Chemically Fueled Self-Sorted Hydrogels

Abstract

Narcissistic self-sorting in supramolecular assemblies can help to construct materials with more complex hierarchies. Whereas controlled changes in pH or temperature have been used to this extent for two-component self-sorted gels, here we show that a chemically fueled approach can provide three-component materials with high precision. The latter materials have interesting mechanical properties, such as enhanced or suppressed stiffness, and intricate multistep gelation kinetics. In addition, we show that we can achieve supramolecular templating, where pre-existing supramolecular fibers first act as a templates for growth of a second gelator, after which they can selectively be removed.

Temporally programmed polymer – solvent interactions using a chemical reaction network

“…In contrast, the deactivation mechanism (excluding enzymatic reactions) for chemically fuelled non-equilibrium CRNs at present relies frequently on hydrolysis 9 , 15 , 22 – 25 or internal pH change 10 – 13 . Notable exceptions 26 , 27 concern deactivation reactions that use either redox chemistry 17 , 28 – 30 , alkene cross-metathesis 31 , chemical clocks 32 or spontaneous chemical degradation 18 .…”

In Situ Self-Sorting Peptide Assemblies in Living Cells for Simultaneous Organelle Targeting

“…Self-sorting is a common phenomenon in cells and is essential for the formation of complex biological structures on the basis of the selective association of the corresponding components . This natural phenomenon has inspired for the development of self-sorted hierarchical supramolecular structures or hydrogels via rationally tailoring the structural features of supramolecular monomers. − However, the design of self-sorted peptide assemblies remains challenging due to the difficulty in guiding the selective peptide interactions that are predominately associated with the homogeneous components (amino acids). One interesting instance of the self-sorted peptide network was reported by Adams and co-workers through chemically programming the order of the assembly of two aromatic peptide monomers in a kinetically controlled manner .…”

Heat triggered molecular restructuring results in triple gel–gel–gel transformations in a Li+-integrated metallogel

“…Therefore, inclusive of all the experimental evidence presented here, we propose that thermal stimuli driven in situ dissipation of the H 4 TL motif yielded a non-gelating azine scaffold HY (non-gelator) which acted as an efficient in situ ligand dopant. 70 The reason why the non-gelator HY molecule exerts a synergistic effect on the gelation ability of H 4 TL might be attributed to their closely related chemical structures in terms of the DEAS functionality appended as side-chains in both the H 4 TL and HY species. The unique effects of introducing chemical species with close structural similarity in supramolecular self-assembly have been emphasized recently.…”