multi STimuli Responsive Aqueous Polymer Assemblies – STRAPA

The development and application of multistimuli responsive materials is a burgeoning field of study in leading research groups in the USA, Asia and mainland Europe (at present this field is underrepresented in France).Such soft advanced materials are expected to revolutionize nano-science, engineering and technology and, therefore, they are key to many countries future technological competitiveness. However, there is no doubt that the creation of such high performance materials relies directly on our ability to manipulate these “smart” materials in a controllable, predictable and orchestrated fashion at the molecular and also at supramolecular level.
In this context, we propose to engineer and study a new class of supramolecular polymer materials including block copolymers, branched polymers, star (co)polymers, networks and biohybrid structures capable of responding to multiple external stimuli in a controllable and predictable fashion in aqueous environments. The architectures of these materials will be constructed by specifically bringing together complementary well-defined polymer building blocks (prepared by CRP) with specially designed host/guest motifs attached in specific locations on polymer backbones. Polymeric building blocks will be orthogonally held together through pseudorotaxane linkages, thereby offering materials with reversible and switchable properties. More importantly, in this proposal, we will exploit well-defined polymer building blocks whereby the “periphery” can be reversibly modified, via the formation/disruption of non-covalent host-guest complexes both under electrochemical (oxidation and/or reduction) and phase transition control or upon the addition of a competitive guest molecule. This lock and key approach will offer the unique opportunity to control polymer structure (e.g topology and morphology) and properties. Furthermore, the inherent reversibility of supramolecular architectures will allow “on demand” modular and tunable modification of structure and properties of appropriately functionalised macromolecules, and thus will afford novel systems with applications in materials science and nanotechnology.
Such smart supramolecular polymer materials, with tunable structures and properties are expected to find novel advanced technology applications in: i) new generation of tunable nanosized self-assembled structures such as micelles, nanotubes and polymersomes, ii) new class of multiresponsive rheological fluids, self-healing and self-repairing materials, iii) new family of smart bioconjugates. Another objective of this research program is to gain a better understanding of the basic concepts of self-assembly in water that should, therefore, help to bridge the gap between synthetic polymer and material chemists, and biochemical researchers.
To accomplish this challenging research program, a consortium combining skills and expertise on organic chemistry, controlled radical polymerisation, supramolecular chemistry and physical-chemistry will be assembled.