The quest for function in systems with two dynamic covalent bonds: supramolecular self-assembly, self-replication and hydrogels for biomedical applications

Inspired by nature, chemists have envisioned that it is possible to obtain organized structures (and functions) using complex networks of interacting molecules in a synthetic setting. Thus far, functional molecular systems have been recognized as fruitful platforms, suitable to challenge and complement prevalent strategies for innovation in areas ranging from biology and medicine to energy sustainability.

To this end, this thesis describes studies on self-assembling systems and their emergent properties and functions. The research presented teeters at the interface of fundamental and applied research as we address conceptually very different topics from a unique starting point. The work in Chapters 3 and 4 utilizes reversibility of covalent and non-covalent interactions to explore the modes of organization in peptide-based systems. In particular, we investigated the tendency of self-assemblies towards post-modification, self-replication and folding. In Chapters 5 and 6 we explored an alternative synthetic mimic of the extracellular matrix (ECM). The basic scaffold was designed in such a way to facilitate chemical modifications on demand (easily and quickly). In this approach, only minimal synthetic efforts are required to readily diversify a polymeric material using various bioactive entities (e.g., cell adhesion ligands, RGD or LDV).

In the future, functional systems that make use of dynamic bonds will continue to address highly compelling and challenging questions. By answering those, we aim to make advancements in fundamental topics such as the origin of life, as well as health and technology.