Complex Pathways Drive Pluripotent Fmoc-Leucine Self-Assemblies.

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Biomimetic Systems

Background:

• Nature achieves diverse functional non-equilibrium self-assemblies using complex pathways.
• Synthetic control over pathway complexity to avoid thermodynamic equilibrium remains a challenge.

Purpose of the Study:

• To demonstrate versatile non-equilibrium assemblies from the same monomer using alternate pathways.
• To achieve on-demand control over self-assembly outcomes, diverging from equilibrium structures.

Main Methods:

• Utilizing classical and non-classical nucleation routes to initiate assembly.
• Employing initial chemical and thermal inputs to direct monomers down specific pathways.
• Tuning dynamics via chemical or thermal stimuli to control dissolution or kinetic trapping.

Main Results:

• Successfully generated distinct metastable (transient hydrogels), kinetic (stable hydrogels), and thermodynamic (crystals, 2D sheets) structures from identical monomers.
• Demonstrated that initial conditions dictate assembly pathways, leading to non-equilibrium molecular arrangements.
• Showcased the ability to kinetically trap hydrogels or direct assembly towards equilibrium products.

Conclusions:

• Developed a versatile method to control self-assembly pathways for generating diverse non-equilibrium soft-materials.
• This approach offers potential for biomimetic systems to create novel materials with tunable properties.
• The findings open avenues for designing materials with specific transient or stable characteristics.