Complex Pathways Drive Pluripotent Fmoc-Leucine Self-assemblies

04 April 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Nature uses complex self-assembly pathways to access distinct functional non-equilibrium self-assemblies. This remarkable ability to steer same set of biomolecules into different self-assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over ‘Pathway Complexity’ to access self-assemblies different from equilibrium structures remains challenging. Here we show versatile non-equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non-classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)-crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft-materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self-assembly states can find potential use in similar biomimetic systems to access new materials for various applications.


Pathway complexity
Non-classical nucleation

Supplementary materials

Supporting Information- Complex Pathways Drive Pluripotent Fmoc-Leucine Self-assemblies
This is supporting information including extra characterization, methods and images in support of the main manuscript.
Supporting Videos
This compressed folder includes videos depicting self-assembly evolution under various conditions discussed and referred to in the manuscript.


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