Dissipative particle dynamics simulation study on self-assembly of amphiphilic hyperbranched multiarm copolymers with different degrees of branching

Abstract

Hyperbranched multiarm copolymers (HMCs) have shown great potential to be excellent precursors in self-assembly to form various supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the self-assembly of HMCs, especially the self-assembly dynamics and mechanisms, have been greatly lagging behind the experimental progress. Herein, we investigate the effect of degree of branching (DB) on the self-assembly structures of HMCs by dissipative particle dynamics (DPD) simulation. Our simulation results demonstrate that the self-assembly morphologies of HMCs can be changed from spherical micelles, wormlike micelles, to vesicles with the increase of DBs, which are qualitatively consistent with the experimental observations. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these three aggregates have been systematically disclosed through the simulations. These self-assembly details are difficult to be shown by experiments and are very useful to fully understand the self-assembly behaviors of HMCs.

Mesoscale Modeling of Agglomeration of Molecular Bottlebrushes: Focus on Conformations and Clustering Criteria

“…Chang et al [68] demonstrated a transition of micellar aggregates into unilamellar vesicles and then to "onion-like" multilayered vesicles with the decrease in the affinities between the side chain and solvent. This morphology was observed for the relatively short MBB molecules [68,69] and hyperbranched multi-arm copolymers [70,71].…”

DPD Modelling of the Self- and Co-Assembly of Polymers and Polyelectrolytes in Aqueous Media: Impact on Polymer Science

“…Great attention has been devoted to assembly in copolymer solutions and melts, to the structure of assembled nanoparticles and to morphological transformations upon variation of solvent composition, polymer concentration, ionic strength, etc. The behaviour of flexible polyelectrolytes and/or amphiphilic copolymers [69,91,105,106,174,178,193,[202][203][204][205][206], copolymers composed of linear and rigid blocks [127,128,207,208] and also hyperbranched copolymers [209][210][211] has been simulated and the decisive principles and trends of underlying processes have been described. Besides the above systems, the multicore assemblies forming in mixtures of linear copolymers [212], the self-assembling amphiphilic homopolymers [213], side-chain discotic liquid crystalline polymers [214], polymers tethered to nanoparticles and mixtures of copolymers with nanoparticles [215,216] and the 'shape amphiphiles' [217][218][219][220][221] have been successfully studied by DPD.…”

Dissipative Particle Dynamics Simulation: A Review on Investigating Mesoscale Properties of Polymer Systems

“…The self‐assembly process of amphiphilic, hyperbranched, multi‐arm copolymers (HMCs) has also been simulated using DPD. [ 60–65 ] The degree of branching greatly influences the self‐assembled structure of HMCs. With the aid of DPD simulations, the study of different branching conditions revealed the self‐assembly mechanism and the kinetic formation process.…”