Quantification of energy of activation to supramolecular nanofibre formation reveals enthalpic and entropic effects and morphological consequence.

We show a self-assembly process leading to fibres from a system that starts far from equilibrium because of fast solvent - anti-solvent mixing and analyse the activation energies associated with the aggregation. It is in some ways reminiscent of diverse natural fibrous materials that have kinetic behaviour dominated by a rate limiting induction period followed by rapid growth. A full thermodynamic rationale for these systems and related synthetic ones is required for a full understanding of the driving force of their non-equilibrium self-assembly. Here we determine quantitatively the enthalpy and entropy of activation for the processes leading to the growth of fibres of this type, that contrasts with analysis of other systems where final energetic states are analysed. A dramatic effect is revealed whereby comparatively small changes in temperature or solvent composition (the ratio of water to ethanol) lead to alterations in the relative importance of enthalpy and entropy of activation and massive changes in the speed of fibre formation. The characteristics of the kinetic model adopted show a correlation with the fibre morphology of the self-assembled materials, which are isostructural according to diffraction experiments: the control of growth can lead to fibres only two bilayers thick. The crossover in behaviour is characteristic of the solvent mixture and the thermodynamic analysis points to the origins of this effect where different assembly routes are viable under only marginally different conditions.