53 research outputs found

    Binding of Small Molecules and Metallic Complexes to DNA: A Methodological Approach

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    International audienc

    Self-Assembly of Polynuclear Arrays for Sensing Purposes.

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    International audienc

    Unravelling self-assembly of lanthanide helicates: Switching from deduction to induction

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    International audienceClassical supramolecular approach involving thermodynamic and kinetic characterisation is discussed for polymetallic lanthanide complexes with neutral ligands. These experimental studies allow (i) to obtain the stability constants of the self-assembled species and (ii) to establish the formation mechanism. Consequently, the analysis of these data with thermodynamic models promotes a deeper rationalization of self-assembly. The quantitative energetic parametrization of inter- and intra-molecular processes together with intermetallic and interligand interactions is obtained for europium(III) complexes of similar structure. To confirm the predictive ability of this thermodynamic modelling, the stability constant of the homologous tetrametallic helicate [Eu4(L4)3]12+ has been computed. An excellent agreement between the predicted and the experimental value of demonstrates the power of this innovative approach for supramolecular programming

    How to Adapt Scatchard Plot for Graphically Addressing Cooperativity in Multicomponent Self-Assemblies

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    International audienceA graphical method has been developed for the reliable detection of cooperativity in polymetallic complexes involving intra- and intermolecular complexation processes. The method relies on the determination of the partial occupancy r(AL)n, which represents the average number of metals bound per preassembled receptor AL(n) made up of n ligands bound to a linker A. We observe nonlinear, i.e., nonstatistical, Scatchard-like plots (r(AL)n/[M] vs r(AL)n) for metal-binding in double-stranded helicates. The present concept is extended to a virtual, pre-organized receptor L(n), in which no specific linker is involved. Applications to several polymetallic helicates reveal the presence of negatively cooperative processes attributed mainly to intermetallic repulsions, in agreement with recent thermodynamic models
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