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Molecular dynamics simulations are used to demonstrate that a binary solvent can be used to stratify colloidal mixtures when the suspension is rapidly dried. 

Ionizable copolymers assembly in solutions is driven by the formation of ionic clusters. Fast clustering of the ionizable blocks often leads to the formation of far-from equilibrium assemblies that ultimately impact the structure of polymer membranes and affect their many applications. Using large-scale atomistic molecular dynamics simulations, we probe the effects of electrostatics on the formation of ionizable copolymer micelles that dominate their solution structure, with the overarching goal of defining the factors that control the assembly of structured ionizable copolymers. A symmetric pentablock ionizable copolymer, with a randomly sulfonated polystyrene center tethered to polyethylene-r-propylene block, terminated by poly(t-butyl styrene), in solvents of varying dielectric constants from 2 to 20, serves as the model system. We find that independent of the solvents, this polymer forms a core–shell micelle with the ionizable segment segregating to the center of the assembly. The specific block conformation, however, strongly depends on the sulfonation levels and the dielectric constant and the polarity of the solvents. 

Soft nanoparticles (NPs) are emerging candidates for nano medicine, particularly for intercellular imaging and targeted drug delivery. Their soft nature, manifested in their dynamics, allows translocation into organisms without damaging their membranes. A crucial step towards incorporating soft dynamic NPs in nano medicine, is to resolve their interrelation with membranes. Here using atomistic molecular dynamics (MD) simulations we probe the interaction of soft NPs formed by conjugated polymers with a model membrane. These NPs, often termed polydots, are confined to their nano dimensions without any chemical tethers, forming dynamic long lived nano structures. Specifically, polydots formed by dialkyl para poly phenylene ethylene (PPE), with a varying number of carboxylate groups tethered to the alkyl chains to tune the interfacial charge of the surface of the NP are investigated at the interface with a model membrane that consists of di-palmitoyl phosphatidylcholine (DPPC). We find that even though polydots are controlled only by physical forces, they retain their NP configuration as they transcend the membrane. Regardless of their size, neutral polydots spontaneously penetrate the membrane whereas carboxylated polydots must be driven in, with a force that depends on the charge at their interface, all without significant disruption to the membrane. These fundamental results provide a means to control the position of the nanoparticles with respect to the membrane interfaces, which is key to their therapeutic use. 

A method of simulating the drying process of a soft matter solution with an implicit solvent model by moving the liquid-vapor interface is applied to various solution films and droplets. For a solution of a polymer and nanoparticles, we observe “polymer-on-top” stratification, similar to that found previously with an explicit solvent model. Furthermore, “polymer-on-top” is found even when the nanoparticle size is smaller than the radius of gyration of the polymer chains. For a suspension droplet of a bidisperse mixture of nanoparticles, we show that core-shell clusters of nanoparticles can be obtained via the “small-on-outside” stratification mechanism at fast evaporation rates. “Large-on-outside” stratification and uniform particle distribution are also observed when the evaporation rate is reduced. Polymeric particles with various morphologies, including Janus spheres, core-shell particles, and patchy particles, are produced from drying droplets of polymer solutions by combining fast evaporation with a controlled interaction between the polymers and the liquid-vapor interface. Our results validate the applicability of the moving interface method to a wide range of drying systems. The limitations of the method are pointed out and cautions are provided to potential practitioners on cases where the method might fail. 

Branched polymers stress relaxation is at the center to their function as viscosity modifiers, though the fundamentals that underlie the correlation between the polymer topology and their impact on viscosity remains an open question. Here, the stress relaxation of short, branched polyethylene comb polymer melts is studied by molecular dynamics simulations. A coarse-grained model where four methylene groups constitute one bead is used, and the results are transposed to the atomistic level. For arms of length comparable to entanglement length ne of the linear polymer, we show that while increasing the number of branches with the same arm length decreases the plateau modulus, the terminal diffusive time does not change significantly. Increasing the arm length decreases the plateau modulus and increases the terminal time. As arms shorter than ne relax by the entanglement time, both the chain mobility and stress relaxation can be described by reptation of the backbone with an increased tube diameter and an increas