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Communication Dans Un Congrès Année : 2022

Supramolecular polymeric systems featuring memory function(s)


Memory refers to any information processing system that can encode, store, retain, and restitute information, for which the brain is an unsurpassed example. Over the past decade, the demand for polymeric materials that have the ability to store their physical and/or physicochemistry state at a given time and provide access to this information at a later time has increased enormously. In essence, such polymeric systems featuring a memory function require hysteresis in a certain property when subjected to stimuli-dependent perturbations, thereby allowing to store information in a metastable, kinetically trapped state. Temperature is undoubtedly the most fundamental thermodynamic parameter that is not only important in our everyday life but also in Science as it plays an important role in the intrinsic characteristics and the functioning of a plethora of biological, physical and chemical systems and processes. As a result, temperature measurements cover a broad scope of needs and countless applications. Herein, we propose a supramolecular approach that enables polymeric systems to remember the heat treatment at which it was exposed. To the end, a different supramolecular and thermoresponsive polymeric memory devices were designed based on a poly(N-isopropylacrylamide) (PNIPAm) functionalized with of electron rich dialkoxynaphthalene guest units (Napht-co-PNIPAmGel). This polymeric system can be complexed through host-guest interactions with the tetracationic cyclobis(paraquat-p-phenylene) (CBPQT4+,4Cl-) host leading to an important increase of their hydrophilic character. For linear funtuonalized side chain, the therloresponsivenss . . Above the volume phase transition temperature (VPTT) of the complexed hydrogel, the collapse of the PNIPAM chains induces both decomplexation of the host-guest complexes within the hydrogel and shrinking due to LCST-driven dehydration. As the extend of dehydration of the hydrogel depends on the temperature, the release rate of the free host by diffusion out of the hydrogel was hypothesized to also depend on the temperature, thereby providing the basis for the time-memory function at a certain temperature. Controlled deformation processes are ubiquitous both in biological systems and materials science. For example, muscles may undergo expansion or contraction as a result of an external physiological stimuli. Similarly, synthetic smart polymer gels, capable of swelling or deswelling in response to various physical and/or chemical stimuli, have been developed during the last decades. Complexes fabricated from the electron deficient cyclobis(paraquat-p-phenylene) (CBPQT4+) and electron-rich guests have become one of the most important building blocks for the synthesis of colored self-assembled architectures.1 Here, we report on the successful engineering of new multi-stimuli responsive macromolecular hydrogels featuring CBPQT4+ based complexes. More particularly, we have exploited these colored CBPQT4+ based interactions to i) control the swelling/shrinking processes of materials by applying different stimuli (T, V, competitive macromolecules)2 i) to impart both thermal and temporary memory function to hydrogels3 and iii) to develop polymeric hydrogel systems capable of swelling via a supramolecular transmission. An important practical aspect of these new functional materials is that all relevant phenomena (swelling/shrinking processes, memory function) have an associated visible readout. both the temperature and the duration of whereby the temperature is monitored through heating induced decomplexation of a host-guest complex while the time is monitored through diffusion-controlled release of the free host into the surrounding medium.
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Dates et versions

hal-04361211 , version 1 (22-12-2023)


  • HAL Id : hal-04361211 , version 1


Patrice Woisel, Khaled Belal, Lieselot de Smet, Aurélien Vebr, Joël Lyskawa, et al.. Supramolecular polymeric systems featuring memory function(s). EPF 2022, Jun 2022, Prague, Czech Republic. ⟨hal-04361211⟩
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