In an attempt to generate supramolecular assemblies able to function as self-healing hydrogels, a novel ureidopyrimidinone (UPy) monomer, 2-(N 0 -methacryloyloxyethylureido)-6-(1-adamantyl)-4[1H]-pyrimidinone, was synthesized and then copolymerized with N,N-dimethylacrylamide at four different feed compositions, using a solution of lithium chloride in N,N-dimethylacetamide as the polymerization medium. The assembling process in the resulting copolymers is based on crosslinking through the reversible quadruple hydrogen bonding between side-chain UPy modules. The adamantyl substituent was introduced in order to create a "hydrophobic pocket" that may protect the hydrogen bonds against the disruptive effect of water molecules. Upon hydration to equilibrium, all copolymers generated typical hydrogels when their concentration in the hydrated system was at least 15%. The small-deformation rheometry showed that all hydrated copolymers were hydrogels that maintained a solid-like behavior, and that their extrusion through a syringe needle did not affect significantly this behavior, suggesting a self-healing capacity in these materials. An application as injectable substitutes for the eye's vitreous humor was proposed. V C 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39932.

International audienceThe ring opening polymerization (ROP) of γ-benzyl-L-glutamate N-carboxyanhybride (BLG-NCA) and Nε-trifluroactetyl-L-lysine N-carboxyanhybride (TFALys-NCA) by thiol was investigated at 0°C in DMF as solvent. The use of 2-(trimethylsilyl)-ethanethiol as initiator and its incorporation in the macromolecular chain showed the efficient ring opening polymerization of BLG-NCA by the so called “amine” mechanism. Thus, we proposed a novel synthetic pathway for the synthesis of diblock copolypeptides [poly(N,Ndiethylacrylamide)- b-poly(γ-benzyl-L-glutamate) and poly(N,N-diethylacrylamide)-bpoly( Nε-trifluoroacetyl-L-lysine)] using thiol based macroinitiator. This last was obtained by cleavage of a dithioester end group of poly(N,N-diethylacrylamide) synthesized by RAFT polymerization