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  • Publication
    Accès libre
    Double Targeting of Tumours with Pyrenyl-Modified Dendrimers Encapsulated in an Arene–Ruthenium Metallaprism
    (2011)
    Pitto-Barry, Anaïs
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    Barry, Nicolas P. E.
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    Zava, Olivier
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    Dyson, Paul J.
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    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
    Combining coordination and hydrogen-bonds to form arene ruthenium metalla-assemblies
    Appavoo, Divembal
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    Carnevale, Diego
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    ;
    Three ureido-pyrimidone derivatives (N-LH) were used to generate in combination with four dinuclear arene ruthenium clips, (p-cymene) 2Ru2(OO boolean AND OO)Cl2 (OO boolean AND OO = oxalato, 2,5-dioxido-1,4-benzoquinonato, 2,5-dichloro-1,4-benzoquinonato, 5,8-dioxido-1,4-naphtoquinonato), twelve cationic arene ruthenium metalla-cycles of the general formula [(p-cymene)2Ru2(OO boolean AND OO)(N-LH)2]2 (CF3SO3)4. The ureidopyrimidone moieties are able to form strong hydrogen-bonds by self-pairing, thus giving rise to dimeric structures in solution. In addition, to better understand the behavior of the tetranuclear metallacycles in solution, the neutral dinuclear arene ruthenium ureido-pyrimidone complexes of the general formula ((p-cymene)RuCl2(N-LH)} 2 were also prepared and characterized. All metalla-assemblies were studied in solution by NMR spectroscopy, confirming the high stability of the metalla- cycles and the usefulness of hydrogen-bonds in constructing supramolecular assemblies