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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
    Synthesis, molecular structure and cytotoxicity of molecular materials based on water soluble half-sandwich Rh(III) and Ir(III) tetranuclear metalla-cycles
    (2013)
    Gupta, Gajendra
    ;
    Murray, Benjamin S.
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The neutral dinuclear complexes [(?5-C5Me5)2Rh2(?-dhnq)Cl2] (1) and [(?5-C5Me5)2Ir2(?-dhnq)Cl2] (2) (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(?5-C5Me5)M(?-Cl)Cl]2 (M = Rh, Ir) with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4'-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(?5-C5Me5)4M4(?-dhnq)2(?-L)2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4'-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by IR, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure anal. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest mols. In addn., the antiproliferative activity of the metalla-cycles 3-8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range. [on SciFinder(R)]
  • Publication
    Accès libre
    Thiolato-Bridged Arene–Ruthenium Complexes: Synthesis, Molecular Structure, Reactivity, and Anticancer Activity of the Dinuclear Complexes [(arene)2Ru2 (SR)2Cl2]
    (2012)
    Ibao, Anne-Flore
    ;
    Gras, Michaël
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    Treatment of an arene–ruthenium dichloride dimer with thiols RSH to lead to cationic trithiolato complexes of the type [(arene) 2Ru2(SR)3]+ was shown to proceed through the neutral thiolato complexes [(arene)2Ru2(SR)2Cl2], which have been isolated and characterized for arene = p-MeC6H4iPr and R = CH2Ph (1), CH2CH2Ph (2), CH2C6H4-p-tBu (3), and C6H11 (4). The single-crystal X-ray structure analysis of the p-tert-butylbenzyl derivative 3 reveals that the two ruthenium atoms are bridged by the two thiolato ligands without a metal–metal bond. The neutral dithiolato complexes[(arene)2Ru2(SR)2Cl2] (1–3) are intermediates in the formation of the cationic trithiolato complexes [(arene)2Ru2(SR)3]+ (5–7). Of the new [(arene)2Ru2(SR)2Cl2] complexes, derivative 2 is highly cytotoxic against human ovarian cancer cells, with IC50 values of 0.20 μM for the A2780 cell line and 0.31 for the cisplatin-resistant cell line A2780cisR.
  • Publication
    Accès libre
    Excellent Correlation between Drug Release and Portal Size in Metalla-Cage Drug-Delivery Systems
    (2011)
    Barry, Nicolas P.E.
    ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    A series of large cationic hexanuclear metalla-prisms, [Ru6(p-iPrC6H4Me)6(tpt)2(donq)3]6+, [Ru6(p-iPrC6H4Me)6(tpt)2(doaq)3]6+ and [Ru6(p-iPrC6H4Me)6(tpt)2(dotq)3]6+, composed of p-cymene–ruthenium building blocks bridged by OO∩OO ligands (donq=5,8-dioxido-1,4-naphthoquinonato; doaq=5,8-dioxido-1,4-anthraquinonato, dotq=6,11-dioxido-5,12-naphthacenedionato) and connected by two 2,4,6-tripyridin-4-yl-1,3,5-triazine (tpt) panels, which encapsulate the guest molecules 1-(4,6-dichloro-1,3,5-triazin-2-yl)pyrene and Pd(acac)2, have been prepared. The host–guest properties of these water-soluble delivery systems were studied in solution by NMR and fluorescence spectroscopy, providing the stability constants (K) for these host–guest systems. Moreover, the ability of the hosts to deliver the guests into cancer cells was evaluated and the uptake mechanism studied; the rate of release of the guest molecule was found to depend on the portal size of the host.
  • Publication
    Accès libre
    Double Targeting of Tumors with Pyrenyl-Modified Dendrimers Encapsulated in an Arene-Ruthenium Metallaprism
    (2011)
    Pitto-Barry, Anais
    ;
    Barry, Nicolas P. E.
    ;
    Zava, Olivier
    ;
    Deschenaux, Robert 
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The self-assembly of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine (tpt) triangular panels with p-cymene-ruthenium building blocks and 5,8-dioxido-1,4-naphthoquinonato (donq) bridges, in the presence of pyrenyl-contg. dendrimers of different generations (P0, P1 and P2), affords the triangular prismatic host-guest compds. [Pn?Ru6(p-cymene)6(tpt)2(donq)3]6+ ([Pn?1]6+). The host-guest nature of these systems, with the pyrenyl moiety being encapsulated in the hydrophobic cavity of the cage and the dendritic functional group pointing outwards, was confirmed by NMR spectroscopy (1H, 2D and DOSY). The host-guest properties of these systems were studied in soln. by NMR and UV/Vis spectroscopic methods, allowing the detn. of their affinity consts. (Ka). Moreover, the ability of these water-sol. host-guest systems to carry the pyrenyl-contg. dendrimers into cancer cells was evaluated on human ovarian cancer cells. The host-guest systems are all more cytotoxic than the empty cage [1][CF3SO3]6 (IC50?4 ?M), with the most active compd., [P0?1][CF3SO3]6, being an order of magnitude more cytotoxic. [on SciFinder(R)]
  • Publication
    Accès libre
    Double Targeting of Tumours with Pyrenyl-Modified Dendrimers Encapsulated in an Arene–Ruthenium Metallaprism
    (2011)
    Pitto-Barry, Anaïs
    ;
    Barry, Nicolas P. E.
