CE06 - Polymères, composites, physique et chimie de la matière molle

REdox-Controlled Hybridization of ElectRoactive Homo- and Heteroduplexes based on foldamErs – RECHERCHE

Submission summary

Over the last two decades, the family of synthetic foldamers has focused a considerable interest, for applications as diverse as HIV treatment, catalysis, photo-controlled folding, or selective guest encapsulation. A special attention has also been paid to the rich supramolecular chemistry of foldamers, since some of them tend to hybridize to form multistranded helices (double in general), exhibiting specific physico-chemical properties
Therefore, an obvious research interest concerns the parameters governing these equilibria (simple vs multiple helices), which are intrinsically associated to solute-solute and solute-solvent interactions. For instance, it was proven possible to shift the equilibrium towards the hybridized structures by increasing the concentration, by lowering the temperature or by taking advantage of solvophobic effects. The presence of a cavity inside the loops of miscellaneous foldameric backbones has been also explored to evaluate the impact of guest binding over the hybridization process.
It is worth noting that while it is sometimes possible to shift this equilibrium by controlling the temperature in a reversible manner, reversibility is hardly reached when diluting a solution, changing the solvent or introducing guests. It remains indeed complicated to evaporate/extract a solvent or a given guest, without modifying the composition of the medium.

Therefore, triggering in a reversible way the equilibrium between single and hybridized helices constitutes a fundamental exciting challenge to tackle, which is the central concept of the RECHERCHE project.

In this context, the coordinator and his partners have recently synthesized and characterized a foldamer from the oligopyridinedicarboxamide family endowed with tetrathiafulvalene units at both extremities. By taking advantage of a recent interaction of the supramolecular toolbox (radical-cation dimerization processes), the dimerization constant of the corresponding homoduplex structures proved to be two orders of magnitude higher once TTF units are oxidized.
This result constitutes the foundation of the RECHERCHE project, which will exploit this innovative approach to drive interstrands contacts thanks to redox-controlled non-covalent interactions.
On this ground, the RECHERCHE project was constructed around three main objectives: 1) generalizing the former approach by using alternative pi-functional units capable of radical cation dimerization (e.g. viologen, porphyrin) ; 2) synthesizing original heteroduplex structures through donor-acceptor interactions in a selective manner and controlling their formation through redox stimulations ; 3) transferring the RECHERCHE concepts to self-assembled monolayers (SAMs) on gold electrodes and nanoparticles. Thereby, the supramolecular chemistry of the foldamers will be studied after the grafting process, and in particular to synthesize redox-controlled networks of nanoparticles, a field of strong current interest.
Finally, the RECHERCHE project is also characterized by a highly multidisciplinary approach, gathering experts with young various skills, while allowing a researcher to lead a research line in an independent manner.

Project coordination

David Canevet (INSTITUT DES SCIENCES ET TECHNOLOGIES MOLECULAIRES D'ANGERS (MOLTECH-Anjou))

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

INSTITUT DES SCIENCES ET TECHNOLOGIES MOLECULAIRES D'ANGERS (MOLTECH-Anjou)

Help of the ANR 210,816 euros
Beginning and duration of the scientific project: January 2020 - 48 Months

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