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We use computer simulations to study a system of two unlinked ring polymers, whose length and bending stiffness are systematically varied. We derive the effective potentials between the rings, calculate the areas of minimal surfaces of the same, and characterize the threading between them. When the two rings are of the same kind, threading of a one ring through the surface of the other is immanent for small ring-ring separations. Flexible rings pierce the surface of the other ring several times but only shallowly, as compared to the stiff rings which pierce less frequently but deeply. Typically, the ring that is being threaded swells and flattens up into an oblate-like conformation, while the ring that is threading the other takes a shape of an elongated prolate. The roles of the threader and the threaded ring are being dynamically exchanged. If, on the other hand, the rings are of different kinds, the symmetry is broken and the rings tend to take up roles of the threader and the threaded ring with unequal probabilities. We propose a method how to predict these probabilities based on the parameters of the individual rings. Ultimately, our work captures the interactions between ring polymers in a coarse-grained fashion, opening the way to large-scale modelling of materials such as kinetoplasts, catenanes or topological brushes.

We study active topological glass under spherical confinement, allowing us to exceed the chain lengths simulated previously and determine the critical exponents of the arrested conformations. We find a previously unresolved "tank-treading" dynamic mode of active segments along the ring contour. This mode can enhance active-passive phase separation in the state of active topological glass when both diffusional and conformational relaxation of the rings are significantly suppressed. Within the observational time, we see no systematic trends in the positioning of the separated active domains within the confining sphere. The arrested state exhibits coherent stochastic rotations. We discuss possible connections of the conformational and dynamic features of the system to chromosomes enclosed in the nucleus of a living cell.

The behavior of unknotted and trefoil-knotted ring polymers under shear flow is here examined by means of mesoscopic simulations. In contrast to most polymers, ring polymers in a hydrodynamic solvent at high shear rates do not get shortened in the vorticity direction. This is a consequence of the backflow produced by the interaction of the sheared solvent with the end-free polymer topology. The extended structures of the ring in the vorticity-flow plane, when they are aligned in a constant velocity plane, favor ring contour fluctuations. This variety of conformations largely suppresses the tank-treading type of rotation with extended conformations in favor of the tumbling type of rotations, where stretched and collapsed conformations alternate. The extension of trefoil knots is also enhanced, so that the knots become delocalized. We anticipate that these effects, which disappear in the absence of hydrodynamic interactions, will have a crucial impact on the rheological properties of concentrated ring solutions, and will also influence the behavior of more complicated systems such as mixtures of polymers with different topologies.

We combine state-of-the art synthesis, simulations, and physical experiments to explore the tunable, responsive character of telechelic star polymers as models for soft patchy particles. We focus on the simplest possible system: a star comprising three asymmetric block copolymer arms with solvophilic inner and solvophobic outer blocks. Our dilute solution studies reveal the onset of a second slow mode in the intermediate scattering functions as the temperature decreases below the θ-point of the outer block, as well as the size reduction of single stars upon further decreasing temperature. Clusters comprising multiple stars are formed and their average dimensions, akin to the single star size, counterintuitively decrease upon cooling. A similar phenomenology is observed in simulations upon increasing attraction between the outer blocks and is rationalized as a result of the interplay between interstar associations and steric repulsion between the star cores. Since our simulations are able to describe the experimental findings reliably, we can use them with confidence to make predictions at conditions and flow regimes that are inaccessible experimentally. Specifically, we employ simulations to investigate flow properties of the system at high shear rates, revealing shear thinning behavior caused by the breakup of interstar associations under flow. On the other hand, the zero-shear viscosity obtained experimentally exhibits a rather weak activation energy, which increases upon rising star concentration. These findings demonstrate the unusual properties of telechelic star polymers even in the dilute regime. They also offer a powerful toolbox for designing soft patchy particles and exploring their unprecedented responsive properties further on.

