Search

Nature uses systems of high complexity coordinated by the precise spatial and temporal control of associated processes, working from the molecular to the macroscopic scale. This living organization is mainly ensured by enzymatic actions. Herein, we review the concept of Localized Enzyme-Assisted Self-Assembly (LEASA). It is defined and presented as a straightforward and insightful strategy to achieve high levels of control in artificial systems. Indeed, the use of immobilized enzymes to drive self-assembly events leads not only to the local formation of supramolecular structures but also to tune their kinetics and their morphologies. The possibility to design tailored complex systems taking advantage of self-assembled networks through their inherent and emergent properties offers new perspectives for the design of novel, more adaptable materials. As a result, some applications have already been developed and are gathered in this review. Finally, challenges and perspectives of LEASA are introduced and discussed.

Hydrogel coating is highly suitable in biomaterial design. It provides biocompatibility and avoids protein adsorption leading to inflammation and rejection of implants. Moreover, hydrogels can be loaded with biologically active compounds. In this field, hyaluronic acid has been largely studied as an additional component since this polysaccharide is naturally present in extracellular matrix. Strategies to direct hydrogelation processes exclusively from the surface using a fully biocompatible approach are rare. Herein we have applied the concept of localized enzyme-assisted self-assembly to direct supramolecular hydrogels in the presence of HA. Based on electronic and fluorescent confocal microscopy, rheological measurements and cell culture investigations, this work highlights the following aspects: (i) the possibility to control the thickness of peptide-based hydrogels at the micrometer scale (18–41 µm) through the proportion of HA (2, 5 or 10 mg/mL); (ii) the structure of the self-assembled peptide nanofibrous network is affected by the growing amount of HA which induces the collapse of nanofibers leading to large assembled microstructures underpinning the supramolecular hydrogel matrix; (iii) this changing internal architecture induces a decrease of the elastic modulus from 2 to 0.2 kPa when concentration of HA is increasing; (iv) concomitantly, the presence of HA in supramolecular hydrogel coatings is suitable for cell viability and adhesion of NIH 3T3 fibroblasts. View Full-Text Keywords: supramolecular hydrogel; enzyme-assisted self-assembly; hyaluronic acid; peptide; coating