    ;
    Zava, Olivier
    ;
    Deschenaux, Robert 
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The self-assembly of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine (tpt) triangular panels with p-cymene–ruthenium building blocks and 5,8-dioxido-1,4-naphthoquinonato (donq) bridges, in the presence of pyrenyl-containing dendrimers of different generations (P0, P1 and P2), affords the triangular prismatic host–guest compounds [Pn⊂Ru6(p-cymene)6(tpt)2(donq)3]6+ ([Pn⊂1]6+). The host–guest nature of these systems, with the pyrenyl moiety being encapsulated in the hydrophobic cavity of the cage and the dendritic functional group pointing outwards, was confirmed by NMR spectroscopy (1H, 2D and DOSY). The host–guest properties of these systems were studied in solution by NMR and UV/Vis spectroscopic methods, allowing the determination of their affinity constants (Ka). Moreover, the ability of these water-soluble host–guest systems to carry the pyrenyl-containing dendrimers into cancer cells was evaluated on human ovarian cancer cells. The host–guest systems are all more cytotoxic than the empty cage [1][CF3SO3]6 (IC50≈4 μM), with the most active compound, [P0⊂1][CF3SO3]6, being an order of magnitude more cytotoxic.
  • Publication
    Accès libre
    Thiophenolato-bridged dinuclear arene ruthenium complexes: a new family of highly cytotoxic anticancer agents
    (2010)
    Gras, Michaël
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    New cationic diruthenium complexes of the type [(arene)2Ru2(SPh)3]+ , arene being C6H6, p-iPrC6H4Me, C6Me6, C6H5R, where R = (CH2)nOC(O)C6H4-p-O(CH2)6CH3 or (CH2)nOC(O)CH[double bond, length as m-dash]CHC6H4-p-OCH3 and n = 2 or 4, are obtained from the reaction of the corresponding precursor [(arene)RuCl2]2 and thiophenol and isolated as their chloride salts. The complexes have been fully characterised by spectroscopic methods and the solid state structure of [(C6H6)2Ru2(SPh)3]+, crystallised as the hexafluorophosphate salt, has been established by single crystal X-ray diffraction. The complexes are highly cytotoxic against human ovarian cancer cells (cell lines A2780 and A2780cisR), with the IC50 values being in the submicromolar range. In comparison the analogous trishydroxythiophenolato compounds [(arene)2Ru2(S-p-C6H4OH)3]Cl (IC50 values around 100 μM) are much less cytotoxic. Thus, it would appear that the increased antiproliferative effect of the arene ruthenium complexes is due to the presence of the phenyl or toluyl substituents at the three thiolato bridges.
  • Publication
    Accès libre
    Drug delivery of lipophilic pyrenyl derivatives by encapsulation in a water soluble metalla-cage
    (2010)
    Mattsson, Johan
    ;
    Zava, Olivier
    ;
    Renfrew, Anna K.
    ;
    Sei , Yoshihisa
    ;
    Yamaguchi, Kentaro
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The self-assembly of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine (tpt) triangular panels with p-cymene (p-PriC6H4Me) ruthenium building blocks and 2,5-dioxydo-1,4-benzoquinonato (dobq) bridges, in the presence of a functionalised pyrenyl derivative (pyrene–R), affords the triangular prismatic host–guest compounds [(pyrene–R) ⊂ Ru6(p-PriC6H4Me)6(tpt)2 (dobq)3]6+ ([(pyrene–R) ⊂ 1]6+). The inclusion of eight mono-substituted pyrenyl derivatives including biologically relevant structures (a = 1-pyrenebutyric acid, b = 1-pyrenebutanol, c = 1-pyrenemethylamine, d = 1-pyrenemethylbutanoate, e = 1-(4,6-dichloro-1,3,5-triazin-2-yl)pyrene, f = N-hexadecylpyrene-1-sulfonamide, g = pyrenyl ethacrynic amide and h = 2-(pyren-1-ylmethylcarbamoyl) phenyl acetate), and a di-substituted pyrenyl derivative (i = 1,8-bis(3-methyl-butyn-1-yl-3-ol)pyrene), has been accomplished. The carceplex nature of these systems with the pyrenyl moiety being firmly encapsulated in the hydrophobic cavity of the cage with the functional groups pointing outwards was confirmed by NMR (1H, 2D, DOSY) spectroscopy and electrospray ionization mass spectrometry (ESI-MS). The cytotoxicities of these water-soluble compounds have been established using human ovarian A2780 cancer cells. All the host–guest systems are more cytotoxic than the empty cage itself [1][CF3SO3]6 (IC50 = 23 μM), the most active carceplex [f ⊂ 1][CF3SO3]6 is an order of magnitude more cytotoxic.