By means of multiscale molecular simulation, we show that solvophilic-solvophobic AB diblock copolymer brushes in the semi-dilute regime present a re-entrant disorder/order/disorder transition. The latter is fully controllable through two parameters: the grafting density and the solvophobic to solvophilic ratio of the tethered macromolecules. Upon increasing density, chains first aggregate into patches, then further order into a crystalline phase and finally melt into a disordered phase. We demonstrate that the order/disorder transition can be explained through the peculiar properties of the aggregates: upon increasing density, the aggregation number grows as expected. On the contrary, their projection on the plane shrinks, thus melting the emergent ordered phase. Such a density dependent shrinkage, seen for the first time as the cause to an order/disorder phase transition, is as a consequence of the entropic/enthalpic competition that characterises the hierarchical self-assembly of the brush.

Block copolymer stars (BCSs) have been demonstrated to constitute versatile, self-assembling building blocks with tunable softness, functionalization, and shape. We investigate the dynamical properties of suspensions of short-arm BCSs under linear shear flow by means of extensive particle-based multiscale simulations. We determine the properties of the system for representative values of monomer packing fraction ranging from semidilute to concentrate regimes. We systematically analyze the formed network structures as a function of both shear rate and packing fraction, the reorganization of solvophobic patches, and the corresponding radial correlation functions. Connecting our findings with rheology, we calculate the viscosity as a function of shear rate and discuss the implications of the found shear thinning behavior.

We combine synthesis, physical experiments, and computer simulations to investigate self-assembly patterns of low-functionality telechelic star polymers (TSPs) in dilute solutions. In particular, in this work, we focus on the effect of the arm composition and length on the static and dynamic properties of TSPs, whose terminal blocks are subject to worsening solvent quality upon reducing the temperature. We find two populations, single stars and clusters, that emerge upon worsening the solvent quality of the outer block. For both types of populations, their spatial extent decreases with temperature, with the specific details (such as temperature at which the minimal size is reached) depending on the coupling between inter- and intra-molecular associations as well as their strength. The experimental results are in very good qualitative agreement with coarse-grained simulations, which offer insights into the mechanism of thermoresponsive behavior of this class of materials.

Cluster glass-phase ring suspensions exposed to weak shear stress exhibit a stable reorientation of stacks as well as of individual ring polymers with the flow direction and into the flow-vorticity...

We use the replica method to study the dynamical glass transition of the Gaussian core model, a system of ultrasoft repulsive spheres interacting via a Gaussian potential, focusing on low temperatures and low-to-moderate densities. At constant temperature, an amorphous glassy state is entered upon a first compression but this glass melts as the density is further increased. In addition to this reentrant transition, a second, smooth transition is discovered between a continuous and a discretized glass. The properties of the former are continuous functions of temperatures, whereas the latter exhibits a succession of stripes, characterized by discontinuous jumps of the glassiness parameters. The glass physics of ultrasoft particles is hence richer than that of impenetrable particles for reasons that can be attributed to the ability of the former to create and break out-of-equilibrium clusters of overlapping particles.

We investigate the effects of topological constraints in catenanes composed of interlinked ring polymers on their size in a good solvent as well as on the location of their θ-point when the solvent quality is worsened. We mainly focus on poly[n]catenanes consisting of n ring polymers each of length m interlocked in a linear fashion. Using molecular dynamics simulations, we study the scaling of the poly[n]catenane's radius of gyration in a good solvent, assuming in general that Rg ∼ mμnν and we find that μ = 0.65 ± 0.02 and ν = 0.60 ± 0.01 for the range of n and m considered. These findings are further rationalized with the help of a mean-field Flory-like theory yielding the values of μ = 16/25 and ν = 3/5, consistent with the numerical results. We show that individual rings within catenanes feature a surplus swelling due to the presence of NL topological links. Furthermore, we consider poly[n]catenanes in solvents of varying quality and we demonstrate that the presence of topological links leads to an increase of its θ-temperature in comparison to isolated linear and ring chains with the following ordering: Tθcatenane > Tθlinear > Tθring. Finally, we show that the presence of links similarly raises the θ-temperature of a single linked ring in comparison to an unlinked one, bringing its θ-temperature close to the one of a poly[n]catenane.

We investigate mixtures of ring and linear polymers in solution at various number ratios, ranging from pure chains to pure rings, and at densities around the overlap concentration. In bulk and at r...

