Oligomer-assisted self-assembly of bisurea in organic solvent media

Abstract

We report on molecular dynamics simulation evidence revealing that an oligomer additive can be used to greatly facilitate the self-assembly of a bisurea in organic solvent media, through the initial regular packing and the subsequent stiffening of the self-assembly filament. The underlying physics is attributed to the substantially reduced diffusivities of the solute and, in particular, solvent molecules, featuring a generally weakened (thermal) Brownian force under ambient conditions. Without such oligomer-induced molecular cooling—in contrast to the usual external cooling, the original solvent medium is noted to foster instead more stabilized and disordered aggregates and, in particular, it would require a temperature reduction that is practically inaccessible in order to sustain similar stiffness of the self-assembly filament. These features, in accord with recent experimental observations, highlight the open opportunity of promoting the self-assembly of small functional molecules in general solvent media without requiring substantial changes of the system temperature, as is crucial for many practical applications including the biological/biomedical ones.