Biomedical subjects

C N Likos

Publications and source records attributed to C N Likos.

14 recordsLinked to original sources

PubMed2004

Soft effective interactions between weakly charged polyelectrolyte chains.

We apply extensive molecular dynamics simulations and analytical considerations in order to study the conformations and the effective interactions between weakly charged, flexible polyelectrolyte chains in salt-free conditions. We focus on charging fractions lying below 20%, for which case there is no Manning condensation of counterions and the latter can be thus partitioned in two states: those that are trapped within the region of the flexible chain and the ones that are free in the solution. We examine the partition of counterions in these two states, the chain sizes and the monomer distributions for various chain lengths, finding that the monomer density follows a Gaussian shape. We calculate the effective interaction between the centers of mass of two interacting chains, under the assumption that the chains can be modeled as two overlapping Gaussian charge profiles. The analytical calculations are compared with measurements from molecular dynamics simulations. Good quantitative agreement is found for charging fractions below 10%, where the chains assume coil-like configurations, whereas deviations develop for charge fraction of 20%, in which case a conformational transition of the chain towards a rodlike configuration starts to take place.

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PubMed2004

Is there a reentrant glass in binary mixtures?

By employing computer simulations for a model binary mixture, we show that a reentrant glass transition upon adding a second component occurs only if the ratio alpha of the short-time mobilities between the glass-forming component and the additive is sufficiently small. For alpha approximately 1, there is no reentrant glass, even if the size asymmetry between the two components is large, in accordance with the two-component mode-coupling theory. For alpha<<1, on the other hand, the reentrant glass is observed and reproduced only by an effective one-component mode-coupling theory.

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PubMed2004

Tunable effective interactions between dendritic macromolecules.

We employ extensive Monte Carlo and molecular-dynamics simulations to investigate the effective interactions between the centers of mass of dendritic macromolecules of variable flexibility and generation number. Two different models for the connectivity and steric interactions between the monomers are employed, the first one being purely entropic in nature and the second explicitly involving energetic interactions. We find that the effective potentials have a generic Gaussian shape, whose range and strength can be tuned via modifications in the generation number and flexibility of the spacers. We supplement our simulation analysis by a density-functional approach in which the connectivity between the monomers is approximated by an external confining potential that holds the monomer beads together. Using a simple density functional for the interactions between the monomers, we find semiquantitative agreement between theory and simulation. The implications of our findings for the interpretation of scattering data from concentrated dendrimer solutions are also discussed.

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PubMed2004

Phase behavior of ionic microgels.

We employ effective interaction potentials between spherical polyelectrolyte microgels in order to investigate theoretically the structure, thermodynamics, and phase behavior of ionic microgel solutions. Combining a genetic algorithm with accurate free energy calculations we are able to perform an unrestricted search of candidate crystal structures. Hexagonal, body-centered orthogonal, and trigonal crystals are found to be stable at high concentrations and charges of the microgels, accompanied by reentrant melting behavior and fluid-fcc-bcc transitions below the overlap concentration.

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PubMed2003

Crystal structures of two-dimensional magnetic colloids in tilted external magnetic fields.

The stability of different crystal lattices of two-dimensional superparamagnetic suspensions that are confined to a planar liquid-gas interface and exposed to a tilted external magnetic field is studied theoretically by lattice sum minimizations. The magnetic field induces magnetic dipoles onto the colloidal particles along its direction, whose strength can be controlled by the amplitude of the external field. The mutual interaction between the colloids is governed by dipole-dipole forces and a short-ranged repulsion having its physical origin at the presence of the colloidal cores. If the direction of the magnetic field is perpendicular to the liquid-gas interface, there is a purely repulsive interaction leading to stable triangular crystals. By tilting the external field, the interaction becomes anisotropic and a mutual attraction appears upon a threshold tilt angle. We have calculated the full phase diagram at zero temperature varying the tilt angle, the colloidal density, and the strength of the magnetic field. Apart from the triangular lattice we find a variety of stable crystal lattices including rectangular, oblique, chainlike oblique, and rhombic structures. We also present the accurate derivation of the Hamiltonian of two polarizable particles of finite arbitrary geometries in external magnetic and electric fields.

Colloids↗

PubMed2003

Depletion forces in nonequilibrium.

The concept of effective depletion forces between two fixed big colloidal particles in a bath of small particles is generalized to a nonequilibrium situation where the bath of small Brownian particles is flowing around the big particles with a prescribed velocity. In striking contrast to the equilibrium case, the nonequilibrium forces violate Newton's third law; they are nonconservative and strongly anisotropic, featuring both strong attractive and repulsive domains.

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PubMed2003

Structural arrest in dense star-polymer solutions.