We present a systematic investigation of the structure and dynamic properties of model soft–hard colloidal mixtures. Results of a coarse-grained theoretical model are contrasted with rheological data, where the soft and hard colloids are mimicked by large star polymers with high functionality as the soft component and smaller stars with ultrahigh functionality as the hard one. Previous work by us revealed the recovery of the ergodicity of glassy soft star solutions and subsequent arrested phase separation and re-entrant solid transition upon progressive addition of small hard depletants. Here, we use different components to show that a small variation in softness has a significant impact on the state diagram of such mixtures. In particular, we establish that rendering the soft component more penetrable and modifying the size ratio bring about a remarkable shift in both the phase separation region and the glass-melting line so that the region of restored ergodicity can be notably enhanced and extended to much higher star polymer concentrations than for pure systems. We further rationalize our findings by analyzing the features of the depletion interaction induced by the smaller component that result from the interplay between the size ratio and the softness of the large component. These results demonstrate the great sensitivity of the phase behavior of entropic mixtures to small changes in the molecular architecture of the soft stars and point to the importance of accounting for details of the internal microstructure of soft colloidal particles for tailoring the flow properties of soft composites.

We explore effective interactions in dilute polydisperse ring polymer solutions. Based on a topological and threading analysis, we deduce the steric, topological and threading contributions to the ...

We perform simulations to compute the effective potential between the centers-of-mass of two polymers with reversible bonds. We investigate the influence of the topology on the potential by employing linear and ring backbones for the precursor (unbonded) polymer, finding that it leads to qualitatively different effective potentials. In the linear and ring cases the potentials can be described by Gaussians and generalized exponentials, respectively. The interactions are more repulsive for the ring topology, in analogy with known results in the absence of bonding. We also investigate the effect of the specific sequence of the reactive groups along the backbone (periodic or with different degrees of randomness), establishing that it has a significant impact on the effective potentials. When the reactive sites of both polymers are chemically orthogonal so that only intramolecular bonds are possible, the interactions become more repulsive the closer to periodic the sequence is. The opposite effect is found if both polymers have the same types of reactive sites and intermolecular bonds can be formed. We test the validity of the effective potentials in solution, in a broad range of concentrations from high dilution to far above the overlap concentration. For this purpose, we compare simulations of the effective fluid and test particle route calculations with simulations of the real all-monomer system. Very good agreement is found for the reversible linear polymers, indicating that unlike in their nonbonding counterparts many-body effects are minor even far above the overlap concentration. The agreement for the reversible rings is less satisfactory, and at high concentration the real system does not show the clustering behavior predicted by the effective potential. Results similar to the former ones are found for the partial self-correlations in ring/linear mixtures. Finally, we investigate the possibility of creating, at high concentrations, a gel of two interpenetrated reversible networks. For this purpose we simulate a 50/50 two-component mixture of reversible polymers with orthogonal chemistry for the reactive sites, so that intermolecular bonds are only formed between polymers of the same component. As predicted by both the theoretical phase diagram and the simulations of the effective fluid, the two networks in the all-monomer mixture do not interpenetrate, and phase separation (demixing) is observed instead., We acknowledge Grant PGC2018-094548-B-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. We also acknowledge Grant IT-1175-19 funded by Eusko Jaurlaritza (Basque Government).

We investigate the effects of crowding on the conformations and assembly of confined, highly charged, and thick polyelectrolyte brushes in the osmotic regime. Particle tracking experiments on increasingly dense suspensions of colloids coated with ultra-long double stranded DNA (dsDNA) fragments reveal non-monotonic particle shrinking, aggregation and re-entrant ordering. Theory and simulations show that shrinking is induced by the osmotic pressure exerted by the counterions absorbed in neighbor brushes, while aggregation and re-entrant ordering are the effect of a short-range attraction competing with the electrostatic repulsion. Blunt-end interactions between dsDNA fragments of neighboring brushes are responsible for the attraction and can be tuned by inducing free-end backfolding through the addition of monovalent salt. Our results show that base stacking is a mode parallel to hybridization to steer colloidal assembly, in which attractions can be fine-tuned through salinity and, potentially, grafting density and temperature., Comment: 56 pages, 11 figures

This work shows how glassy behavior emerges from the active, directed polymer dynamics that is triggered by the non-equilibrium phase separation.

