Telechelic star polymers as self-assembling units from the molecular to the macroscopic scaleBarbara Capone

TL;DR

This study uses multiscale molecular simulations to demonstrate that telechelic-star polymers can hierarchically self-assemble into soft-patchy particles and crystalline structures, with tunable properties influenced by molecular architecture.

Contribution

It introduces a controllable, self-assembling system of telechelic-star polymers that form stable ordered structures across various scales, revealing new mechanisms for crystal stabilization.

Findings

Self-assembly into soft-patchy particles controlled by arm number and end-group fraction

Formation of gel-like networks and ordered crystals at higher densities

Stabilization of diamond and simple cubic crystals over a wide density range

Abstract

By means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust and tunable system, which hierarchically self-assembles first into soft-patchy particles and then into targeted crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks and stable ordered structures, preserve properties as particle size, number and arrangement of patches per particle. In particular, we demonstrate that the flexibility inherent in the soft-patchy particles brings forward a novel mechanism that leads to the stabilisation of diamond and simple cubic crystals over a wide range of densities, and for molecular sizes ranging from about 10 nm up to the micrometer scale.