No abstract

The liquid crystal phase behavior of linear and partially flexible hard-sphere chain fluids and the solubility of hard spheres in hard-sphere chain fluids are studied by constant pressure Monte Carlo simulations. An extensive study on the phase behavior of linear fluids with a length of 7,8,9,10,11,12,13,14,15, and 20 beads is carried out. The phase behavior of partially flexible fluids with a total length of 8, 10, 14, and 15 beads and with different lengths for the linear part is also determined. A precise description of the reduced pressure and of the packing fraction change at the isotropicnematic coexistence was achieved by performing long simulation runs. For linear fluids, a maximum in the isotropic to nematic packing fraction change is observed for a chain length of 15 beads. The infinite dilution solubility of hard spheres in linear and partially flexible hard-sphere chain fluids is calculated by the Widom test-particle insertion method. To identify the effect of chain connectivity and molecular anisotropy on free volume, solubility is expressed relative to that of hard spheres in a hard sphere fluid at same packing fraction as relative Henry's law constants. A linear relationship between relative Henry's law constants and packing fraction is observed for all linear fluids. Furthermore, this linearity is independent of liquid crystal ordering and seems to be independent of chain length for linear chains of 10 beads and longer. The same linear relationship was observed for the solubility of hard spheres in nematic forming partially flexible fluids for packing fractions up to a value slightly higher than the nematic packing fraction at the isotropic-nematic coexistence. At higher packing fractions, the small flexibility of these fluids seems to improve solubility in comparison with the linear fluids. © 2013 AIP Publishing LLC. [http://dx

We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

The possibility of prescribing local interactions between nano-and microscopic components that direct them to assemble in a predictable fashion is a central goal of nanotechnology research. In this article we advance a new paradigm in which self-assembly of DNA-functionalized colloidal particles is programmed using linker oligonucleotides dispersed in solution. We find a phase diagram that is surprisingly rich compared to phase diagrams typical of other DNA-functionalized colloidal particles that interact by direct hybridization, including a re-entrant melting transition upon increasing linker concentration, and show that multiple linker species can be combined together to prescribe many interactions simultaneously. A new theory predicts the observed phase behavior quantitatively without any fitting parameters. Taken together, these experiments and model lay the groundwork for future research in programmable self-assembly, enabling the possibility of programming the hundreds of specific interactions needed to assemble fully-addressable, mesoscopic structures, while also expanding our fundamental understanding of the unique phase behavior possible in colloidal suspensions.arXiv:1902.08883v2 [cond-mat.soft]

An extension of Onsager's second virial theory is developed to describe the isotropic-nematic phase transition of tangent hard-sphere chain fluids. Flexibility is introduced by the rod-coil model. The effect of chain-flexibility on the second virial coefficient is described using an accurate, analytical approximation for the orientation-dependent pair-excluded volume. The use of this approximation allows for an analytical treatment of intramolecular flexibility by using a single pure-component parameter. Two approaches to approximate the effect of the higher virial coefficients are considered, i.e., the Vega-Lago rescaling and Scaled Particle Theory (SPT). The Onsager trial function is employed to describe the orientational distribution function. Theoretical predictions for the equation of state and orientational order parameter are tested against the results from Monte Carlo (MC) simulations. For linear chains of length 9 and longer, theoretical results are in excellent agreement with MC data. For smaller chain lengths, small errors introduced by the approximation of the higher virial coefficients become apparent, leading to a small under-and overestimation of the pressure and density difference at the phase transition, respectively. For rod-coil fluids of reasonable rigidity, a quantitative comparison between theory and MC simulations is obtained. For more flexible chains, however, both the Vega-Lago rescaling and SPT lead to a small underestimation of the location of the phase transition. © 2013 AIP Publishing LLC. [http://dx