Emily R. Draper

Spatially resolved multicomponent gels

Multicomponent supramolecular systems could be used to prepare exciting new functional materials, but it is often challenging to control the assembly across multiple length scales. Here we report a simple approach to forming patterned, spatially resolved multicomponent supramolecular hydrogels. A multicomponent gel is first formed from two low-molecular-weight gelators and consists of two types of fibre, each formed by only one gelator. One type of fibre in this ‘self-sorted network’ is then removed selectively by a light-triggered gel-to-sol transition. We show that the remaining network has the same mechanical properties as it would have done if it initially formed alone. The selective irradiation of sections of the gel through a mask leads to the formation of patterned multicomponent networks, in which either one or two networks can be present at a particular position with a high degree of spatial control. Multicomponent supramolecular hydrogels have been prepared using a self-sorting mixture of two different gelators—one of which is photosensitive. Irradiation of the gels through a mask leads to the photosensitive network being selectively removed by a light-triggered gel-to-sol transition in a process that can be used to produce patterned gels with spatially controlled properties.

Air-stable photoconductive films formed from perylene bisimide gelators

We show that amino acid-PBIs can form one-dimensional structures at high pH and then gels at low pH. Both the dried solutions and dried gels are photoconductive. Interestingly, photoconductivity of these materials requires that the incident light has a wavelength shorter than 400 nm, in stark contrast with the absorption maxima of the PBIs. The photoconductivity correlates with the formation of the perylene radical anion, which is unusually highly stable in air for many hours.

Kinetically Controlled Coassembly of Multichromophoric Peptide Hydrogelators and the Impacts on Energy Transport

We report a peptide-based multichromophoric hydrogelator system, wherein π-electron units with different inherent spectral energies are spatially controlled within peptidic 1-D nanostructures to create localized energy gradients in aqueous environments. This is accomplished by mixing different π-conjugated peptides prior to initiating self-assembly through solution acidification. We can vary the kinetics of the assembly and the degree of self-sorting through the choice of the assembly trigger, which changes the kinetics of acidification. The hydrolysis of glucono-δ-lactone (GdL) provides a slow pH drop that allows for stepwise triggering of peptide components into essentially self-sorted nanostructures based on subtle pKa differences, whereas HCl addition leads to a rapid formation of mixed components within a nanostructure. Using 1H NMR spectroscopy and fiber X-ray diffraction, we determine the conditions and peptide mixtures that favor self-sorting or intimate comixing. Photophysical investigations in the solution phase provide insight into the correlation of energy-transport processes occurring within the assemblies to the structural organization of the π-systems.

Hydrogels formed from Fmoc amino acids

A number of Fmoc amino acids can be effective low molecular weight hydrogelators. The type of gel formed depends on the amino acid used and, in the case of FmocF, the final pH of the system. The single crystal structure of two of the gelators (FmocF and FmocY) have been determined and the data compared to the fibre X-ray diffraction data. FmocF, which forms metastable gels, crystallises easily and the data for the fibre phase and crystal phase are relatively similar. For FmocF, the fibre axis in b is consistent with the hydrogen bonding repeat distances and the diffraction pattern calculated from the single crystal structure is a good match with the experimental fibre X-ray diffraction data. On the other hand, there are significant differences between the crystalline phase determined and the fibre phase for FmocY. The packing of FmocY within the crystal structure is created by interactions between the planar Fmoc groups, whilst it is clear that hydrogen bonding drives the self-assembly into fibrillar structures within the gels. This shows that understanding the packing in gel phase by analogy to isolated crystal structures has the potential to lead to erroneous conclusions.

Architecture-driven aqueous stability of hydrophobic, branched polymer nanoparticles prepared by rapid nanoprecipitation

The first nanoprecipitation study of hydrophobic branched vinyl polymers is presented with control across a wide range of particle diameters (approximately 60–800 nm) from control of degree of polymerisation and precipitation parameters. In contrast to linear polymers of identical primary chain length, the formation of stable nanoparticles in aqueous media appears to be architecture driven with a contribution from oligomeric chain-ends with measureable water-solubility. The aqueous nanoparticles dispersions are robust and stable to dilution, solvent addition, sonication and temperature. The addition of small amounts of NaCl led to a destabilisation indicating charge stabilisation is also a major contributor to stability.

Using the hydrolysis of anhydrides to control gel properties and homogeneity in pH-triggered gelation

The pH of an aqueous solution of a low molecular weight gelator can be adjusted through the hydrolysis of a number of anhydrides to the corresponding acids. The rate of hydrolysis and hence of pH change can be used to control the rate of gel formation. This rate does not affect the primary assembly of the low molecular weight gelator, but does affect the mechanical properties of the resulting gels, as well as the homogeneity and reproducibility of the gels. The mechanical properties are compared by both rheology and dynamic nanoindentation.

Probing gelation ability for a library of dipeptide gelators.

Functionalised dipeptides are a class of interesting and useful low molecular weight hydrogelators. Here, we report a significantly expanded library of materials, including dipeptides conjugated to carbazole, phenanthracene, anthracene, pyrene and substituted naphthalenes. We assess the effect of using two different gelation methods; a pH-switch and a solvent switch on the gelation behaviour and properties of the dipeptides. Importantly, we investigate the relationship between the structure of these dipeptides and their ability to form gels. From an analysis of the gelation ability of all these dipeptides, it is clear that those containing a phenylalanine as either of the constituent amino acids are much more likely to lead to a gelator being formed as opposed to using non-aromatic amino acids only.

On the syneresis of an OPV functionalised dipeptide hydrogel

We describe a new dipeptide hydrogel based on an oligophenylene vinylene core. After gelation, the initial network evolves, expelling solvent and resulting in syneresis. We describe this process and the effects in the bulk properties of the material.

Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides

Abstract A simple heat/cool cycle can be used to significantly affect the properties of a solution of a low‐molecular‐weight gelator at high pH. The viscosity and extensional viscosity are increased markedly, leading to materials with very different properties than when the native solution is used.

Self-sorted Oligophenylvinylene and Perylene Bisimide Hydrogels

We describe two component hydrogels with networks composed of self-sorted fibres. The component gelators are based on 1,4-distyrylbenzene (OPV3) and perylene bisimide (PBI) units. Self-sorted gels can be formed by a slow decrease in pH, which leads to sequential assembly. We demonstrate self-sorting by NMR, rheology and small angle X-ray scattering (SAXS). Photoconductive xerogels can be prepared by drying these gels. The wavelength response of the xerogel is different to that of the PBI alone.