The influence of arm composition on the self-assembly of low-functionality telechelic star polymers in dilute solutions

Abstract

We combine synthesis, physical experiments, and computer simulations to investigate self-assembly patterns of low-functionality telechelic star polymers (TSPs) in dilute solutions. In particular, in this work, we focus on the effect of the arm composition and length on the static and dynamic properties of TSPs, whose terminal blocks are subject to worsening solvent quality upon reducing the temperature. We find two populations, single stars and clusters, that emerge upon worsening the solvent quality of the outer block. For both types of populations, their spatial extent decreases with temperature, with the specific details (such as temperature at which the minimal size is reached) depending on the coupling between inter- and intra-molecular associations as well as their strength. The experimental results are in very good qualitative agreement with coarse-grained simulations, which offer insights into the mechanism of thermoresponsive behavior of this class of materials.

Shape control of soft patchy nanoparticles under confinement

“…26 In this work we explore, by means of full-monomer numerical simulations, the properties of diblock copolymer brushes grafted to a spherical colloidalso referred to as diblock copolymer star (DCS) brush. Diblock copolymer brushes composed of polybutadine-polysterene have been recently synthesized using state-of-the-art techniques, 27,28 and the accompanying numerical simulations have shown that the simple modeling we put forward here is capable of capturing the salient characteristics under both dilute and semidilute conditions. First, we consider a DCS brush in the bulk and show that, as the solvophobic sections of the brush aggregate, we can identify patches as clusters of monomers belonging to different arms, as prescribed in the literature; 23 DCS brushes thus constitute examples of soft patchy particles.…”

Interpenetrated and Bridged Nanocylinders from Self-Assembled Star Block Copolymers

“…The central message from the rheological and SAXS studies is the unambiguous tunability of the dynamic response of micelles and TSPs as the temperature is reduced from the amorphous liquid regime. However, the formed ordered phases in the intermediate-temperature and the low-temperature re-entrant regimes are not as coherent and unambiguous as in other block copolymer cylindrical phases …”

“…Finally, note that the model employed is not a result of systematic coarse-graining that would retain the details of microscopic interactions necessary for a quantitative comparison against the experiments. Rather, it aims at rationalizing generic trends in system assembly as a function of the main control parameters. ,,, …”

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

“…Moghimi et al 192 combined synthesis, experiments and computer simulations to investigate self‐assembly patterns of low‐functionality telechelic star polymers (TSPs) in dilute solutions as a function of temperature and solvent quality, the main focus being the effect of the arm composition and length. Zhang et al 193 compared the self‐assembly and pH/oxidation responsivity of a linear and cyclic toothbrush copolymer.…”