Hydrogels can be formed by the self-assembly of certain small molecules in water. Self-assembly occurs via non-covalent interactions. The self-assembly leads to the formation of fibrous structures which form the matrix of the gel. The mechanical properties of the gels arise from the properties of the fibres themselves (thickness, persistence length etc.), the number and type of cross-links and also how the fibres are distributed in space (the microstructure). We discuss here the effect of assembling the molecules under different conditions, i.e. the self-assembly process. There is sufficient literature showing that how the molecules are assembled can have a significant effect on the properties of the resulting gels.

Controlling the order and spatial distribution of self-assembly in multicomponent supramolecular systems could underpin exciting new functional materials, but it is extremely challenging. When a solution of different components self-assembles, the molecules can either coassemble, or self-sort, where a preference for like-like intermolecular interactions results in coexisting, homomolecular assemblies. A challenge is to produce generic and controlled 'one-pot' fabrication methods to form separate ordered assemblies from 'cocktails' of two or more self-assembling species, which might have relatively similar molecular structures and chemistry. Self-sorting in supramolecular gel phases is hence rare. Here we report the first example of the pH-controlled self-sorting of gelators to form self-assembled networks in water. Uniquely, the order of assembly can be predefined. The assembly of each component is preprogrammed by the pK a of the gelator. This pH-programming method will enable higher level, complex structures to be formed that cannot be accessed by simple thermal gelation.

Fmoc-diphenylalanine (FmocFF or FmocPhePhe) is an important low molecular weight hydrogelator. Gelation can be induced by either lowering the pH of an aqueous solution of FmocFF or by the addition of water to a solution of FmocFF in a solvent such as DMSO. Despite the volume of literature on FmocFF, the mechanical properties reported for the gels vary significantly over four orders of magnitude and the origins of this variability is unclear. Here, we study systematically the mechanical properties of FmocFF gels prepared with different protocols. We demonstrate that the final pH of the gels is the principal determinant of the mechanical properties independently of the method of gel formation. We also show that additional variability arises from experimental factors such as the fraction of DMSO or the nature of the buffers used in selected systems.Scheme 1 Structure of FmocFF.Scheme 2 Hydrolysis of GdL to gluconic acid.

Low molecular weight gelators (LMWG) self-assemble in solution into one-dimensional objects such as fibres or tapes. The entanglement of these fibres or tapes results in the formation of a network and a gel. In general, LMWG are investigated as single component systems. However, there are significant potential opportunities from mixed LMWG systems, which are rarely investigated. Here, we discuss the potential of multicomponent systems, and critically discuss the challenges.