A dissipative particle dynamics simulation study on phase diagrams for the self-assembly of amphiphilic hyperbranched multiarm copolymers in various solvents

Abstract

Self-assembly of amphiphilic hyperbranched multiarm copolymers (HMCs) has shown great potential for preparing all kinds of delicate supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the influencing factors for the self-assembly of HMCs have been greatly lagging behind. The phase diagram of HMCs in selective solvents is very necessary but has not been disclosed up to now. Here, the self-assembly of HMCs with different hydrophilic fractions in various solvents was studied systematically by using dissipative particle dynamics (DPD) simulations. Three morphological phase diagrams are constructed and a rich variety of morphologies, ranging from spherical micelles, worm-like micelles, membranes, vesicles, vesosomes, small micellar aggregates (SMAs), and aggregates of spherical and worm-like micelles to helical micelles, are obtained. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these self-assemblies have been systematically investigated. The simulation results are consistent with available experimental observations. Besides, several novel structures, like aggregates of spherical and worm-like micelles, vesosomes and helical micelles, are firstly discovered for HMC self-assembly. We believe the current work will extend the knowledge on the self-assembly of HMCs, especially on the control of supramolecular structures and on fabricating novel self-assemblies.

Using reactive dissipative particle dynamics to understand local shape manipulation of polymer vesicles

“…Vesicle self-assembly via DPD While numerous DPD simulations of polymer vesicles have been achieved, 34,37,82 and much has been said about the equilibrium morphology of micellar polymer solutions, 35,83 the literature does not provide simple, universal relationships between model parameters and vesicle morphology. Indeed such an endeavor is complicated by the formation of neighboring metastable morphologies and defective states that have similar free energies.…”

Nanocarrier systems assembled from PEGylated hyperbranched poly(arylene oxindole)

“…This indicates that about 90 % of the reactive groups would still be available for further post-assembly functionalization with bioactive molecules to form multi-potent NPs that have the potential to target specific cells [68]. In addition, by keeping the Mw of the HBP constant, the experimentally derived Mw values, percentages of functionalized end groups, and measured NP diameters provide valuable input parameters for stochastic simulation techniques such as dissipative particle dynamics [56,69]. These methods, to some extent, would allow for prediction of the impact of postgrafting hydrophobic and/or hydrophilic molecules on the surface of the NPs, but this will need further investigation.…”

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.…”

“…The transformation of the polymer morphology from spherical to helical micelles was observed. [ 61 ] DPD can be employed to reveal the self‐assembly mechanisms of polymers and predict their new self‐assembled morphology. The self‐assembly behavior of multilayer onion‐like vesicles has been systematically investigated as well.…”