We employ genetic algorithms (GA), which allow for an unbiased search for the global minimum of energy landscapes, to identify the ordered equilibrium configurations formed by binary dipolar systems confined on a plane. A large variety of arrangements is identified, the complexity of which grows with increasing asymmetry between the two components and with growing concentration of the small particles. The effects of the density are briefly discussed and a comparison with results obtained via conventional lattice-sum minimization is presented. Our results can be confirmed by experiments involving Langmuir monolayers of polystyrene dipolar spheres or superparamagnetic colloids confined on the air–water interface and polarized by an external, perpendicular magnetic field.

We demonstrate that star-branched polyelectrolytes are a versatile soft component forming a variety of well-characterised conformations upon electrostatic complexation on oppositely charged planar surfaces. We discover and characterise five complexation shapes, described by a two-dimensional morphological order parameter. These shapes are distinguished on the basis of their deviations from sphericity, the orientation of the polyelectrolyte arms, and the equilibrium centre-to-surface distance of the stars. Conformational transformations can be steered by changing the electrostatic surface–star coupling and/or the star functionality. For low functionalities and/or strong external fields, full collapse of the star onto the wall, forming a starfish configuration, is observed. Otherwise, partially adsorbed states with a fraction of chains pointing away from the surface and with the star core being detached from the wall are formed.

In this review we present a summary of recent progress achieved in examining the equilibrium and dynamical properties of concentrated solutions of two novel kinds of soft matter systems: star-shaped polymers and starburst molecules known as dendrimers. The two systems share a host of interesting properties. The both consist of highly branched polymers, they allow for tuning of their properties through modification of the macromolecular architecture and they are both representatives of a quite novel class of colloidal particles, termed ultrasoft colloids. On the other hand there are also important differences, reflecting the fundamental difference in their architecture. It will be shown that a combination of scattering techniques and rheology with computer simulations and analytical methods from the realm of theoretical physics can shed light on the unusual properties of such systems. In this fashion, new ways appear for the manipulation of soft matter systems under external influences and promising perspectives for the fabrication of new materials are opened up and the versatility in manipulating soft matter is underlined.

The structural properties of a system of ionic microgels under the influence of an alternating electric field are investigated both theoretically and experimentally. This combined investigation aims to shed light on the structural transitions that can be induced by changing either the driving frequency or the strength of the applied field, which range from string-like formation along the field to crystal-like structures across the orthogonal plane. In order to highlight the physical mechanisms responsible for the observed particle self-assembly, we develop a coarse-grained description, in which effective interactions among the charged microgels are induced by both equilibrium ionic distributions and their time-averaged hydrodynamic responses to the applied field. These contributions are modeled by the buildup of an effective dipole moment at the microgels backbones, which is partially screened by their ionic double layer. We show that this description is able to capture the structural properties of this system, allowing for very good agreement with the experimental results. The model coarse-graining parameters are indirectly obtained via the measured pair distribution functions and then further assigned with a clear physical interpretation, allowing us to highlight the main physical mechanisms accounting for the observed self-assembly behavior.

The separation of polymers based on their size, rigidity, and topology is an essential but also highly challenging task for nanoscience and engineering. Using hybrid molecular dynamics simulations that correctly take into account hydrodynamics, we have designed microfluidic channels for separating linear from ring polymers in dilute solutions. We establish that the transport velocity of the polymers is independent of their topology and rigidity when the channel walls are smooth and repulsive. However, when the walls are decorated with attractive spots arranged on lines parallel to the flow, ring polymers exhibit an order of magnitude higher transport velocity compared to linear chains. The spots induce a homeotropic-like reorientation of ring polymers close to walls leading to a tank treading motion along them, whereas linear chains are immobilized upon adsorption. This mechanism becomes more enhanced with increasing polymer rigidity. The presented technique holds thus promise for reliably separating nanoparticles based on their topology.

Inverse patchy colloids are nano- to micro-scale particles with a surface divided into differently charged regions. This class of colloids combines directional, selective bonding with a relatively simple particle design: owing to the competitive interplay between the orientation-dependent attraction and repulsion — induced by the interactions between like/oppositely charged areas — experimentally accessible surface patterns are complex enough to favor the stabilization of specific structures of interest. Most important, the behavior of heterogeneously charged units can be ideally controlled by means of external parameters, such as the pH and the salt concentration. We present a concise review about this class of systems, spanning the range from the synthesis of model inverse patchy particles to their self-assembly, covering their coarse-grained modeling and the related numerical/analytical treatments.

Molecular building blocks undergoing a hierarchical assembly process form nano-scale objects which can further assemble into supramolecular structures. When the intermediate units have a limited valence in bonding, complex structures with tailored properties can be created. Here, we consider a composite, star-shaped particle made of f diblock copolymer chains uniformly grafted on a spherical colloid and investigate its first self-assembly stage both in the bulk and under lateral confinement. By means of numerical simulations, we show that, in the bulk, this system develops aggregates whose number and size depend on the temperature as well as on the relative ratio of solvophobic monomers. The emerging aggregates are referred to as patches and impart directionality in bonding to the complex particle. We further characterize how we can control, by changing the lateral confinement, the shape of the brush and the patch properties as a function of the distance between the confining walls. We find that the number of the patches can be determined by tuning the degree of confinement imposed on the particle. Finally, we employ a continuum mechanics model, known as the Liquid Drop Model, to gain insight into the elastic properties of the system. This theoretical approach allows to connect the patch properties to the elastic response of the composite particle.

Semiflexible ring polymers are known to exhibit clustering behavior and form stacks in concentrated solutions. Recently, weak shear was suggested to re-orient these stacks with flow, a phenomenon more easily visible in more concentrated solutions [Liebetreu et al., ACS Appl. Polym. Mater., 2020, 2(8), 3505–3517, DOI: 10.1021/acsapm.0c00522]. In this work, we investigate the impact of mixing linear chains and rings in a similar system under shear, studying clustering in the presence of semiflexible, rod-like chains. We present a correlation between chain monomer fraction and clustering behavior as linear chains take up less space, thus decreasing the system's effective density and, subsequently, clustering. However, we suggest mixtures with a low chain concentration to maintain or potentially enhance clustering at equilibrium while this effect is destroyed under shear. The mixing of chains and rings may therefore be used to create more strongly organized structures susceptible to reorientation via weak shear.

The self-assembly of Janus ring polymers is studied via a coarse-grained molecular dynamics employing a bead spring model including bending rigidity contributions to the Hamiltonian. We examine the formation and the morphology of amphiphilicity-driven clusters in the system using the number density ρN, the temperature T, the fraction of solvophobic monomers α, and the stiffness of the polymer rings κ as control parameters. We present a quantitative analysis of several characteristics for the formed clusters of Janus rings. Measured quantities include the distribution of the cluster size MC and the shape of the clusters in the form of the prolate/oblate factor Q and shape factors sf. We demonstrate Janus rings form polymorphic micelles that vary from a spherical shape, akin to that known for linear block copolymers, to a novel type of toroidal shape, and we highlight the role played by the key physical parameters leading to the stabilization of such structures.

We have used computer simulations to reveal how colloidal crystals may be assembled by engineering the shape and charge of polymeric additives, which act as structure-directing agents (SDAs). Using these agents, only a single desired polymorph may be obtained from a crystallizing mixture of colloids and polymers, which would otherwise result in a defective crystal in the absence of these agents. Building on previous work, which demonstrated this principle in the limiting case of high-density, close-packed crystals, we have now achieved this control over low-density, open crystals, which have broad utility especially in optical applications. These results reveal the general utility of the SDA paradigm in assembling tailored colloidal crystals, which represents a new design method that does not rely on any modification of the colloids themselves.

