Non-linear osmotic brush regime: Simulations and mean-field theory

We investigate polyelectrolyte brushes in the osmotic regime using both theoretical analysis and molecular dynamics simulation techniques. In the simulations at moderate Bjerrum length, we observe that the brush height varies weakly with grafting density, in contrast to the accepted scaling law, which predicts a brush thickness independent of the grafting density. We show that such behavior can be explained by considering lateral electrostatic effects (within the non-linear Poisson-Boltzmann theory) combined with the coupling between lateral and longitudinal degrees of freedom due to the conserved polymer volume (which are neglected in scaling arguments). We also take the non-linear elasticity of polyelectrolyte chains into consideration, which makes significant effects as chains are almost fully stretched in the osmotic regime. It is shown that all these factors lead to a non-monotonic behavior for the brush height as a function of the grafting density. At large grafting densities, the brush height increases with increasing the grafting density due to the volume constraint. At small grafting densities, we obtain a re-stretching of the chains for decreasing grafting density, which is caused by lateral electrostatic contributions and is controlled by the counterion-condensation process around polyelectrolyte chains. These results are obtained assuming all counterions to be trapped within the brush, which is valid for sufficiently long chains of large charge fraction.Received: 14 May 2003, Published online: 11 November 2003PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 36.20.-r Macromolecules and polymer molecules - 61.20.Qg Structure of associated liquids: electrolytes, molten salts, etc.     

Binding of similarly charged plates with counterions only

Similarly and highly charged plates in the presence of multivalent counterions attract each other and form electrostatically bound states. Using Monte-Carlo simulations, we obtain the interplate pressure in the global parameter space. The equilibrium plate separation, where the pressure changes from attractive to repulsive, exhibits a novel unbinding transition. A systematic and asymptotically exact strong-coupling field theory yields the bound state from a competition between counterion entropy and electrostatic attraction, in agreement with simple scaling arguments and simulations.     

Oscillatory melting temperature of the vortex smectic phase in layered superconductors

We report on transport measurements of YBa 2Cu 3O (7-delta) single crystals with different oxygen contents in the geometry B, J ||ab (J perpendicularB). Our data show that the vortices become confined between the Cu-O planes below a well-defined temperature at which the effective size 2xi of the vortex core is approximately equal to the period of the Cu-O layers. This confinement strongly increases the vortex liquid freezing temperature. A new melting line is found separating a vortex liquid and a smectic phase, which shows an oscillatory field dependence reflecting differences between commensurate and incommensurate smectic states.     

Electrostatistics of counter-ions at and between planar charged walls: From Poisson-Boltzmann to the strong-coupling theory

The European Physical Journal E - The Poisson-Boltzmann (PB) approach gives asymptotically exact counter-ion density profiles around macroscopic charged objects and forces between macroscopic...     

Synthesis of Novel Chiral Diol Ligands for the Enantioselective Reactions

The chiral diols ((,(,((,((-Tetraaryl-1,3-dioxolane-4,5-dimethanols) have been used for the formation of cyclic titanates and similar derivatives of Mg, Al and Zr. These complexes of oxophilic metal centers were employed in catalytic and stiochiometric enantioselective reactions such as enantioselective addition reactions of carbon-centered nucleophiles to aldehydes1, [2+2] cycloadditions2, and Diels-Alder reactions3. So far, the two hydrogen atoms of all this type of diols are in trans form…     

The diffraction of elastic waves by an imperfect fusion bond

We consider diffraction by a semi-infinite crack located alonga fusion interface between two differing elastic media. Twotypes of crack, namely open and partially closed cracks, areinvestigated. An open crack is modelled by a stress-free contactboundary condition and a partially closed crack is modelledby a spring contact boundary condition. For the latter, thejump in the stress across the crack is assumed to be proportionalto the jump in the displacement across the crack. This situationarises in, for example, a K-weld where the fine grain of theparent material (for example, ferritic or forged austeniticsteel) is in stark contrast with the coarse-grained weld metal(for example, austenitic weld metal). In the metal weld thedirection of the grain axis varies through the metal. However,diffraction is a local phenomenon and so the austenitic steelis assumed to have a zonal axis so that it may be modelled bya transversely isotropic composite. The ferritic or forged austeniticsteel will be modelled as an isotropic material.     

The quadrupole moment of the 535 keV state of 133La

The quadrupole moment of the 535 keV $\text{3}\text{2}{}^{\mathrm{?}}$ state of ¹³³La has been derived from a time-differential perturbed angular correlation measurement in an environment of La metal. The effective electric gradient is known from a nuclear quadrupole resonance measurement with the ground state of ¹³⁹La. The result Q = 0.35 ± 0.03 b does not confirm a proposed shape isomerism.     

Time-dependent electric quadrupole interactions in (NH4)3HfF7

Spinrotation spectra of polycrystalline (NH₄)₃HfF₇ in which radioactive¹⁸¹Hf was incorporated have been measured in the temperature range from ?196 °C to + 70 °C. The spectra were interpretated on the base of the stochastic model of M. Blume. It was assumed that reorientations of the [HfF₇]^3? polyhedra take place at random. The resulting fluctuation rates can be understood as to be caused by an activation process. The activation energy was determined to 0.324(12) eV in agreement with NMR measurements on¹⁹F in this compound.     

Viscous compressible hydrodynamics at planes,spheres and cylinders with finite surface slip

We consider the linearized time-dependent Navier-Stokes equation including finite compressibility and viscosity. We first constitute the Green's function, from which we derive the flow profiles and response functions for a plane, a sphere and a cylinder for arbitrary surface slip length. For high driving frequency the flow pattern is dominated by the diffusion of vorticity and compression, for low frequency compression propagates in the form of sound waves which are exponentially damped at a screening length larger than the sound wave length. The crossover between the diffusive and propagative compression regimes occurs at the fluid's intrinsic frequency w \omega ∼ c ² r₀ \rho_{0}^{}/h \eta , with c the speed of sound, r₀ \rho_{0}^{} the fluid density and h \eta the viscosity. In the propagative regime the hydrodynamic response function of spheres and cylinders exhibits a high-frequency resonance when the particle size is of the order of the sound wave length. A distinct low-frequency resonance occurs at the boundary between the propagative and diffusive regimes. Those resonant features should be detectable experimentally by tracking the diffusion of particles, as well as by measuring the fluctuation spectrum or the response spectrum of trapped particles. Since the response function depends sensitively on the slip length, in principle the slip length can be deduced from an experimentally measured response function.