Enhanced stability of crosslinked and charged unimolecular micelles from multigeometry triblock copolymers with short hydrophilic segments: dissipative particle dynamics simulation

Macromol. Rapid Commun.

Sun

Lyu

et al. 2019

Self‐assembly of asymmetric block copolymers (BCPs) around active pore edges has emerged as an important strategy to produce smart membranes with tunable pathways for solute transport. However, thus far, it is still challenging to manipulate pore shape and functionality for directional transformation under external stimuli. Here, a versatile strategy by mesoscale simulations to design stimuli‐responsive pores with various edge decorations in hybrid membranes is reported. Dopant BCPs are used as decorators to stabilize pore edges and extend their function in reconfiguring pores in response to repeated membrane stretching/shrinking caused by external stimuli. The decoration morphologies are predictable since the assemblies of dopant BCPs around pore edges are closely related to their self‐assemblies in solution. The coassembly between different BCPs in the hybrid membrane for the control of pore morphology is featured, and the parameter settings, including block incompatibility and molecular architecture for the construction of a specific pore, are determined. Results show that harnessed dopant BCPs in the hybrid membrane can enhance pore formation and induce directional pore shape and functionality transformation. Diversified pore decorations exhibit potential that can be further explored in selective solute transport and the design of stimuli‐responsive smart nanodevices.

Section: Methodssupporting

confidence: 70%

Harnessed Dopant Block Copolymers Assist Decorating Membrane Pores: A Dissipative Particle Dynamics Study

Macromol. Rapid Commun.

Sun

Lyu

et al. 2019

“…Based on the DPD theory proposed by Groot and Warren, the repulsive parameter a ii between the neutral same species was chosen to be 25, such as the interaction of core–core ( a 11 ) and water–water ( a 33 ). If the repulsive interaction existed in the same components, for example, the repulsive interaction between microgel shell ( a 22 ), the a ii was usually adjusted to >25 …”

Section: Methodsmentioning

confidence: 99%

“…To achieve the high crosslinking density of microgels, each subchain only contained one bead. This kind of microgel with high crosslinking density was built and studied through DPD simulation in the previous study . Patchy microgels possessed the hydrophobic core and hydrophilic shell on different sides, where red and green beads represented the core and shell structure, respectively (Figure a).…”

Section: Methodsmentioning

confidence: 99%

Directed Self‐Assembly of Patchy Microgels into Anisotropic Nanostructures

Macromol. Rapid Commun.

Zhang

et al. 2019

Self Cite

recent years, some DSA strategies have been developed. [4] The building blocks were organized into ordered structures indirectly using templates (e.g., DNA, [5] capillary, [6] topographically patterned substrates [7,8] ) or external fields (e.g., electric [9] and magnetic fields, [10] flow field [11] ). Besides, a rich interplay of multiple chemically distinct components and geometrical complexity of assembly units could be directly tailored to achieve the DSA behavior. Obviously, the latter is a simple and robust "bottom-up" way.The DSA process can be controlled precisely by the intrinsic characteristics of nanoparticles, like imparting directionality in molecular interactions and controlling particle geometry. Recent attention in particle design and synthesis has focused on the "patches" onto the particle surface to effectively regulate the interaction directionality. Soft patchy assemblies with different symmetries from triblock terpolymers could be further co-assembled into substructured and compartmentalized materials with predictable and tunable nanoscale periodicities. [12] Triblock Janus colloidal spheres with two hydrophobic poles and an electrically charged middle band were induced to form a complex predetermined colloidal crystal-kagome structure via the hydrophobic attraction and electrostatic repulsion. [13] By utilizing the anion-π interaction as the driving force, long-distance self-assembly with coherent particle formation was achieved, on which the cavity orientation of the bismacrocycle components had a significant influence. [14] On the basis of "patch" strategy, the geometry of nanoscale building blocks also plays key roles in the hierarchical assembly of ordered superstructures, especially for anisotropic nanoparticles with nonspherical shapes. [15] Patchy ellipsoidal polymer particles with sticky interactions near the tips were produced by the thermo/mechanical stretching and following wet chemical treatment. [16] The patchy, inverse pom-pom ellipsoids could interact directionally and self-assemble into chains or denser structures in bulk. Snowman-type Janus nanoparticles (JNPs) were used as a model to study the effect of colloidal geometries on their assembled superstructures. [17] Both finite (capsules with different curvatures) and nonfinite superstructures (free-standing single-layered or double-layered JNPs sheets) Multi-geometry nanostructures with high-order, complex, and controllable geometries have attracted extensive attention in the development of functional nanomaterials. A simple and versatile strategy is proposed to construct various anisotropic nanostructures through the directed self-assembly (DSA) of patchy microgels. A general criterion for interaction parameters is developed by the variance analysis method to achieve the formation of 1Dnanorods by the single directional DSA process, and 2D or 3D polymorphs including V/T/h/cross shapes, multiple arms, multi-directional bending, single/multiple rings, nanocages, etc., by the multi-directional DSA process of binary microgel b...

“…In fact, in the author's literature survey, it is found that the application of DPD simulation to chemical reaction models represented by FRP is quite extensive. Researchers have also done a lot of work in polymer crosslinking, [ 45–47 ] polymerization‐induced self‐assembly, [ 48 ] and so on. The effect of hydrogen bonds between water and polymer particles on the structure of cross‐linked polyethylene glycol was studied by G. Kacar et al.…”

Section: Application Of Dpd On Mesoscale Properties Of Polymermentioning

confidence: 99%

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

Han

et al. 2021

Macro Materials & Eng

Polymer systems have typical multiscale characteristics, both in space and time. The mesoscopic properties of polymers are difficult to describe through traditional experimental approaches. Dissipative particle dynamics (DPD) is a simulation method used for solving mesoscale problems of complex fluids and soft matter. The mesoscopic properties of polymer systems, such as conformation, dynamics, and transport properties, have been studied extensively using DPD. This paper briefly summarizes the application of DPD to research involving microchannel flow, electrospinning, free‐radical polymerization, polymer self‐assembly processes, polymer electrolyte fuel cells, and biomedical materials. The main features and possible development avenues of DPD are described as well.