Regulating Higher-Order Organization through the Synergy of Two Self-Sorted Assemblies

Area of Science:

• Biomaterials Science
• Supramolecular Chemistry
• Nanotechnology

Background:

• The extracellular matrix (ECM) provides a natural scaffold regulating cell behavior.
• Mimicking ECM dynamics is key to developing advanced biomaterials.
• Molecular self-assembly (SA) offers a route to engineer complex nanostructures.

Purpose of the Study:

• To develop higher-order molecular self-assembly (SA) by mimicking extracellular matrix (ECM) dynamics.
• To engineer dynamic nanostructures with controllable growth and hierarchical architecture.
• To investigate the spatial-temporal regulation of nanostructure formation.

Main Methods:

• Designed and synthesized two self-sorted coumarin-based gelators: a peptide and a benzoate molecule.
• Investigated the self-assembly of these gelators into nanofibers and nanobelts with distinct dynamic profiles.
• Utilized light and enzymatic triggers to modify the spatial-temporal growth of the assembled nanostructures.

Main Results:

• Peptide gelators self-assembled into nanofibers, while benzoate gelators formed nanobelts.
• Dynamic growth of the peptide nanofiber scaffold induced the transformation of benzoate nanobelts into layer-by-layer nanosheets.
• Achieved a ninefold increase in the height of the higher-order architecture.
• Demonstrated in situ spatial-temporal regulation of the scaffold's height using external stimuli.

Conclusions:

• Successfully developed a biomimetic higher-order molecular self-assembly (SA) system.
• The dynamic interplay between different self-assembling components allows for controlled hierarchical structure formation.
• External stimuli (light, enzyme) provide precise control over nanostructure growth and architecture, opening avenues for advanced materials design.