Libération de NO photocontrôlée : complexes de ruthénium à ligand nitrosyle pour des applications innovantes en photothérapie

Abstract : Nitric oxide NO• is involved in numerous biological processes. It takes part to vasodilatation, neurotransmission, it can trigger cell proliferation or apoptosis and it also has bactericidal properties. Thus, NO• release control is of high interest for biomedical applications such as photo-activated chemotherapy (PACT) or photodynamic inactivation (PDI). The strategy here is to synthesize photoreactive ruthenium complexes with nitrosyl ligand which can release NO• under one and two-photon absorption. Compared with one-photon excitation, two-photon excitation allows high focalization and deep penetration of the beam, while exciting in the therapeutic window. This thesis is dedicated to the synthesis of [RuNO] complexes and their biological applications. The first chapter develops the state of the art in the field of ruthenium nitrosyl complexes and presents the biological issues. The second chapter presents the NO• photorelease properties of complexes with 4'-(2-fluorenyl)-2,2':6',2''-terpyridine ligand under one and two-photon excitation by spectroscopic studies. Photoproducts are characterized by X-ray diffraction. In a third chapter, cis (Cl,Cl)- and trans (Cl,Cl)-[RuII(2-fluorene-terpyridine)Cl2NO]PF6 are studied in water. The photorelease capacities of trans (NO,OH)-[RuII(fluorene-terpyridine)(Cl)(OH)(NO)]PF6 are studied in biological conditions. The fourth chapter presents the synthesis of new complexes with 4'-(2-fluorenyl)-2,2':6',2''-terpyridine ligand derivatives and their photorelease properties. The fifth chapter describes the phototoxic studies of these complexes on cancer cells (HCT 116 and FaDu). Finally, in the sixth chapter, the outstanding properties of these systems in the falling of antibiotic resistance in Staphylococcus epidermidis are exposed.
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Mathilde Bocé. Libération de NO photocontrôlée : complexes de ruthénium à ligand nitrosyle pour des applications innovantes en photothérapie. Chimie thérapeutique. Université Paul Sabatier - Toulouse III, 2018. Français. ⟨NNT : 2018TOU30158⟩. ⟨tel-02301091⟩

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