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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Accès libre
    Combined arene ruthenium porphyrins as chemotherapeutics and photosensitizers for cancer therapy
    (2009)
    Schmitt, Frédéric
    ;
    Govindaswamy, Padavattan
    ;
    Zava, Olivier
    ;
    Süss-Fink, Georg 
    ;
    Juillerat-Jeanneret, Lucienne
    ;
    Therrien, Bruno 
    Mononuclear 5-(4-pyridyl)-10,15,20-triphenylporphyrin and 5-(3-pyridyl)-10,15,20-triphenylporphyrin as well as tetranuclear 5,10,15,20-tetra(4-pyridyl)porphyrin (tetra-4-pp) and 5,10,15,20-tetra(3-pyridyl)porphyrin) (tetra-3-pp) arene ruthenium(II) derivatives (arene is C6H5Me or p-PriC6H4Me) were prepared and evaluated as potential dual photosensitizers and chemotherapeutics in human Me300 melanoma cells. In the absence of light, all tetranuclear complexes were cytotoxic (IC50 ≤ 20 μM), while the mononuclear derivatives were not (IC50 ≥ 100 μM). Kinetic studies of tritiated thymidine and tritiated leucine incorporations in cells exposed to a low concentration (5 μM) of tetranuclear p-cymene derivatives demonstrated a rapid inhibition of DNA synthesis, while protein synthesis was inhibited only later, suggesting arene ruthenium–DNA interactions as the initial cytotoxic process. All complexes exhibited phototoxicities toward melanoma cells when exposed to laser light of 652 nm. At low concentration (5 μM), LD50 of the mononuclear derivatives was between 5 and 10 J/cm2, while for the tetranuclear derivatives LD50 was approximately 2.5 J/cm2 for the [Ru4 (η6-arene)4 (tetra-4-pp)Cl8] complexes and less than 0.5 J/cm2 for the [Ru4 (η6-arene)4 (tetra-3-pp)Cl8] complexes. Examination of cells under a fluorescence microscope revealed the [Ru4 (η6-arene)4 (tetra-4-pp)Cl8] complexes as cytoplasmic aggregates, whereas the [Ru4(η6-arene)4(tetra-3-pp)Cl8] complexes were homogenously dispersed in the cytoplasm. Thus, these complexes present a dual synergistic effect with good properties of both the arene ruthenium chemotherapeutics and the porphyrin photosensitizer.
  • Publication
    Accès libre
    Encapsulation of Triphenylene Derivatives in the Hexanuclear Arene Ruthenium Metallo-Prismatic Cage [Ru6 (p-PriC6H4Me)6(tpt)2 (dhbq)3]6+ (tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, dhbq = 2,5-dihydroxy-1,4-benzoquinonato)
    (2008)
    Govindaswamy, Padavattan
    ;
    Furrer, Julien
    ;
    Süss-Fink, Georg 
    ;
    Therrien, Bruno 
    A large cationic triangular metallo-prism, [Ru6(p-PriC6H4Me)6 (tpt)2 (dhbq)3]6+ (1)6+, incorporating p-cymene ruthenium building blocks, bridged by 2,5-dihydroxy-1,4-benzoquinonato (dhbq) ligands, and connected by two 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) subunits, allows the permanent encapsulation of the triphenylene derivatives hexahydroxytriphenylene, C18H6 (OH)6 and hexamethoxytriphenylene, C18H6 (OMe)6. These two cationic carceplex systems [C18H6 (OH)6⊂1]6+ and [C18H6 (OMe)6⊂1]6+ have been isolated as their triflate salts. The molecular structure of these systems has been established by one-dimensional 1H ROESY NMR experiments as well as by the single-crystal structure analysis of [C18H6 (OMe)6⊂1][O3SCF3]6.
  • Publication
    Accès libre
    Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry
    (2007)
    Govindaswamy, Padavattan
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Štěpnička, Petr
    ;
    Ludvík, Jiří
    The mononuclear complexes [(η5-C5Me5)IrCl(L1)] (1), [(η5-C5Me5)RhCl(L1)] (2), [(η6-p-PriC6H4Me)RuCl(L1)] (3) and [(η6-C6Me6)RuCl(L1)] (4) have been synthesised from pyrazine-2-carboxylic acid (HL1) and the corresponding complexes [{(η5-C5Me5)IrCl2}2], [{(η5-C5Me5)RhCl2}2], [{(η6-p-PriC6H4Me)RuCl2}2], and [{(η6-C6Me6)RuCl2}2], respectively. The related dinuclear complexes [{(η5-C5Me5)IrCl}2 (μ-L2)] (5), [{(η5-C5Me5)RhCl}2 (μ-L2)] (6), [{(η6-p-PriC6H4Me)RuCl}2 (μ-L2)] (7) and [{(η6-C6Me6)RuCl}2 (μ-L2)] (8) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H2L2). Compounds isomeric to the latter series, [{(η5-C5Me5)IrCl}2 (μ-L3)] (9), [{(η5-C5Me5)RhCl}2 (μ-L3)] (10), [{(p-PriC6H4Me)RuCl}2 (μ-L3)] (11) and [{(η6-C6Me6)RuCl}2 (μ-L3)] (12), have been prepared by using pyrazine-2,3-dicarboxylic acid (H2L3) instead of H2L2. The molecular structures of 2 and 3, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an N,O-chelating ligand, while the structure analyses of 5–7, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques.