Rheological properties of polymer chains at a copper oxide surface: Impact of the chain length, surface coverage, and grafted polymer shape.

We employ a recently derived semirealistic set of coarse-grained interactions to simulate polymer brushes of cis-1,4-polybutadiene grafted on a cuprous-oxide surface within the framework of dissipative particle dynamics. We consider two types of brushes, I and Y, that differ in the way they are connected to the surface. Our model explores the impact of free polymer chain length, grafting density of the brush, and imposed shear rate on the structural and dynamic properties of complex metal oxide polymer interfaces.

Strain induced crystallization of polymers at and above the crystallization temperature by coarse-grained simulations.

We examine the behavior of short and long polymers by means of coarse-grained computer simulations of a by-polyvinyl alcohol inspired model. In particular, we focus on the structural changes in the monomer and polymer scales during cooling and the application of uni-axial true strain. The straining of long polymers results in the formation of a semi-crystalline system at temperatures well above the crystallization temperature, which allows for the study of strain induced crystallization.

Assessing the derivation of time parameters from branched polymer coarse-grain model.

The parameterization of rheological models for polymers is often obtained from experiments via the top-down approach. This procedure allows us to determine good fitting parameters for homogeneous materials but is less effective for polymer mixtures. From a molecular simulation point of view, the timescales needed to derive those parameters are often accessed through the use of coarse-grain potentials.

Heterogeneity Effects in Highly Cross-Linked Polymer Networks.

Despite their level of refinement, micro-mechanical, stretch-based and invariant-based models, still fail to capture and describe all aspects of the mechanical properties of polymer networks for which they were developed. This is for an important part caused by the way the microscopic inhomogeneities are treated. The Elastic Network Model (ENM) approach of reintroducing the spatial resolution by considering the network at the level of its topological constraints, is able to predict the macroscopic properties of polymer networks up to the point of failure.

Backbone oriented anisotropic coarse grains for efficient simulations of polymers.

Despite the fact that anisotropic particles have been introduced to describe molecular interactions for decades, they have been poorly used for polymers because of their computing time overhead and the absence of a relevant proof of their impact in this field. We first report a method using anisotropic beads for polymers, which solves the computing time issue by considering that beads keep their principal orientation alongside the mean local backbone vector of the polymer chain, avoiding the computation of torques during the dynamics. Applying this method to a polymer bulk, we study the effect of anisotropic interactions vs isotropic ones for various properties such as density, pressure, topology of the chain network, local structure, and orientational order.

Quenching of fully symmetric mixtures of oppositely charged microgels: the role of soft stiffness.

Using molecular dynamics simulations, we investigate the self-assembly of a coarse-grained binary system of oppositely charged microgels, symmetric in size and concentration. The microgel pair interactions are described by an effective pair potential which implicitly accounts for the averaged ionic contributions, in addition to a short-range elastic repulsion that accounts for the overlapping of the polymer chains, the latter being described by the Hertzian interaction. Particular emphasis is placed on the role played by the strength of the soft repulsive interaction on the resulting particle aggregation.

Pressure and compressibility factor of bidisperse magnetic fluids.

In this work, we investigate the pressure and compressibility factors of bidisperse magnetic fluids with relatively weak dipolar interactions and different granulometric compositions. In order to study these properties, we employ the method of diagram expansion, taking into account two possible scenarios: (1) dipolar particles repel each other as hard spheres; (2) the polymer shell on the surface of the particles is modelled through a soft-sphere approximation. The theoretical predictions of the pressure and compressibility factors of bidisperse ferrofluids at different granulometric compositions are supported by data obtained by means of molecular dynamics computer simulations, which we also carried out for these systems.

Self-assembly of magnetically functionalized star-polymer nano-colloids.

We explore the potential of star-polymers that carry super-paramagnetic nano-particles as end-groups with respect to the single-molecule self-assembly process. With the aid of molecular dynamics simulation, the configurations of these macromolecules are analyzed as a function of functionality, magnetic interaction strength, and the length of the polymeric arms. By means of an external magnetic field the nano-particles can be controlled to form static or dynamic dipolar chains, resulting in conformations of isolated stars that can be characterized by the average number of chains and length.

Concentration-induced planar-to-homeotropic anchoring transition of stiff ring polymers on hard walls.

We study the structure and interfacial ordering of stiff ring polymers close to repulsive walls. For this purpose, we employ an anisotropic effective model in which the rings are pictured as soft, penetrable discs [P. Poier, C.

Thermodynamic stability and structural properties of cluster crystals formed by amphiphilic dendrimers.

We pursue the goal of finding real-world examples of macromolecular aggregates that form cluster crystals, which have been predicted on the basis of coarse-grained, ultrasoft pair potentials belonging to a particular mathematical class [B. M. Mladek et al.

Anisotropic effective interactions and stack formation in mixtures of semiflexible ring polymers.

By means of extensive computer simulations, we investigate the formation of columnar structures (stacks) in concentrated solutions of semiflexible ring polymers. To characterize the stacks we employ an algorithm that identifies tube-like structures in the simulation cell. Stacks are found both in the real system and in the fluid of soft disks interacting through the effective anisotropic pair potential derived for the rings [P.

An Anisotropic Effective Model for the Simulation of Semiflexible Ring Polymers.

We derive and introduce anisotropic effective pair potentials to coarse-grain solutions of semiflexible ring polymers of various lengths. The system has been recently investigated by means of full monomer-resolved computer simulations, revealing a host of unusual features and structure formation, which, however, cannot be captured by a rotationally averaged effective pair potential between the rings' centers of mass [Bernabei M.; Soft Matter2013, 9, 1287].

Effective Interactions between Multilayered Ionic Microgels.

Using a one-component reduction formalism, we calculate the effective interactions and the counterion density profiles for microgels that feature a multilayered shell structure. We follow a strategy that involves second order perturbation theory and obtain analytical expressions for the effective interactions by modeling the layers of the particles as linear superpostion of homogeneously charged spheres. The general method is applied to the important case of core-shell microgels and compared with the well-known results for a microgel that can be approximated by a macroscopic, and homogeneously charged, spherical macroion.

Telechelic star polymers as self-assembling units from the molecular to the macroscopic scale.

By means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust, and tunable system, which hierarchically self-assembles into soft-patchy particles and mechanically stabilizes selected, open crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks, preserve properties as particle size, number, and arrangement of patches per particle.

Microscopically resolved simulations prove the existence of soft cluster crystals.

We perform extensive monomer-resolved computer simulations of suitably designed amphiphilic dendritic macromolecules over a broad range of densities, proving the existence and stability of cluster crystals formed in these systems, as predicted previously on the basis of effective pair potentials [B. M. Mladek et al.

Complexation and overcharging of polyelectrolyte stars and charged colloids.

We examine the complexation behavior of polyelectrolyte stars on oppositely charged colloidal particles with similar sizes by means of computer simulations employing the molecular dynamics approach. In particular the overcharging phenomenon is considered and its dependence on the charge and functionality of the stars. The complexes thus formed are a realization of inverse patchy particles (Bianchi et al 2011 Soft Matter 7 8313) for which both the number of patches and the total charge can be tuned.

Structural properties of dendrimer-colloid mixtures.

We consider binary mixtures of colloidal particles and amphiphilic dendrimers of the second generation by means of Monte Carlo simulations. By using the effective interactions between monomer-resolved dendrimers and colloids, we compare the results of simulations of mixtures stemming from a full monomer-resolved description with the effective two-component description at different densities, composition ratios, colloid diameters and interaction strengths. Additionally, we map the two-component system onto an effective one-component model for the colloids in the presence of the dendrimers.

The effects of pH, salt and bond stiffness on charged dendrimers.

We have performed molecular dynamics simulations of charged dendrimers with various charge distributions, and including both rigid and soft bonds between the monomers. Whereas the rigid bonds result in a shell-like structure, the soft bonds lead to a larger dendrimer size and a more homogeneous monomer distribution. The measured density profiles of counter-ions and co-ions are compared with those stemming from Poisson-Boltzmann theory.

Topological characteristics of model gels.

The Euler characteristic of an object is a topological invariant determined by the number of handles and holes that it contains. Here, we use the Euler characteristic to profile the topology of model three-dimensional gel-forming fluids as a function of increasing length scale. These profiles act as a 'topological fingerprint' of the structure, and can be interpreted in terms of three types of topological events.

Patchy colloids: state of the art and perspectives.

Recently, an increasing experimental effort has been devoted to the synthesis of complex colloidal particles with chemically or physically patterned surfaces and possible specific shapes that are far from spherical. These new colloidal particles with anisotropic interactions are commonly named patchy particles. In this Perspective article, we focus on patchy systems characterized by spherical neutral particles with patchy surfaces.

Monomer-resolved simulations of cluster-forming dendrimers.

We present results of monomer-resolved Monte Carlo simulations for a system of amphiphilic dendrimers of the second generation. Our investigations validate a coarse-grained level description based on the zero-density limit effective pair-interactions for low and intermediate densities, which predicted the formation of stable, finite aggregates in the fluid phase. Indeed, we find that these systems form a homogeneous fluid for low densities, which, on increasing the density, spontaneously transforms into a fluid of clusters of dendrimers.

Dynamical arrest in low density dipolar colloidal gels.

We report the results of extensive molecular dynamics simulations of a simple, but experimentally achievable model of dipolar colloids. It is shown that a modest elongation of the particles and dipoles to make dipolar dumbbells favors branching of the dipolar strings that are routinely observed for point dipolar spheres (e.g.

Dielectric response of a polar fluid trapped in a spherical nanocavity.

We present extensive molecular dynamics simulation results for the structure and the static and dynamical responses of a droplet of 1000 soft spheres carrying extended dipoles and confined to spherical cavities of radii R=2.5, 3, and 4 nm embedded in a dielectric continuum of permittivity epsilon(')>or=1. The polarization of the external medium by the charge distribution inside the cavity is accounted for by appropriate image charges.

Crystal nucleation of colloidal suspensions under shear.

We use Brownian dynamics simulations in combination with the umbrella sampling technique to study the effect of shear flow on homogeneous crystal nucleation. We find that a homogeneous shear rate leads to a significant suppression of the crystal nucleation rate and to an increase of the size of the critical nucleus. A simple, phenomenological extension of classical nucleation theory accounts for these observations.