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.
Gels can be formed by dissolving Fmoc-diphenylalanine (Fmoc-PhePhe or FmocFF) in an organic solvent and adding water. We show here that the choice and amount of organic solvent allows the rheological properties of the gel to be tuned. The differences in properties arise from the microstructure of the fibre network formed. The organic solvent can then be removed post-gelation, without significant changes in the rheological properties. Gels formed using acetone are meta-stable and crystals of FmocFF suitable for X-ray diffraction can be collected from this gel.
Some functionalised dipeptides can form hydrogels when salts are added to solutions at high pH. We have used surface tension, conductivity, rheology, optical, confocal and scanning electron microscopy, (1)H NMR and UV-Vis spectroscopy measurements to characterise fully the phase behaviour of solutions of one specific gelator, 2NapFF, at 25 °C at pH 10.5. We show that this specific naphthalene-dipeptide undergoes structural transformations as the concentration is increased, initially forming spherical micelles, then worm-like micelles, followed by association of these worm-like micelles. On addition of a calcium salt, gels are generally formed as long as worm-like micelles are initially present in solution, although there are structural re-organisations that occur at lower concentrations, allowing gelation at lower than expected concentration. Using IR and SANS, we show the differences between the structures present in the solution and hydrogel phases.
We discuss the effect of the kinetics of pH change on the mechanical properties of dipeptide hydrogels. Data from other peptide-based low molecular weight gelator (LMWG) systems suggest that the rheological properties are often highly dependent on the assembly rate. To examine kinetics here, we have used the hydrolysis of glucono-8-lactone (GdL). The hydrolysis of GdL to gluconic acid results in a decrease in pH, the rate of which is temperature sensitive. Hence, we can adjust the rate of pH decrease, whilst achieving the same absolute final pH. Our data shows that at all temperatures the rheological profile is very similar, with an increase to a plateau, followed by a second increase in moduli, despite very different kinetics of assembly. Surprisingly, the final mechanical properties are very similar in all cases. We also show that the structures formed at the plateau can be accessed by adjusting the pH using CO2. By carefully balancing the pKa. of the gelator with the pH achievable using CO2, flexible hydrogel membranes can be formed as opposed to a bulk gel. The rheological characteristics of the membranes are typical of a highly entangled polymer network. These membranes can be rigidified by post-addition of GdL to further lower the pH.
The magnetic-field-induced alignment of the fibrillar structures present in an aqueous solution of a dipeptide gelator, and the subsequent retention of this alignment upon transformation to a hydrogel upon the addition of CaCl2 or upon a reduction in solution pH is reported. Utilising the switchable nature of the magnetic field coupled with the slow diffusion of CaCl2, it is possible to precisely control the extent of anisotropy across a hydrogel, something that is generally very difficult to do using alternative methods. The approach is readily extended to other compounds that form viscous solutions at high pH. It is expected that this work will greatly expand the utility of such low-molecular-weight gelators (LMWG) in areas where alignment is key.
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