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We investigate the rich phase behavior of strongly confined semi-flexible (SFC) polymer–nanoparticle (NP) systems using the graphics processing unit accelerated Langevin dynamics simulation. Hard nanoparticles (HNP) that repel each other and ideal nanoparticles (INP) that do not interact with the same species are used as model additives to a strongly confined semiflexible polymer fluid. Both types of NPs exclude the monomer beads in the same way, but they have qualitatively different effects on the SFC isotropic–nematic (I–N) transition. For the total volume fraction ϕtot < 0.16, adding a low volume fraction of HNPs (ϕp) disrupts the long range nematic order of the polymers, whereas adding HNPs in a moderately packed system (0.16 < ϕtot < 0.32) facilitates polymer alignment due to the restricted polymer orientational degree of freedom. For dense packing (ϕtot > 0.32), polymers and NPs separate into layers along the slit height and the NPs form crystalline microdomains. In contrast, INP additives always promote inter-polymer alignment for low to moderate monomer volume fractions (ϕm). Furthermore, we found that INPs form a droplet-like fluid domain in dense nematic polymer systems. [ABSTRACT FROM AUTHOR]

We have studied the effect of chain topology on the structural properties and diffusion of polymers in a dilute solution in a good solvent. Specifically, we have used three different simulation techniques to compare the chain size and diffusion coefficient of linear and ring polymers in solution. The polymer chain is modeled using a bead-spring representation. The solvent is modeled using three different techniques: molecular dynamics (MD) simulations with a particulate solvent in which hydrodynamic interactions are accounted through the intermolecular interactions, multiparticle collision dynamics (MPCD) with a point particle solvent which has stochastic interactions with the polymer, and the lattice Boltzmann method in which the polymer chains are coupled to the lattice fluid through friction. Our results show that the three methods give quantitatively similar results for the effect of chain topology on the conformation and diffusion behavior of the polymer chain in a good solvent. The ratio of diffusivities of ring and linear polymers is observed to be close to that predicted by perturbation calculations based on the Kirkwood hydrodynamic theory. [ABSTRACT FROM AUTHOR]

A simplified mode-coupling theory (MCT) of ergodic–nonergodic transitions, in conjunction with an accurate two-component polymer reference interaction site model (PRISM) theory for equilibrium structural correlations, has been systematically applied to investigate gelation, localization, and elasticity of flexible polymer-hard particle suspensions. The particle volume fraction at the fluid–gel transition is predicted to depend exponentially on reduced polymer concentration and size asymmetry ratio at relatively high colloid concentrations. In contrast, at lower particle volume fractions, a power-law dependence on polymer concentration is found with effective exponents and prefactors that depend systematically on the polymer/particle size ratio. Remarkable power-law and near universal scaling behavior is found for the localization length and elastic shear modulus. Multiple experiments for gel boundaries and shear moduli are in good agreement with the no adjustable parameter theory. The one exception is the absolute magnitude of the shear modulus which is strongly overpredicted, apparently due to nonequilibrium dense cluster formation. The simplified MCT-PRISM theory also captures the qualitative aspects of the weak depletion-driven “glass melting” phenomenon at high particle volume fractions. Calculations based on an effective one-component model of structure within a low particle volume fraction framework yield qualitatively different features than the two-component approach and are apparently all in disagreement with experiments. This suggests that volume fraction and size asymmetry dependent many-body screening of polymer-mediated depletion attractions at finite particle concentrations are important. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We investigate the conformation and dynamics of a semi-flexible polymer near an attractive plane or a cylindrical post using Langevin dynamics. We characterize the transition from the desorbed to absorbed state and quantify how absorption depends on the attraction interaction, polymer molecular weight, polymer flexibility, intra-polymer interaction, and micro-confinement. We find that the critical point of adsorption for ideal flexible polymers only weakly depends on confinement. However, the critical point of adsorption increases significantly for self-avoiding flexible polymers and under confinement, deviating from scaling theory predictions. These findings provide insights into DNA surface adsorption in nanoslits and nanochannels.

We investigated nanoparticle (NP)-induced coil-to-globule transition of a semi-flexible polymer in a confined suspension of ideal NP using Langevin dynamics. DNA molecules are often found to be highly compact, bound with oppositely charged proteins in a crowded environment within cells and viruses. Recent studies found that high concentration of electrostatically neutral NP also condenses DNA due to entropically induced depletion attraction between DNA segments. Langevin dynamics simulations with a semi-flexible chain under strong confinement were performed to investigate the competition between NP-induced monomer-monomer and monomer-wall attraction under different confinement heights and NP volume fractions. We found that whether NP induce polymer segments to adsorb to the walls and swell or to attract one another and compact strongly depends on the relative strength of the monomer-wall and the NP-wall interactions.

The complexity of the coupling between soft particle deformation and fluid perturbation has limited studies of soft particle hydrodynamics to dilute suspensions. A hybrid Brownian dynamics-lattice Boltzmann method is presented that models nondilute soft spherical deformable particle (DP) suspensions in flow. Dependences on particle size and density are investigated for suspensions with over 100 DP. Multi-DP interactions lead to complex dependence of particle distributions on concentration and flow rate. Flow-induced DP migration toward channel center for DP in narrow channels is found. In wide channels, off-center peaks in the center of mass distribution for DP are found. The migration of DP leads to faster average speed of DP than the flow, which can be exploited for fractionating DPs of different sizes.

Phase separation of asymmetric diblock copolymer near surfaces in selective solvents is theoretically investigated by using the real-space version of self-consistent field theory (SCFT). Several morphologies are predicted and the phase diagram is constructed by varying the distance between two parallel hard surfaces (or the film thickness) W and the block copolymer concentration f(P). Morphologies of the diblock copolymer in dilute solution are found to change significantly with different film thicknesses. In confined systems, stable morphologies found in the bulk solution become unstable due to the loss of polymer conformation entropy. The vesicle phase region contracts when the repulsive interaction between the blocks is strong (strong segregation regime). The mixture of vesicles, rodlike and spherelike micelles and the mixture of vesicles and sphere-like micelles disappear in contrast to the weakly segregating regime. The walls strongly affect the phase separation of block copolymer in selective solvent, and the depletion layer near the surface contributes much to the micelle formation of the block copolymer. Interestingly, the self-assembled morphologies stay near the walls with the distance on the order of the radius of gyration of the block copolymer. The oscillation of the polymer distribution near the walls allows the surface phase separation to be observed due to the strong repulsion between the blocks A and B.