The equilibrium properties of block copolymer star networks (BCS) are studied via computer simulations. We employ both molecular dynamics and multiparticle collisional dynamics simulations to investigate the self-organization of BCS with f = 9 functionalized arms close to their overlap concentrations under conditions of different fractions of functionalization and varying attraction strength. We find three distinct macroscopic self-organized states depending on fraction of attractive end-monomers and the strength of the attraction. At weak attractions, ergodic, diffusive liquids result, with short-lived bonds between the stars. As the attraction strength grows, the whole system forms a percolating cluster, while at the same time the individual molecules are diffusive. Finally, arrested gels emerge when the attractions become strong. The conformation of the BCS in these solutions is found to be strongly affected by the concentration, with the stars assuming typically spherical, open configurations in seeking to maximize inter-star associations as opposed to the inter-star collapse that results at infinite dilution, giving rise to strongly aspherical shapes and reduced sizes.

Star polymers with magnetically functionalized end groups are presented as a novel polymeric system whose morphology, self-aggregation, and orientation can easily be tuned by exposing these macromolecules simultaneously to an external magnetic field and to shear forces. Our investigations are based on a specialized simulation technique which faithfully takes into account the hydrodynamic interactions of the surrounding, Newtonian solvent. We find that the combination of magnetic field (including both strength and direction) and shear rate controls the mean number of magnetic clusters, which in turn is largely responsible for the static and dynamic behavior. While some properties are similar to comparable non-magnetic star polymers, others exhibit novel phenomena; examples of the latter include the breakup and reorganization of the clusters beyond a critical shear rate, and a strong dependence of the efficiency with which shear rate is translated into whole-body rotations on the direction of the magnetic field.

Single and double layers of polymer coated surfaces are investigated by means of Dissipative Particle Dynamics (DPD), focusing on the difference between grafted ring and linear chains. Several different surface coverages σ , as well as chain lengths N and brush separations D, are analyzed for athermal, i.e., good solvent, conditions. The size in the form of the radius of gyration R g , the shape as asphericity δ ∗ , and orientation β ∗ , as well as density profiles as functions of distance from grafting plane ρ ( z ) , are studied. The effect of an added bond repulsion potential to suppress bond crossing in DPD is analyzed. Scaling laws of R g and its components R g ⊥ and R g ∥ are investigated. We find R g ∝ N ν , ν = 0.588 for surface coverages below the overlap surface concentration σ ∗ . For σ &gt, σ ∗ we find R g ⊥ ∝ N ν ⊥ , ν ⊥ ≅ 1 and R g ∥ ∝ N ν ∥ , ν ∥ = 1 / 2 of ring brushes with the standard DPD model and ν ∥ ≅ 2 / 5 with added bond repulsion. The σ dependence of the radius of gyration was found to be R g ∝ σ μ with μ = 1 / 3 for surface coverages grater than σ ∗ . The perpendicular component R g ⊥ scales independent of the bond repulsion potential as R g ⊥ ∝ σ μ ⊥ , μ ⊥ = 1 / 3 , whereas the scaling of the parallel component exhibits a topological repulsion dependence R g ∥ ∝ σ μ ∥ , μ ∥ = − 1 / 12 for standard DPD and μ ∥ = − 1 / 6 for bond repulsion.

We present a generic coarse-grained model to describe molecular motors acting on polymer substrates, mimicking, for example, RNA polymerase on DNA or kinesin on microtubules. The polymer is modeled as a connected chain of beads; motors are represented as freely diffusing beads which, upon encountering the substrate, bind to it through a short-ranged attractive potential. When bound, motors and polymer beads experience an equal and opposite active force, directed tangential to the polymer; this leads to motion of the motors along the polymer contour. The inclusion of explicit motors differentiates our model from other recent active polymer models. We study, by means of Langevin dynamics simulations, the effect of the motor activity on both the conformational and dynamical properties of the substrate. We find that activity leads, in addition to the expected enhancement of polymer diffusion, to an effective reduction of its persistence length. We discover that this effective "softening" is a consequence of the emergence of double-folded branches, or hairpins, and that it can be tuned by changing the number of motors or the force they generate. Finally, we investigate the effect of the motors on the probability of knot formation. Counter-intuitively our simulations reveal that, even though at equilibrium a more flexible substrate would show an increased knotting probability, motor activity leads to a marked decrease in the occurrence of knotted conformations with respect to equilibrium., 26 pages, 8 figures

