UPR 5301

Temperature-triggered formation of a cellulose II nanocrystal network through regioselective derivatization

We took advantage of the antiparallel arrangement of the chains within the cellulose II nanocrystals to graft gold nanoparticles or thermosensitive polymer chains to both ends of these rods. In the latter case, a temperature variation induces the formation of a network with a gel-like behaviour by the end-to-end association of the rods.


« The two ends of rodlike cellulose II nanocrystals (CNC-II) were regioselectively functionalized either with gold nanoparticles or thermosensitive polymer chains. In the first case, after the introduction of sulfur atoms at both ends of the rods, CNC-II were labelled using a method based on the in situ nucleation and growth of gold nanoparticles (AuNPs) from soluble derivatives. Transmission electron microscopy (TEM) images showed that such a method resulted in the grafting of one monodisperse AuNP at each extremity of the CNC-II, i.e. to the formation of hybrid dumbbell-shaped objects. No AuNP was detected on the lateral surfaces of the CNC-II and almost all observed CNC-II exhibited this dual labeling. This result confirmed with a good statistics when compared to previous works the possibility to derivatize only the two ends of the CNC-II, thanks to the antiparallel arrangement of cellulose chains in these nanoparticles. In the second case, the localized grafting of temperature-sensitive macromolecules onto the ends of the CNC-II was performed using an oxidation reaction followed by a peptide coupling. This end-specific grafting of thermosensitive chains onto CNC-II enhanced their colloidal stability when the temperature was below the lower critical solution temperature (LCST) of the polymer. Above the LCST, the TEM images revealed the formation of a network extending to tens of microns resulting from end-to-end associations of the derivatized rods through attractive interactions between collapsed polymer chains. Rheology experiments further evidenced a temperature-induced sol–gel transition from a liquid-like (sol) behavior below the LCST to solid-like (gel) behavior above the LCST, in agreement with a change from purely repulsive interactions to interconnections via the hydrophobic collapsed chains. Importantly, all results concurred with a full reversibility of the phenomena upon cooling and reproducibility when samples were subjected to temperature cycles around the LCST. This work reveals that the dual site-specific derivatization of CNC-II can provide symmetric hybrid particles with innovative assembling and macroscopic properties that cannot be obtained through homogeneous chemical modifications. »

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