The dynamics of star polymers is investigated via extensive molecular and Brownian dynamics simulations for a large range of functionality f and packing fraction eta. The calculated isodiffusivity curves display both minima and maxima as a function of eta and minima as a function of f. Simulation results are compared with theoretical predictions based on different approximations for the structure factor. In particular, the ideal glass transition line predicted by mode-coupling theory is shown to exactly track the isodiffusivity curves, offering a theoretical understanding for the observation of disordered arrested states in star-polymer solutions.

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PubMed2003

Azimuthal frustration and bundling in columnar DNA aggregates.

The interaction between two stiff parallel DNA molecules is discussed using linear Debye-Hückel screening theory with and without inclusion of the dielectric discontinuity at the DNA surface, taking into account the helical symmetry of DNA. The pair potential furthermore includes the amount and distribution of counterions adsorbed on the DNA surface. The interaction does not only depend on the interaxial separation of two DNA molecules, but also on their azimuthal orientation. The optimal mutual azimuthal angle is a function of the DNA-DNA interaxial separation, which leads to azimuthal frustrations in an aggregate. On the basis of the pair potential, the positional and orientational order in columnar B-DNA assemblies in solution is investigated. Phase diagrams are calculated using lattice sums supplemented with the entropic contributions of the counterions in solution. A variety of positionally and azimuthally ordered phases and bundling transitions is predicted, which strongly depend on the counterion adsorption patterns.

Binding Sites↗

PubMed2002

Polymer-mediated melting in ultrasoft colloidal gels.

Star polymers with a high number of arms, f=263, become kinetically trapped when dispersed in an athermal solvent at concentrations above the overlapping one, forming physical gels. We show that the addition of linear chains at different concentrations and molecular weights reduces the modulus of the gel, eventually melting it. We explain this linear polymer-induced gel-liquid transition in terms of effective interactions and star depletion. In the limit of very high linear-chain molecular weight a "reentrant gelation" is detected and attributed to bridging flocculation, analogous to that observed in colloidal dispersions.

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PubMed2002

Phase behavior of columnar DNA assemblies.

The interaction between two stiff parallel DNA molecules depends not only on the distance between their axes but also on their azimuthal orientation. The positional and orientational order in columnar B-DNA assemblies in solution is investigated, on the basis of the electrostatic pair potential that takes into account DNA helical symmetry and the amount and distribution of adsorbed counterions. A phase diagram obtained by lattice sums predicts a variety of positionally and azimuthally ordered phases and bundling transitions strongly depending on the counterion adsorption patterns.

DNA↗

PubMed2001

Conformations and interactions of star-branched polyelectrolytes.

Combining monomer-resolved molecular dynamics simulations with a theory based on a variational free energy, we calculate the conformational properties and the effective interactions of star-branched polyelectrolytes for a large variety of arm numbers, degrees of polymerization, and charge fractions, with and without added salt. We find quantitative agreement between theory and simulation and put forward analytical expressions that allow the calculation of the interaction between such macromolecules.

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PubMed2001

Phase separation in star-polymer-colloid mixtures.

We examine the demixing transition in star-polymer-colloid mixtures for star arm numbers f=2,6,16,32 and different star-polymer-colloid size ratios 0.18< or =q< or =0.50. Theoretically, we solve the thermodynamically self-consistent Rogers-Young integral equations for binary mixtures using three effective pair potentials obtained from direct molecular computer simulations. The numerical results show a spinodal instability. The demixing binodals are approximately calculated and found to be consistent with experimental observations.

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PubMed2001

Sedimentation profiles of systems with reentrant melting behavior.

We examine sedimentation density profiles of star polymer solutions as an example of colloidal systems in sedimentation equilibrium that exhibit reentrant melting in their bulk phase diagram. Phase transitions between a fluid and a fluid with an intercalated solid are observed below a critical gravitational strength alpha*. Characteristics of the two fluid-solid interfaces in the density profiles occurring in Monte Carlo simulations for alpha<alpha* are in agreement with scaling laws put forth in the framework of a phenomenological theory. Furthermore, we detect density oscillations at the fluid-gas interface at high altitudes for high-gravitational fields, which are verified with density-functional theory and should be observable in surface scattering experiments.

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PubMed2001

Criterion for determining clustering versus reentrant melting behavior for bounded interaction potentials.

We examine in full generality the phase behavior of systems whose constituent particles interact by means of potentials that do not diverge at the origin, are free of attractive parts, and decay fast enough to zero as the interparticle separation r goes to infinity. By employing a mean field-density functional theory which is shown to become exact at high temperatures and/or densities, we establish a criterion that determines whether a given system will freeze at all temperatures or it will display reentrant melting and an upper freezing temperature.

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