We study the hydrodynamic transport of knotted ring polymers through modulated channels, establishing that the transport velocity is strongly dependent on the ring topology for Peclet numbers smaller than unity. As soon as convection dominates, transport properties become insensitive to the presence and type of knots. We identify two distinct modes of transport, corresponding to the motion being led by the knotted or unknotted portions of the ring, most surprisingly without impact on separation efficiency. The modes can be selected by the channel geometry, and this could be harnessed to design nanofluidic devices for the continuous topological sorting of entangled biopolymers.

We present a comprehensive theoretical and experimental study of the solution phase properties of DNA-based family of nanoparticles - dendrimer-like DNA molecules (DL-DNA). These charged DNA dendrimers are novel macromolecular aggregates, which hold high promise in targeted self-assembly of soft matter systems in the bulk and at interfaces. To describe the behavior of this family of dendrimers (with generations ranging from G1 to G7), we use a theoretical model in which base-pairs of a single DL-DNA molecule are modeled by charged monomers, whose interactions are chosen to mimic the equilibrium properties of DNA correctly. Experimental results on the sizes and conformations of DL-DNA are based on static and 1dynamic light scattering; at the same time, Molecular Dynamics simulations are employed to model the equilibrium properties of DL-DNA, which compare favorably with the findings from experiments while at the same time providing a host of additional information and insight into the molecular structure of the nanostructures. We also examine the salt-responsiveness of these macromolecules, finding that despite the strong screening of electrostatic interactions, brought about by the added salt, the macromolecules shrink only slightly, their size robustness stemming from the high bending rigidity of the DNA-segments. The study of these charged dendrimer systems is an important field of research in the area of soft matter due to their potential role for various interdisciplinary applications, ranging from molecular cages and carriers for drug delivery in a living organism to the development of dendrimer- and dendron-based ultra-thin films in the area of nanotechnology. These findings are essential to determine if DL-DNA is a viable candidate for the experimental realization of cluster crystals in the bulk, a novel form of solids with multiple site occupancy., 38 pages, 17 figures

Star block-copolymers (SBCs) are macromolecules formed by a number of diblock copolymers anchored to a common central core, being the internal monomers solvophilic and the end monomers solvophobic. Recent studies have demonstrated that SBCs constitute self-assembling building blocks with specific softness, functionalization, shape and flexibility. Depending on different physical and chemical parameters, the SBCs can behave as flexible patchy particles. In this paper, we study the rotational dynamics of isolated SBCs using a hybrid mesoscale simulation technique. We compare three different approaches to analyze the dynamics: the laboratory frame, the non-inertial Eckart&rsquo, s frame and a geometrical approximation relating the conformation of the SBC to the velocity profile of the solvent. We find that the geometrical approach is adequate when dealing with very soft systems, while in the opposite extreme, the dynamics is best explained using the laboratory frame. On the other hand, the Eckart frame is found to be very general and to reproduced well both extreme cases. We also compare the rotational frequency and the kinetic energy with the definitions of the angular momentum and inertia tensor from recent publications.

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. It is found that the possibility of particle inter-penetration in oppositely charged soft particles results in a much wider variety of cluster morphologies in comparison with their hard-spheres counterparts. Specifically, the softness of the steric interactions enhances the competition between repulsive and attractive electrostatic interactions, leading to the formation of aggregates that are comprised of strongly bounded charged particles displaying a low degree of charge ordering.

