Phase Transition to Bundles of Flexible Supramolecular Polymers

Abstract

We report Monte Carlo simulations of the self-assembly of supramolecular polymers based on a model of patchy particles. We find a first-order phase transition, characterized by hysteresis and nucleation, toward a solid bundle of polymers, of length much greater than the average gas phase length. We argue that the bundling transition is the supramolecular equivalent of the sublimation transition, which results from a weak chain-chain interaction. We provide a qualitative equation of state that gives physical insight beyond the specific values of the parameters used in our simulations.

Hierarchical self-assembly of chiral fibres from achiral particles

“…There is some debate, however, as to the origins of the chirality observed in various of these structures [2,13] A number of simulation studies of fibre self-assembly have been published in recent years employing coarsegrained models of cylindrically symmetric particles. Bolhuis [14] considered the behaviour of hard spheres decorated with attractive interaction sites on their poles. This patch potential not only promoted thread formation but also led to weak thread-thread interactions.…”

Self-assembly of amphiphilic peanut-shaped nanoparticles

“…(We note that colloidal silica dumbbells can be synthesized by other routes [19], and that micrometer-scale peanuts show potential as Pickering stabilizers of * swhitelam@lbl.gov arXiv:0907.3227v2 [cond-mat.soft] 19 Feb 2010 2 oil-in-water emulsions [20].) In an attempt to answer our posed question we have constructed a model of interacting peanuts whose minimal character is motivated by the insight into self-assembly afforded by similarly simple model systems [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]. Our model can be evolved with computational efficiency sufficient to allow observation of collective, thermally-driven dynamics on timescales of seconds.…”

Self-Limited Self-Assembly of Chiral Filaments

“…Drawing conclusions about self-limited growth in a macroscopic system from simulations with a finite number of subunits is challenging-one must distinguish between simulations in which growth terminates due to physical constraints from those in which the system runs out of subunits [15]. To overcome this limitation, we simulate the grand canonical ensemble (µV T ), in which growth cannot terminate because of subunit depletion, since the system is coupled to an unlimited bath of free subunits.…”

“…[15] filamentous bundle formation is described in terms of the theory of linear polymerization [19,20] and bundling of linear polymers. That analysis would be complicated for our model since the subunit binding free energy depends crucially on the number of bundled filaments due to the twist imposed by chirality.…”