Electrostatic interactions between charge regulated spherical macroions.

We study the interaction between two charge regulating spherical macroions with dielectric interior and dissociable surface groups immersed in a monovalent electrolyte solution. The charge dissociation is modelled via the Frumkin-Fowler-Guggenheim isotherm, which allows for multiple adsorption equilibrium states. The interactions are derived from the solutions of the mean-field Poisson-Boltzmann type theory with charge regulation boundary conditions. For a range of conditions we find symmetry breaking transitions from symmetric to asymmetric charge distribution exhibiting annealed charge patchiness, which results in like-charge attraction even in a univalent electrolyte-thus fundamentally modifying the nature of electrostatic interactions in charge-stabilized colloidal suspensions.

Curvature effects in interfacial acidity of amphiphilic vesicles.

We analyze the changes in the vicinal acidity (pH) at a spherical amphiphilic membrane. The membrane is assumed to contain solvent accessible, embedded, dissociable, charge-regulated moieties. Basing our approach on the linear Debye-Hückel approximation, as well as on the nonlinear Poisson-Boltzmann theory, together with the general Frumkin-Fowler-Guggenheim adsorption isotherm model of the charge-regulation process, we analyze and review the dependence of the local pH on the position, as well as bulk electrolyte concentration, bulk pH, and curvature of the amphiphilic single membrane vesicle. With appropriately chosen adsorption parameters of the charge-regulation model, we find a good agreement with the available experimental data.

Electroviscous drag on squeezing motion in sphere-plane geometry.

Theoretically and experimentally, we study electroviscous phenomena resulting from charge-flow coupling in a nanoscale capillary. Our theoretical approach relies on Poisson-Boltzmann mean-field theory and on coupled linear relations for charge and hydrodynamic flows, including electro-osmosis and charge advection. With respect to the unperturbed Poiseuille flow, we define an electroviscous coupling parameter ξ, which turns out to be maximum where the film height h_{0} is comparable to the Debye screening length λ. We also present dynamic atomic force microscopy data for the viscoelastic response of a confined water film in sphere-plane geometry; our theory provides a quantitative description for the electroviscous drag coefficient and the electrostatic repulsion as a function of the film height, with the surface charge density as the only free parameter. Charge regulation sets in at even smaller distances.

Curvature effects in charge-regulated lipid bilayers.

We formulate a theory of electrostatic interactions in lipid bilayer membranes where both monolayer leaflets contain dissociable moieties that are subject to charge regulation. We specifically investigate the coupling between membrane curvature and charge regulation of a lipid bilayer vesicle using both the linear Debye-Hückel (DH) and the non-linear Poisson-Boltzmann (PB) theory. We find that charge regulation of an otherwise symmetric bilayer membrane can induce charge symmetry breaking, non-linear flexoelectricity and anomalous curvature dependence of free energy. The pH effects investigated go beyond the paradigm of electrostatic renormalization of the mechano-elastic properties of membranes.

Electrostatic pair-interaction of nearby metal or metal-coated colloids at fluid interfaces.

In this paper, we theoretically study the electrostatic interaction between a pair of identical colloids with constant surface potentials sitting in close vicinity next to each other at the fluid interface. By employing a simplified yet reasonable model system, the problem is solved within the framework of classical density functional theory and linearized as well as nonlinear Poisson-Boltzmann (PB) theory. Apart from providing a sound theoretical framework generally applicable to any such problem, our novel findings, all of which contradict common beliefs, include the following: first, quantitative and qualitative differences between the interactions obtained within the linear and the nonlinear PB theories; second, the importance of the electrostatic interaction between the omnipresent three-phase contact lines in interfacial systems; and, third, the occurrence of an attractive electrostatic interaction between a pair of identical metal colloids. The unusual attraction we report largely stems from an attractive line interaction, which although scales linearly with the size of the particle can compete with the surface interactions and can be strong enough to alter the nature of the total electrostatic interaction. Our results should find applications in metal or metal-coated particle-stabilized emulsions where densely packed particle arrays are not only frequently observed but also sometimes required.

Charge regulation radically modifies electrostatics in membrane stacks.

Motivated by biological membrane-containing organelles in plants and photosynthetic bacteria, we study charge regulation in a model membrane stack. Considering (de)protonation as the simplest mechanism of charge equilibration between the membranes and with the bathing environment, we uncover a symmetry-broken charge state in the stack with a quasiperiodic effective charge sequence. In the case of a monovalent bathing salt solution our model predicts complex, inhomogeneous charge equilibria depending on the strength of the (de)protonation reaction, salt concentration, and membrane size. Our results shed light on the basic reorganization mechanism of thylakoid membrane stacks.

Electrostatic interaction of particles trapped at fluid interfaces: effects of geometry and wetting properties.

