Reshaping elastic nanotubes via self-assembly of surface-adhesive nanoparticles.

Elastic sheets with macroscopic dimensions are easy to deform by bending and stretching. Yet shaping nanometric sheets by mechanical manipulation is hard. Here we show that nanoparticle self-assembly could be used to this end. We demonstrate that spherical nanoparticles adhering to the outer surface of an elastic nanotube can self-assemble into linear structures: rings or helices on stretchable nanotubes, and axial strings on nanotubes with high rigidity to stretching. These self-assembled structures are inextricably linked to a variety of deformed nanotube profiles, which can be controlled by tuning the concentration of nanoparticles, the nanoparticle-nanotube diameter ratio and the elastic properties of the nanotube. Our results open the possibility of designing nanoparticle-laden tubular nanostructures with tailored shapes, for potential applications in materials science and nanomedicine.

Effective elasticity of a flexible filament bound to a deformable cylindrical surface.

We use numerical simulations to show how a fully flexible filament binding to a deformable cylindrical surface may acquire a macroscopic persistence length and a helical conformation. This is a result of the nontrivial elastic response to deformations of elastic sheets. We find that the filament's helical pitch is completely determined by the mechanical properties of the surface, and can be easily tuned by varying the surface stretching rigidity. We propose simple scaling arguments to understand the physical mechanism behind this phenomenon and present a phase diagram indicating under what conditions one should expect a fully flexible chain to behave as a helical semiflexible filament. Finally, we discuss the implications of our results.

Phase behavior of repulsive polymer-tethered colloids.

We report molecular dynamics simulations of a system of repulsive, polymer-tethered colloidal particles. We use an explicit polymer model to explore how the length and the behavior of the polymer (ideal or self-avoiding) affect the ability of the particles to organize into ordered structures when the system is compressed to moderate volume fractions. We find a variety of different phases whose origin can be explained in terms of the configurational entropy of polymers and colloids. Finally, we discuss and compare our results to those obtained for similar systems using simplified coarse-grained polymer models, and set the limits of their applicability.

Phase diagram of Hertzian spheres.

We report the phase diagram of interpenetrating Hertzian spheres. The Hertz potential is purely repulsive, bounded at zero separation, and decreases monotonically as a power law with exponent 5/2, vanishing at the overlapping threshold. This simple functional describes the elastic interaction of weakly deformable bodies and, therefore, it is a reliable physical model of soft macromolecules, like star polymers and globular micelles. Using thermodynamic integration and extensive Monte Carlo simulations, we computed accurate free energies of the fluid phase and a large number of crystal structures. For this, we defined a general primitive unit cell that allows for the simulation of any lattice. We found multiple re-entrant melting and first-order transitions between crystals with cubic, trigonal, tetragonal, and hexagonal symmetries.

Protein shape and crowding drive domain formation and curvature in biological membranes.

Folding, curvature, and domain formation are characteristics of many biological membranes. Yet the mechanisms that drive both curvature and the formation of specialized domains enriched in particular protein complexes are unknown. For this reason, studies in membranes whose shape and organization are known under physiological conditions are of great value. We therefore conducted atomic force microscopy and polarized spectroscopy experiments on membranes of the photosynthetic bacterium Rhodobacter sphaeroides. These membranes are densely populated with peripheral light harvesting (LH2) complexes, physically and functionally connected to dimeric reaction center-light harvesting (RC-LH1-PufX) complexes. Here, we show that even when converting the dimeric RC-LH1-PufX complex into RC-LH1 monomers by deleting the gene encoding PufX, both the appearance of protein domains and the associated membrane curvature are retained. This suggests that a general mechanism may govern membrane organization and shape. Monte Carlo simulations of a membrane model accounting for crowding and protein geometry alone confirm that these features are sufficient to induce domain formation and membrane curvature. Our results suggest that coexisting ordered and fluid domains of like proteins can arise solely from asymmetries in protein size and shape, without the need to invoke specific interactions. Functionally, coexisting domains of different fluidity are of enormous importance to allow for diffusive processes to occur in crowded conditions.

Application of the optimized Baxter model to the hard-core attractive Yukawa system.