Using a model where soft nanocolloids such as spherical polymer brushes and star polymers are viewed as compressible liquid drops, we theoretically explore contact interactions between such particles. By numerically minimizing the phenomenological free energy consisting of bulk and surface terms, we find that at small deformations the drop–drop interaction is pairwise additive and described by a power law. We also propose a theory to describe the small-deformation regime, and the agreement is very good at all drop compressibilities. The large-deformation regime, which is dominated by many-body interactions, is marked by a rich phase diagram which includes the face- and body-centered-cubic, σ, A15, and simple hexagonal lattice as well as isostructural and re-entrant transitions. Most of these features are directly related to the non-convex deformation free energy emerging from many-body effects in the partial-faceting regime. The phase diagram, which depends on just two model parameters, contains many of the condensed phases observed in experiments. We also provide statistical-mechanical arguments that relate the two model parameters to the molecular architecture of the polymeric nanocolloids, chain rigidity, and solvent quality. The model represents a generic framework for the overarching features of the phase behavior of polymeric nanocolloids at high compressions.

Star block-copolymers (SBCs) have been demonstrated to constitute self-assembling building blocks with specific softness, functionalization, shape, and flexibility. In this work, we study the behavior of an isolated SBC under a shear flow by means of particle-based multiscale simulations. We systematically analyze the conformational properties of low-functionality stars, as well as the formation of attractive patches on their corona as a function of the shear rate. We cover a wide range of system parameters, including functionality, amphiphilicity, and solvent quality. It is shown that SBCs display a richer structural and dynamical behavior than athermal star polymers in a shear flow [ Ripoll Phys. Rev. Lett. , 2006 , 96 , 188302 ], and, therefore, they are also interesting candidates to tune the viscoelastic properties of complex fluids. We identify three factors of patch reorganization under shear that lead to patch numbers and orientations depending on the shear rate, namely, free arms joining existing patches, fusion of medium-sized patches into bigger ones, and fission of large patches into two smaller ones under high shear rates. Because the conformation of single SBC is expected to be preserved in low-density bulk phases, the presented results are a first step in understanding and predicting the rheological properties of semidilute suspensions of this kind of polymers., The authors thank support by the European Training Network COLLDENSE (H2020-MCSA-ITN-2014, Grant No. 642774). This publication is based upon work partially supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3073. M.C. thanks VCTI-UAN (Project 2015036) and Colciencias (Project 123365842816).

We put forward a model that allows the calculation of the effective potential of two interacting DNA-stars, i.e., three-armed, Y-shaped, charged macromolecules, built up by three intertwined single-stranded DNAs. These particles are assumed to float on a flat interface separating two media with different dielectric properties. As the only input, our model requires the charge density along the branches and the interaction between two infinitesimally short segments, along two interacting rods. With this effective interaction at hand, a detailed investigations of the self-assembly scenarios of these molecules either via computer simulations or via theoretical frameworks comes within reach.

A coarse-graining approach based on the linear response theory is applied to deduce general expressions for the effective pair potentials in a multi-component system of soft macroions. Within the underlying approximations, the effective pair potentials can be written as simple convolutions between the intrinsic macroion charge distributions and a Yukawa-like potential which effectively contains the averaged contributions from the small ions. Two different charge distributions are assigned to the soft macroions: a Gaussian-like diffuse distribution and a uniform charge distribution inside the particle cores. The resulting effective pair potentials are then used in an effective model based on the hyppernetted chain approximation to investigate the structural properties of a two-component system of oppositely charged particles as a function of the various system parameters. It is found that the condensation of counterions is much stronger in the case of particles with a Gaussian charge distribution, leading ...

We investigate the conformations and shapes of circular polymers close to planar, hard walls as well as the ensuing ring–wall and polymer-induced wall–wall interactions in ring polymer solutions. W...

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. The single-molecule conformation diagram in the plane of magnetic interaction strength vs. the star-functionality is obtained. Further, the molecules are characterized by means of various shape and size order parameters.

We examine the phase behavior of end-functionalized diblock copolymer stars by means of Grand Canonical Monte Carlo simulations. We focus on solutions of diblock copolymer stars with a solvophobic outer block shorter than the solvophilic inner block, which are expected to nucleate microphase aggregates. By tuning the temperature and rigidity of the molecules, we target specific mesoscale structures, which can act as powerful rheology modifiers. In particular, we control the hierarchical self-assembly of single micelles in a "pearl-necklace" fashion, which eventually merge into elongated, wormlike supermicelles.