Nanoparticles can co-assemble with amphiphilic block copolymers (ABPs) in solution to generate nanoaggregates with unique properties, yet the mechanism of such a co-assembly behaviour for Janus nanoparticles (JPs) and ABPs remains unclear. Here, the self-assembly behaviour of JP/ABP mixtures in dilute solution was studied via theoretical simulations. Two kinds of ABPs with different volume fractions fA of hydrophilic blocks were considered: one is symmetric copolymers with fA = 0.5, and the other is asymmetric ABPs with fA = 0.3. In the first case, mixtures of spheres and rods, connected networks and vesicles were formed sequentially as the volume fraction cJP of nanoparticles increases. In the second case, vesicles were constantly formed. For both cases, at lower cJP values, the nanoparticles were located at the core–corona interfaces. By contrast, at higher particle loadings, a large number of particles were involved in clusters embedded in the vesicle walls. Based on the simulation results, a morphological diagram in the space of cJP and fA was constructed to indicate the stability regions of different nanostructures. Specifically, it was found that the vesicles formed by JPs and ABPs with short hydrophilic blocks are stimuli-responsive. By changing the interaction parameters between hydrophobic blocks, controllable pores in the vesicle walls could be created. Our findings not only provide insights into the co-assembly behaviour of Janus nanoparticles and amphiphilic block copolymers in solution, but also offer a novel strategy to prepare nanoreactors with permeable membranes.

Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

•Triblock copolymers with various rod blocks are designed for hierarchical structures.•Hierarchical liquid crystal exhibits diverse ordering degrees and tilt angles.•Smectic C transforms into arrowhead-like smectic C via changing copolymer symmetry.Brownian dynamics simulations are performed to investigate self-assembly behavior of rod-coil-rod triblock copolymers that contain two types of rod blocks. These rod-coil-rod triblock copolymers are capable of self-assembling into liquid crystalline (LC) structures with hierarchy. The morphologies of the hierarchical LC structures can be controlled by temperature, symmetry of LC blocks, and block length. As the temperature decreases, a transition from isotropic lamellae to smectic C lamellae is observed, accompanied by an increase in orientational ordering and tilt angle of rod blocks. For the hierarchical lamellae-in-lamella structures formed by symmetric block copolymers, there are two LC phases with nearly identical ordering and tilt angle for two rod blocks. While for the lamellae-in-lamellae formed by asymmetric block copolymers, the two LC phases exhibit two different length scales with diverse ordering degrees and tilt angles. By adjusting the lengths of coil and rod blocks, the stability regions of the structures are mapped out in space of the block length versus the temperature. The findings in the present work could provide useful information for understanding the self-assembly behavior of rod-coil-rod triblock copolymers and designing hierarchical liquid crystalline structures.

Hierarchical microstructures self-assembled from A(BC)n multiblock copolymers confined between two solid surfaces were explored by dissipative particle dynamics simulations. The strategy using confinement allows us to generate hierarchical microstructures with various numbers and different orientations of small-length-scale lamellae. Except for the hierarchical lamellar microstructures with parallel or perpendicular arrangements of small-length-scale lamellae, the coexistence of two different hierarchical lamellae was also discovered by varying the film thickness. The dynamics of hierarchical microstructure formation was further examined. It was found that the formation of the hierarchical microstructures exhibits a stepwise manner where the formation of small-length-scale structures lags behind that of large-length-scale structures. The present work could provide guidance for controllable manufacture of hierarchical microstructures.

•Self-consistent field theory with Yukawa potentials is developed.•Parallel-to-perpendicular lamellae-in-lamellae transition is predicted.•Observation of tetragonal-to-hexagonal cylinder transition is successfully explained.We extended self-consistent field theory to study the phase behavior of supramolecular blends of diblock copolymers with hydrogen-bonding interactions. The hydrogen-bonding interactions are described by Yukawa potentials. The hydrogen-bonding donors and acceptors were modeled as two blocks smeared with opposite screened charges. Hierarchical microstructures such as parallel and perpendicular lamellae-in-lamellae were observed. The appearance of parallel/perpendicular lamellae-in-lamellae depends on the strength of hydrogen-bonding interactions related to the density of hydrogen bonds and the characteristic lengths of the Yukawa potentials. Phase diagrams were correspondingly mapped out, and the domain size, interfacial width and free energies were examined to gain insight into the phase transitions. It was also found that the revealed mechanism can account for some experimental phenomena that are not well explained yet. The present method can be readily further extended to more complicated supramolecular systems with hydrogen-bonding interactions.A self-consistent field theory was developed to study the phase behavior of supramolecular blends of diblock copolymers with hydrogen-bonding interactions, and the phase transitions such as parallel-to-perpendicular lamellae-in-lamellae transition were predicted.