Transferring Micellar Changes to Bulk Properties via Tunable Self-Assembly and Hierarchical Ordering.

Hierarchical self-assembly is an effective means of preparing useful materials. However, control over assembly across length scales is a difficult challenge, often confounded by the perceived need to redesign the molecular building blocks when new material properties are needed. Here, we show that we can treat a simple dipeptide building block as a polyelectrolyte and use polymer physics approaches to explain the self-assembly over a wide concentration range. This allows us to determine how entangled the system is and therefore how it might be best processed, enabling us to prepare interesting analogues to threads and webs, as well as films that lose order on heating and "noodles" which change dimensions on heating, showing that we can transfer micellar-level changes to bulk properties all from a single building block.

Charge screening wormlike micelles affects extensional relaxation time and noodle formation.

A functionalised dipeptide that self-assembles to form wormlike micelles at high pH can be treated as a surfactant. By varying salt concentration, the self-assembled structures and interactions between them change, resulting in solutions with very different shear and extensional viscosity. From these, gel noodles with different mechanical properties can be prepared.

Using small angle scattering to understand low molecular weight gels.

The material properties of a gel are determined by the underpinning network that immobilises the solvent. When gels are formed by the self-assembly of small molecules into a so-called low molecular weight gel, the network is the result of the molecules forming one-dimensional objects such as fibres or nanotubes which entangle or otherwise cross-link to form a three-dimensional network. Characterising the one-dimensional objects and the network is difficult. Many conventional techniques rely on drying to probe the network, which often leads to artefacts. An effective tool to probe the gel in the solvated state is small angle scattering. Both small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS) can be used. Here, we discuss these approaches and provide a tutorial review to describe how these approaches work, what opportunities there are and how the data treatment should be approached. We aim to show the power of this approach and provide enabling information to make them accessible to the non-specialist.

Exploiting and controlling gel-to-crystal transitions in multicomponent supramolecular gels.

Multicomponent supramolecular gels provide opportunities to form materials that are not accessible when using the single components alone. Different scenarios are possible when mixing multiple components, from complete co-assembly (mixing of the components within the self-assembled structures formed) to complete self-sorting such that each structure contains only one of the components. Most examples of multicomponent gels that currently exist form stable gels. Here, we show that this can be used to control the mechanical properties of the gels, but what is probably most exciting is that we show that we can use a magnetic field to control the shape of the crystals. The gelling component aligns in a magnetic field and so results in anisotropic crystals being formed.

Controlling the formation and alignment of low molecular weight gel 'noodles'.

We show how to control the formation and alignment of gel 'noodles'. Nanostructure alignment can be achieved reproducibly by extensional deformation as the filaments form. Using a spinning technique, very long and highly aligned filaments can be made. The Young's moduli of the gel noodles are similar to that of a bulk gel. By using two syringe pumps in a concentric flow setup, we show that a filament-in-filament morphology can be created.