The electrostatic interaction between pairs of spherical or macroscopically long, parallel cylindrical colloids trapped at fluid interfaces is studied theoretically for the case of small inter-particle separations. Starting from the effective interaction between two planar walls and by using the Derjaguin approximation, we address the issue of how the electrostatic interaction between such particles is influenced by their curvatures and by the wetting contact angle at their surfaces. Regarding the influence of curvature, our findings suggest that the discrepancies between linear and nonlinear Poisson-Boltzmann theory, which have been noticed before for planar walls, also occur for spheres and macroscopically long, parallel cylinders, though their magnitude depends on the wetting contact angle. Concerning the influence of the wetting contact angle θ simple relations are obtained for equally sized particles which indicate that the inter-particle force varies significantly with θ only within an interval around 90°. This interval depends on the Debye length of the fluids and on the size of the particles but not on their shape. For unequally sized particles, a more complicated relation is obtained for the variation of the inter-particle force with the wetting contact angle.

Electrostatic interaction between dissimilar colloids at fluid interfaces.

The electrostatic interaction between two nonidentical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann density functional theory. The resulting interaction comprises a surface and a line part, both of which, as functions of the interparticle separation, show a rich behavior including monotonic as well as nonmonotonic variations. In almost all cases, these variations cannot be captured correctly by using the superposition approximation. Moreover, expressions for the surface tensions, the line tensions and the fluid-fluid interfacial tension, which are all independent of the interparticle separation, are obtained. Our results are expected to be particularly useful for emulsions stabilized by oppositely charged particles.

Spontaneous symmetry breaking of charge-regulated surfaces.

The interaction between two chemically identical charge-regulated surfaces is studied using the classical density functional theory. In contrast to common expectations and assumptions, under certain realistic conditions we find a spontaneous emergence of disparate charge densities on the two surfaces. The surface charge densities can differ not only in their magnitude, but quite unexpectedly, even in their sign, implying that the electrostatic interaction between the two chemically identical surfaces can be attractive instead of repulsive. Moreover, an initial symmetry with equal charge densities on both surfaces can also be broken spontaneously upon decreasing the separation between the two surfaces. The origin of this phenomenon is a competition between the adsorption of ions from the solution to the surface and the interaction between the adsorbed ions already on the surface. These findings are fundamental for the understanding of the forces between colloidal objects and, in particular, they are bound to strongly influence the present picture of protein interaction.

Rotational motion of dimers of Janus particles.

We theoretically study the motion of a rigid dimer of self-propelling Janus particles. In a simple kinetic approach without hydrodynamic interactions, the dimer moves on a helical trajectory and, at the same time, it rotates about its center of mass. Inclusion of the effects of mutual advection using superposition approximation does not alter the qualitative features of the motion but merely changes the parameters of the trajectory and the angular velocity.

Electrostatic interaction between colloidal particles trapped at an electrolyte interface.

The electrostatic interaction between colloidal particles trapped at the interface between two immiscible electrolyte solutions is studied in the limit of small inter-particle distances. Within an appropriate model analytic expressions for the electrostatic potential as well as for the surface and line interaction energies are obtained. They demonstrate that the widely used superposition approximation, which is commonly applied to large distances between the colloidal particles, fails qualitatively at small distances, and is quantitatively unreliable even at large distances. Our results contribute to an improved description of the interaction between colloidal particles trapped at fluid interfaces.

Specific salt effects on thermophoresis of charged colloids.

We study the Soret effect of charged polystyrene particles as a function of temperature and electrolyte composition. As a main result we find that the Soret coefficient is determined by charge effects, and that non-ionic contributions are small. In view of the well-known electric-double layer interactions, our thermal field-flow fractionation data lead us to the conclusion that the Soret effect originates to a large extent from diffusiophoresis in the salt gradient and from the electrolyte Seebeck effect, both of which show strong specific-ion effects. Moreover, we find that thermophoresis of polystyrene beads is fundamentally different from proteins and aqueous polymer solutions, which show a strong non-ionic contribution.

Flow pattern in the vicinity of self-propelling hot Janus particles.

We study the temperature field and the resulting flow pattern in the vicinity of a heated metal-capped Janus particle. If its thickness exceeds about 10 nm, the cap forms an isotherm and the flow pattern comprises a quadrupolar term that decays with the square of the inverse distance ~r(-2). For much thinner caps the velocity varies as ~r(-3). These findings could be relevant for collective effects in dense suspensions and for the circular tracer motion observed recently in the vicinity of a tethered Janus particle.

Charging of heated colloidal particles using the electrolyte Seebeck effect.

We propose a novel actuation mechanism for colloids, which is based on the Seebeck effect of the electrolyte solution: Laser heating of a nonionic particle accumulates in its vicinity a net charge Q, which is proportional to the excess temperature at the particle surface. The corresponding long-range thermoelectric field E is proportional to 1/r(2) provides a tool for controlled interactions with nearby beads or with additional molecular solutes. An external field E(ext) drags the thermocharged particle at a velocity that depends on its size and absorption properties; the latter point could be particularly relevant for separating carbon nanotubes according to their electronic band structure.

Collective thermoelectrophoresis of charged colloids.

Thermally driven colloidal transport is, to a large extent, due to the thermoelectric or Seebeck effect of the charged solution. We show that, contrary to the generally adopted single-particle picture, the transport coefficient depends on the colloidal concentration. For solutions that are dilute in the hydrodynamic sense, collective effects may significantly affect the thermophoretic mobility. Our results provide an explanation for recent experimental observations on polyelectrolytes and charged particles and suggest that for charged colloids collective behavior is the rule rather than the exception.