Emergence of Compartments Formed from Unconventional Surfactants in Dynamic Combinatorial Libraries.

Assembly processes can drive the selection of self-assembling molecules in dynamic combinatorial libraries, yielding self-synthesizing materials. We now show how such selection in a dynamic combinatorial library made from an amphiphilic building block which, by itself, assembles into micelles, can yield membranous aggregates ranging from vesicles to sponge phases. These aggregates are made from a mixture of unconventional surfactant molecules, showing the power of dynamic combinatorial selection approaches for the discovery of new, not readily predictable, self-assembly motifs.

Multi-step control over self-assembled hydrogels of peptide-derived building blocks and a polymeric cross-linker.

We present a detailed study of self-assembled hydrogels of bundled and cross-linked networks consisting of positively charged amyloid-like nanofibers and a triblock copolymer with negatively charged end blocks as a cross-linker. In a first step small oligopeptides self-assemble into macrocycles which are held together by reversible disulfide bonds. Interactions between the peptides cause the macrocycles to assemble into nanofibers, which form a reversible hydrogel. The physical properties of the hydrogel are tuned using various methods such as control over the fibre length, addition of a cross-linking copolymer, and addition of salt. We establish a relationship between the bulk mechanical properties, the properties of the individual fibers and the hydrogel morphology using characterization techniques operating at different length scales such as rheology, atomic force microscopy (AFM) and cryo transmission electron microscopy (Cryo-TEM). This allows for a precise control of the elastic behaviour of these networks.

Controlling the Structure and Length of Self-Synthesizing Supramolecular Polymers through Nucleated Growth and Disassembly.

Directing self-assembly processes out-of-equilibrium to yield kinetically trapped materials with well-defined dimensions remains a considerable challenge. Kinetically controlled assembly of self-synthesizing peptide-functionalized macrocycles through a nucleation-growth mechanism is reported. Spontaneous fiber formation in this system is effectively shut down as most of the material is diverted into metastable non-assembling trimeric and tetrameric macrocycles. However, upon adding seeds to this mixture, well-defined fibers with controllable lengths and narrow polydispersities are obtained. This seeded growth strategy also allows access to supramolecular triblock copolymers. The resulting noncovalent assemblies can be further stabilized through covalent capture. Taken together, these results show that self-synthesizing materials, through their interplay between dynamic covalent bonds and noncovalent interactions, are uniquely suited for out-of-equilibrium self-assembly.

Solvent composition dictates emergence in dynamic molecular networks containing competing replicators.

In Darwinian evolution, species that are better adapted to their environment win the competition for common resources from less well-adapted competitors. Thus, in such scenarios the nature of the environment may dictate the outcome of the competition. We investigated to what degree these biological principles acting at the level of species extend to the molecular level into systems based on fully synthetic self-replicating molecules. We now report two systems in which two replicators compete for a common building block and where the environment dictates which of the two replicators wins. We observed that subtle changes in the environment can lead to dramatic differences in the outcome of the competition.