Elshad Allahyarov

Simulation Study of the Correlation between Structure and Conductivity in Stretched Nafion

We have used coarse-grained simulation methods to investigate the effect of stretching-induced structure orientation on the proton conductivity of Nafion-like polymer electrolyte membranes. Our simulations show that uniaxial stretching causes the hydrophilic regions to become elongated in the stretching direction. This change has a strong effect on the proton conductivity, which is enhanced along the stretching direction, while the conductivity perpendicular to the stretched polymer backbone is reduced. In a humidified membrane, stretching also causes the perfluorinated side chains to tend to orient perpendicular to the stretching axis. This in turn affects the distribution of water at low water contents. The water forms a continuous network with narrow bridges between small water clusters absorbed in head group multiplets. In a dry membrane the side chains orient along the stretching direction.

Attraction between DNA molecules mediated by multivalent ions

The effective force between two parallel DNA molecules is calculated as a function of their mutual separation for different valencies of counter- and salt ions and different salt concentrations. Computer simulations of the primitive model are used and the shape of the DNA molecules is accurately modelled using different geometrical shapes. We find that multivalent ions induce a significant attraction between the DNA molecules whose strength can be tuned by the averaged valency of the ions. The physical origin of the attraction is traced back either to electrostatics or to entropic contributions. For multivalent counter- and monovalent salt ions, we find a salt-induced stabilization effect: the force is first attractive but gets repulsive for increasing salt concentration. Furthermore, we show that the multivalent-ion-induced attraction does not necessarily correlate with DNA overcharging.

Discrete charge patterns, Coulomb correlations and interactions in protein solutions

The effective Coulomb interaction between globular proteins is calculated as a function of monovalent salt concentration cs, by explicit Molecular Dynamics simulations of pairs of model proteins in the presence of microscopic co and counterions. For discrete charge patterns of monovalent sites on the surface, the resulting osmotic virial coefficient B2 is found to be a strikingly non-monotonic function of cs. The non-monotonicity follows from a subtle Coulomb correlation effect which is completely missed by conventional non-linear Poisson-Boltzmann theory and explains various experimental findings.

Semicrystalline Structure–Dielectric Property Relationship and Electrical Conduction in a Biaxially Oriented Poly(vinylidene fluoride) Film under High Electric Fields and High Temperatures

Poly(vinylidene fluoride) (PVDF)-based homopolymers and copolymers are attractive for a broad range of electroactive applications because of their high dielectric constants. Especially, biaxially oriented PVDF (BOPVDF) films exhibit a DC breakdown strength as high as that for biaxially oriented polypropylene films. In this work, we revealed the molecular origin of the high dielectric constant via study of a commercial BOPVDF film. By determination of the dielectric constant for the amorphous phase in BOPVDF, a high value of ca. 21-22 at 25 °C was obtained, and a three-phase (i.e., lamellar crystal/oriented interphase/amorphous region) semicrystalline model was proposed to explain this result. Meanwhile, electronic conduction mechanisms in BOPVDF under high electric fields and elevated temperatures were investigated by thermally stimulated depolarization current (TSDC) spectroscopy and leakage current studies. Space charge injection from metal electrodes was identified as a major factor for electronic conduction when BOPVDF was poled above 75 °C and 20 MV/m. In addition, when silver or aluminum were used as electrodes, new ions were generated from electrochemical reactions under high fields. Due to the electrochemical reactions between PVDF and the metal electrode, a question is raised for practical electrical applications using PVDF and its copolymers under high-field and high-temperature conditions. A potential method to prevent electrochemical degradation of PVDF is proposed in this study.

EFFECT OF GEOMETRICAL CONFINEMENT ON THE INTERACTION BETWEEN CHARGED COLLOIDAL SUSPENSIONS

The effective interaction between charged colloidal particles confined between two planar like-charged walls is investigated using computer simulations of the primitive model describing asymmetric electrolytes. In detail, we calculate the effective force acting onto a single macroion and onto a macroion pair in the presence of slit-like confinement. For moderate Coulomb coupling, we find that this force is repulsive. Under strong coupling conditions, however, the sign of the force depends on the distance to the plates and on the interparticle distance. In particular, the particle-plate interaction becomes strongly attractive for small distances which may explain the occurrence of colloidal crystalline layers near the plates observed in recent experiments.

Heterogeneous crystallization of hard-sphere colloids near a wall

We investigate the most basic situation of heterogeneous crystallization: crystallization of hard-sphere colloids in the presence of a flat hard wall. Using a combination of confocal microscopy and nonequilibrium Brownian dynamics simulations, microscopic time-resolved information is obtained on an individual-particle level. Initially, particles near the wall rearrange before an extended regime of crystal growth is found. During growth, we can directly observe a depletion zone in the fluid next to the progressing crystal–fluid interface due to the single-particle information provided by microscopy and simulations. This also allows us to follow the relaxation of the crystal layers and the progression of the crystal–fluid interface. In good agreement between our experiments and simulations, as well as previous studies, the growth rate shows a maximum in its dependence on the bulk volume fraction.