  • Publication
    Accès libre
    Synthesis, Characterization and Anticancer Activity of Porphyrin-Containing Organometallic Cubes
    (2010)
    Barry, Nicolas P. E.
    ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H2) and 5,10,15,20-tetra(4-pyridyl)porphyrin-M(ii) (M = Ni (tpp-Ni); Zn (tpp-Zn)) tetradentate panels with the dinuclear p-cymene ruthenium clips [Ru2(p-cymene)2(C2O4)Cl2] and [Ru2(p-cymene)2(C6H2O4)Cl2] (C2O4 = oxalato; C6H2O4 = 2,5-dioxydo-1,4-benzoquinonato) affords the cationic organometallic cubes: [Ru8(p-cymene)8(tpp-H2)2(C2O4)4]8+ (1); [Ru8(p-cymene)8(tpp-Ni)2(C2O4)4]8+ (2); [Ru8(p-cymene)8(tpp-Zn)2(C2O4)4]8+ (3); [Ru8(p-cymene)8(tpp-H2)2(C6H2O4)4]8+ (4); [Ru8(p-cymene)8(tpp-Ni)2(C6H2O4)4]8+ (5); and [Ru8(p-cymene)8(tpp-Zn)2(C6H2O4)4]8+ (6). In addition, the new dinuclear arene ruthenium 2,5-dioxydo-1,4-benzoquinonato clips [Ru2(indane)2(C6H2O4)Cl2] (7) and [Ru2(nonylbenzene)2(C6H2O4)Cl2] (8) react in methanol with tpp-H2 in the presence of silver triflate to afford the corresponding cationic cubes [Ru8(indane)8(tpp-H2) 2(C6H2O4)4]8+ (9) and [Ru8 (nonylbenzene)8(tpp-H2)2(C6H2O4)4]8+ (10) respectively. All cationic metalla-cubes were isolated as triflate salts and characterized by NMR, infrared, electro-spray mass spectrometry and UV-visible spectroscopy. Moreover, the formation of unsymmetrical metalla-cubes built using a mixture of the different porphyrin panels during the self-assembly of the 2,5-dioxydo-1,4-benzoquinonato metalla-cubes, [Ru8(p-cymene)8(tpp-H2)(tpp-Ni)(C6H2O4)4]8+ (11), [Ru8(p-cymene)8(tpp-H2)(tpp-Zn)(C6H2O4)4]8+ (12), and [Ru8(p-cymene)8(tpp-Ni)(tpp-Zn)(C6H2O4)4]8+ (13), was studied by electro-spray mass spectrometry. The cytotoxicities of all metalla-cubes as well as the mixtures containing the unsymmetrical metalla-cubes were established on human ovarian A2780 and A2780cisR cancer cell lines. All symmetrical compounds are equally cytotoxic (IC50 = 7–15 μM) (IC50 being the drug concentration necessary for 50% inhibition of cell viability) against both A2780 and cisplatin-resistant A2780cisR cancer cells, with stronger cytotoxicities (IC50 = 2–5 μM) observed for the mixtures containing the unsymmetrical 2,5-dioxydo-1,4-benzoquinonato metalla-cubes.
  • Publication
    Accès libre
    Anticancer activity of opened arene ruthenium metalla-assemblies
    (2010)
    Barry, Nicolas P. E.
    ;
    Zava, Olivier
    ;
    Furrer, Julien
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    Cationic tetranuclear and hexanuclear opened metalla-assemblies incorporating 5,15-bis(4-pyridyl)-10,20-diphenylporphyrin (bpp) or 5,10,15-tris(4-pyridyl)-20-phenylporphyrin (tpp) panels and dinuclear arene ruthenium clips [(p-cymene)2Ru2(OO?OO)2]2+ (OO?OO = oxalato, 2,5-dioxydo-1,4-benzoquinonato (dobq)) have been assembled in the presence of silver triflate. All complexes were characterized by NMR, IR and UV-visible spectroscopy and electrospray ionization mass spectrometry. The cytotoxicities of the tetranuclear and hexanuclear ruthenium complexes have been established on ovarian A2780 and A2780cisR cancer cell lines. The compds. are quite cytotoxic, the most active metalla-assembly being [Ru6(p-cymene)6(dobq)3(tpp)2]6+, with IC50 values of 2.1 ?M and 3.8 ?M against A2780 and A2780cisR cells, resp. [on SciFinder(R)]
  • Publication
    Accès libre