We perform Monte Carlo simulations on the hard-core attractive Yukawa system to test the optimized Baxter model that was introduced by Prinsen and Odijk [J. Chem. Phys. 121, 6525 (2004)] to study a fluid phase of spherical particles interacting through a short-range pair potential. We compare the chemical potentials and pressures from the simulations with analytical predictions from the optimized Baxter model. We show that the model is accurate to within 10% over a range of volume fractions from 0.1 to 0.4, interaction strengths up to three times the thermal energy, and interaction ranges from 6% to 20% of the particle diameter, and performs even better in most cases. We furthermore establish the consistency of the model by showing that the thermodynamic properties of the Yukawa fluid computed via simulations may be understood on the basis of one similarity variable, the stickiness parameter defined within the optimized Baxter model. Finally, we show that the optimized Baxter model works significantly better than an often used, naive method determining the stickiness parameter by equating the respective second virial coefficients based on the attractive Yukawa and Baxter potentials.

Phase and interface behaviors in type-I and type-V Lennard-Jones mixtures: theory and simulations.

Density gradient theory (DGT) and molecular-dynamics (MD) simulations have been used to predict subcritical phase and interface behaviors in type-I and type-V equal-size Lennard-Jones mixtures. Type-I mixtures exhibit a continuum critical line connecting their pure critical components, which implies that their subcritical phase equilibria are gas liquid. Type-V mixtures are characterized by two critical lines and a heteroazeotropic line. One of the two critical lines begins at the more volatile pure component critical point up to an upper critical end point and the other one comes from the less volatile pure component critical point ending at a lower critical end point. The heteroazeotropic line connects both critical end points and is characterized by gas-liquid-liquid equilibria. Therefore, subcritical states of this type exhibit gas-liquid and gas-liquid-liquid equilibria. In order to obtain a correct characterization of the phase and interface behaviors of these types of mixtures and to directly compare DGT and MD results, the global phase diagram of equal-size Lennard-Jones mixtures has been used to define the molecular parameters of these mixtures. According to our results, DGT and MD are two complementary methodologies able to obtain a complete and simultaneous prediction of phase equilibria and their interfacial properties. For the type of mixtures analyzed here, both approaches have shown excellent agreement in their phase equilibrium and interface properties in the full concentration range.

Thermodynamic properties of Lennard-Jones chain molecules: renormalization-group corrections to a modified statistical associating fluid theory.

A modified version of the statistical associating fluid theory (SAFT), the so-called soft-SAFT equation of state (EOS), has been extended by a crossover treatment to take into account the long density fluctuations encountered when the critical region is approached. The procedure, based on White's work from the renormalization group theory [Fluid Phase Equilibria 75, 53 (1992); L. W. Salvino and J. A. White, J. Chem. Phys. 96, 4559 (1992)], is implemented in terms of recursion relations where the density fluctuations are successively incorporated. The crossover soft-SAFT equation provides the correct nonclassical critical exponents when approaching the critical point, and reduces to the original soft-SAFT equation far from the critical region. The accuracy of the global equation is tested by direct comparison with molecular simulation results of Lennard-Jones chains, obtaining very good agreement and clear improvements compared to the original soft-SAFT EOS. Excellent agreement with vapor-liquid equilibrium experimental data inside and outside the critical region for the n-alkane series is also obtained. We provide a set of transferable molecular parameters for this family, unique for the whole range of thermodynamic properties.

Thermodynamic properties and aggregate formation of surfactant-like molecules from theory and simulation.

The goal of this work is twofold: to predict the phase equilibria behavior of simplified surfactant models and to predict the population of aggregates as a function of pressure. We compare Monte Carlo simulation results of these systems with predictions from a modified version of the statistical associating fluid theory (soft-SAFT). Surfactant-like molecules are modeled as Lennard-Jones chains of tangent segments with one or two association sites. We study the influence of the number and location of the association sites on the thermodynamic properties and fraction of nonbonded molecules in all cases. The influence of the chain length is also investigated for a particular location of the sites. Results are compared with NPT Monte Carlo simulations to test the accuracy of the theory, and to study the molecular configurations of the system. Soft-SAFT is able to quantitatively predict the MC PVT results, independently of the location of the association sites. The theory is also able to capture the qualitative trend of the population of aggregates with pressure. Quantitative agreement is only obtained for specific locations of the sites.

Interfacial properties of Lennard-Jones chains by direct simulation and density gradient theory.

We perform a series of molecular dynamics simulations of Lennard-Jones chains systems, up to tetramers, in order to investigate the influence of temperature and chain length on their phase separation and interfacial properties. Simulation results serve as a test to check the accuracy of a statistical associated fluid theory (soft-SAFT) coupled with the density gradient theory. We focus on surface tension and density profiles. The simulations allow us to discuss the success and limitations of the theory and how to estimate the only adjustable parameter, the influence parameter. This parameter is obtained by fitting the surface tension, and then used to obtain the density profiles in a predictive manner. A good agreement is found if the temperature dependence of this parameter is neglected.(c) 2004 American Institute of Physics.