Adsorption of monovalent and multivalent cations and anions on DNA molecules.

Adsorption of monovalent and multivalent cations and anions on a deoxyribose nucleic acid (DNA) molecule from a salt solution is investigated by computer simulation. The ions are modeled as charged hard spheres, the DNA molecule as a point charge pattern following the double-helical phosphate strands. The geometrical shape of the DNA molecules is modeled on different levels ranging from a simple cylindrical shape to structured models which include the major and minor grooves between the phosphate strands. The densities of the ions adsorbed on the phosphate strands in the major and in the minor grooves are calculated. First, we find that the adsorption pattern on the DNA surface depends strongly on its geometrical shape: counterions adsorb preferentially along the phosphate strands for a cylindrical model shape, but in the minor groove for a geometrically structured model. Second, we find that an addition of monovalent salt ions results in an increase of the charge density in the minor groove while the total charge density of ions adsorbed in the major groove stays unchanged. The adsorbed ion densities are highly structured along the minor groove while they are almost smeared along the major groove. Furthermore, for a fixed amount of added salt, the major-groove cationic charge is independent of the counterion valency. For increasing salt concentration the major groove is neutralized while the total charge adsorbed in the minor groove is constant. DNA overcharging is detected for multivalent salts. Simulations for larger ion radii, which mimic the effect of ion hydration, indicate an increased adsorbtion of cations in the major groove.

Crystallization seeds favour crystallization only during initial growth

Crystallization represents the prime example of a disorder–order transition. In realistic situations, however, container walls and impurities are frequently present and hence crystallization is heterogeneously seeded. Rarely the seeds are perfectly compatible with the thermodynamically favoured crystal structure and thus induce elastic distortions, which impede further crystal growth. Here we use a colloidal model system, which not only allows us to quantitatively control the induced distortions but also to visualize and follow heterogeneous crystallization with single-particle resolution. We determine the sequence of intermediate structures by confocal microscopy and computer simulations, and develop a theoretical model that describes our findings. The crystallite first grows on the seed but then, on reaching a critical size, detaches from the seed. The detached and relaxed crystallite continues to grow, except close to the seed, which now prevents crystallization. Hence, crystallization seeds facilitate crystallization only during initial growth and then act as impurities.

Influence of solvent granularity on the effective interaction between charged colloidal suspensions

We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard-sphere solvent. Apart from molecular oscillating forces for nearly touching colloids that arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerably reduced as compared to the prediction based on the primitive model. When these forces are repulsive, the long-distance behavior can be described by an effective Yukawa pair potential with a solvent-renormalized charge. As a function of colloidal volume fraction and added salt concentration, this solvent-renormalized charge behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell model, but there are quantitative differences. For divalent counterions and nanosized colloids, on the other hand, the hydration may lead to overscreened colloids with mutual attraction while the primitive model yields repulsive forces. All these new effects can be accounted for through a solvent-averaged primitive model (SPM) which is obtained from the full model by integrating out the solvent degrees of freedom. The SPM was used to access larger colloidal particles without simulating the solvent explicitly.

DNA condensation and redissolution: interaction between overcharged DNA molecules

The effective DNA-DNA interaction force is calculated by computer simulations with explicit tetravalent counterions and monovalent salt. For overcharged DNA molecules, the interaction force shows a double-minimum structure. The positions and depths of these minima are regulated by the counterion density in the bulk. Using two-dimensional lattice sum and free energy perturbation theories, the coexisting phases for DNA bundles are calculated. A DNA-condensation and redissolution transition and a stable mesocrystal with an intermediate lattice constant for high counterion concentration are obtained. PACS numbers: PACS: 87.15.Kg, 61.20Ja, 82.70.Dd, 87.10+e † To whom correspondence should be addressed (allahyar@thphy.uni-duesseldorf.de) DNA condensation and redissolution: Interaction between overcharged DNA molecules. 2The effective DNA–DNA interaction force is calculated by computer simulations with explicit tetravalent counterions and monovalent salt. For overcharged DNA molecules, the interaction force shows a double-minimum structure. The positions and depths of these minima are regulated by the counterion density in the bulk. Using two-dimensional lattice sums and free energy perturbation theories, the coexisting phases for DNA bundles are calculated. A DNA condensation and redissolution transition and a stable mesocrystal with an intermediate lattice constant for high counterion concentration are obtained.