Aggregate engineering of non-covalent networks endows supramolecular polymers with thermo-mechanical versatility,stimuli-responsive phase transitions and intrinsic damage-healing capabilities.However,most non-covalent...Aggregate engineering of non-covalent networks endows supramolecular polymers with thermo-mechanical versatility,stimuli-responsive phase transitions and intrinsic damage-healing capabilities.However,most non-covalent networks are vulnerable at elevated temperatures,which suppresses the robustness of supramolecular polymers.Herein,ureidocytosine(UCy)motifs,which are capable of forming extensive non-covalent networks and thus robust molecular aggregates via multivalent hydrogen bonds and aromatic stackings,are proposed to enable precise programming of the thermo-mechanical versatility.Molecular simulations reveal that the enthalpic contributions from the UCy aggregates play dominant roles to compensate the entropic loss from the redistributions of polymeric spacers and stabilize the non-covalent networks over wide temperature windows.Such aggregate-level strategy offers prospects for applications which require thermo-mechanical versatility of supramolecular polymers,such as 3D printing,microfabrication and damage-healing coating.展开更多
基金supported by the Research Grant Council of Hong Kong(No.CityU 11305219)City University of Hong Kong(Nos.6000685 and 9610348)Research Grant Council of Hong Kong(No.C1025-14E).
文摘Aggregate engineering of non-covalent networks endows supramolecular polymers with thermo-mechanical versatility,stimuli-responsive phase transitions and intrinsic damage-healing capabilities.However,most non-covalent networks are vulnerable at elevated temperatures,which suppresses the robustness of supramolecular polymers.Herein,ureidocytosine(UCy)motifs,which are capable of forming extensive non-covalent networks and thus robust molecular aggregates via multivalent hydrogen bonds and aromatic stackings,are proposed to enable precise programming of the thermo-mechanical versatility.Molecular simulations reveal that the enthalpic contributions from the UCy aggregates play dominant roles to compensate the entropic loss from the redistributions of polymeric spacers and stabilize the non-covalent networks over wide temperature windows.Such aggregate-level strategy offers prospects for applications which require thermo-mechanical versatility of supramolecular polymers,such as 3D printing,microfabrication and damage-healing coating.
