / Q000737:chemistry*; D004220:Disulfides / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008099:Liver / Q000473:pathology; D053768:Metal Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D011817:Rabbits; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D004220:Disulfides; D013438:Sulfhydryl Compounds; D002563:Cerium; C030583:ceric oxide; D003545:Cysteine