Surface Polaron Effect on the Ion Transfer across the Interface of Two Immiscible Electrolytes

An ion disposed near the interface of two immiscible liquids creates a protrusion of one solvent into the other, subject to hydrophobic or hydrophilic interaction with these solvents. Due to a finite relaxation time the protrusion may not be able to spontaneously follow the ion when it moves across the interface. This, as well as any improper thermal fluctuation of the protrusion, will cause slowdown of the ion transfer. Here we present the results of theoretical analysis in which the stochastic motions of the ion and protrusion are coupled and considered on the same footing. We show that if the equilibrium electrochemical potential for the ion has no barrier, the ion transport is purely diffusional with D _eff = k _B T/{6[r + (4/3)(h _max/)² L]} being the effective diffusion coefficient. Here, is the average viscosity of the liquids, r is the Stokes radius of an ion, L and h _max are the average lateral size and the maximal height of the protrusion, and is the half-width of the function h _eq(z) which characterizes the equilibrium ion-interface coupling [h _eq(z) is the height of the protrusion for a given distance of the ion to the unperturbed interface, if the ion had been infinitely slowly moving]. This function could be obtained from model calculations or molecular dynamic simulations. The second term in the denominator is the one that causes the slowdown of ion transfer across the interface. This expression can easily rationalize an order of magnitude slowdown, but hardly much more than that. This is not inconsistent with recent more careful claims on the true scale of the observed effect. Otherwise, one should invoke models that rest on the existence of the barrier in the electrochemical potential.     

Direct observation of azimuthal correlations between DNA in hydrated aggregates

This study revisits the classical x-ray diffraction patterns from hydrated, noncrystalline fibers originally used to establish the helical structure of DNA. We argue that changes in these diffraction patterns with DNA packing density reveal strong azimuthally dependent interactions between adjacent molecules up to approximately 40 A interaxial or approximately 20 A surface-to-surface separations. These interactions appear to force significant torsional "straightening" of DNA and strong azimuthal alignment of nearest neighbor molecules. The results are in good agreement with the predictions of recent theoretical models relating DNA-DNA interactions to the helical symmetry of their surface charge patterns.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...     

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm （diameter） polystyrene. The liquid mixtures, in the proper proportions of water （H2O）, deuterium oxide （D2O） and methanol （MeOH） as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes （reduction） in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable.     

Double layer in ionic liquids: The nature of the camel shape of capacitance

Monte Carlo simulations of a model ionic liquid show that if ions have charged heads and neutral counterparts, the latter give rise to the camel shape of the voltage dependence of the double layer capacitance. Neutral ‘tails’ of ions play the role of latent voids that can be replaced by charged groups via rotations and translations of ions. This provides extra degrees of freedom for the field-induced charge rearrangements in the double layer which results in the peculiar double-hump capacitance profile.