Advances in Colloid and Interface Science (v.85, #2-3)

Recent advances in understanding dynamic surface tensions (DSTs) of surfactant solutions are discussed. For pre-CMC solutions of non-ionic surfactants, theoretical models and experimental evidence for a mixed diffusion–kinetic adsorption mechanism are covered. For micellar solutions of non-ionics, up to approximately 100×CMC, the DST behaviour can also be accounted for using a mixed mechanism model. Finally, the first reported measurements of the dynamic surface excess Γ(t), using the overflowing cylinder in conjunction with neutron reflection, are described.
Keywords: Dynamic surface tension; Adsorption mechanisms; Surfactants adsorption;

This article is devoted to an overview, comparison and discussion of recent results (both theoretical and experimental) about lateral capillary forces. They appear when the contact of particles or other bodies with a fluid phase boundary causes perturbations in the interfacial shape. The capillary interaction is due to the overlap of such perturbations which can appear around floating particles, vertical cylinders, particles confined in a liquid film, inclusions in the membranes of lipid vesicles or living cells, etc. In the case of floating particles the perturbations are due to the particle weight; in this case the force decreases with the sixth power of the particle size and becomes immaterial for particles smaller than approximately 10 μm. In all other cases the interfacial deformations are due to the particle wetting properties; the resulting ‘immersion’ capillary forces can be operative even between very small particles, like protein globules. In many cases such forces can be responsible for the experimentally observed two-dimensional particle aggregation and ordering. An analogy between capillary and electrostatic forces enables one to introduce ‘capillary charges’ of the attached particles, which characterize the magnitude of the interfacial deformation and could be both positive and negative. Moreover, the capillary interaction between particle and wall resembles the image force in electrostatics. When a particle is moving bound to an interface under the action of a capillary force, one can determine the surface drag coefficient and the surface viscosity supposedly the magnitude of the capillary force is known. Alternative (but equivalent) energy and force approaches can be used for the theoretical description of the lateral capillary interactions. Both approaches require the Laplace equation of capillarity to be solved and the meniscus profile around the particles to be determined. The energy approach accounts for contributions due to the increase of the meniscus area, gravitational energy and/or energy of wetting. The second approach is based on calculating the net force exerted on the particle, which can originate from the hydrostatic pressure, interfacial tension and bending moment. In the case of small perturbations, the superposition approximation can be used to derive an asymptotic formula for the capillary forces, which has been found to agree well with the experiment. Capillary interactions between particles bound to spherical interfaces are also considered taking into account the special geometry and restricted area of such phase boundaries. A similar approach can be applied to quantify the forces between inclusions (transmembrane proteins) in lipid membranes. The deformations in a lipid membrane, due to the inclusions, can be described theoretically in the framework of a mechanical model of the lipid bilayer, which accounts for its ‘hybrid’ rheology (neither elastic body nor fluid). In all considered cases the lateral capillary interaction originates from the overlap of interfacial deformations and is subject to a unified theoretical treatment, despite the fact that the characteristic particle size can vary from 1 cm down to 1 nm.
Keywords: Capillary forces; Lipid membranes containing inclusions; Liquid films containing particles; Surface viscosity measurements; Two-dimensional aggregation;

Dielectric exclusion of ions from membranes by Andrij E Yaroshchuk (193-230).
Dielectric exclusion is caused by the interactions of ions with the bound electric charges induced by ions at interfaces between media of different dielectric constants. It is considered as one of mechanisms of nanofiltration. The transport properties of capillary model are expressed through ion distribution and diffusion coefficients. Due to local equilibrium the distribution coefficient is directly related to the excess solvation energy of ion. First, this energy is considered for single ions in single neutral pores in terms of pore size, ion charge, dielectric constants of solvent and membrane matrix and pore geometry. The dielectric exclusion from pores with closed geometry like circular cylinders is shown to be essentially stronger than that from pores with relatively open geometry like slits. Furthermore, the role of finite membrane porosity is analysed for the model of infinite slabs with alternating dielectric constants. The presence of other ions is accounted for within the scope of a mean-field approach, and the screening of dielectric exclusion is thus introduced and considered in some detail. A fixed electric charge is shown to cause additional screening. At the same time the dielectric exclusion makes the Donnan exclusion of ions stronger. Therefore the interaction between those two rejection mechanisms turns out to be non-trivial. Finally, the effect of solvent molecular structure is considered within the scope of non-local electrostatics. It is shown that the solvent non-locality typically results in somewhat stronger dielectric exclusion, however, its most important effect is slowing down the decline of dielectric exclusion with increasing bulk electrolyte concentration.
Keywords: Membrane; Pore; Ion; Reflection coefficient; Dielectric constant; Classical electrostatics; Non-local electrostatics; Ionic screening; Nanofiltration;

Particle–bubble collision models — a review by Zongfu Dai; Daniel Fornasiero; John Ralston (231-256).
A critical review of the various models existing in the literature for the calculation of the collision efficiency between particles and single, rising gas bubbles is presented. Although all of these collision models predict that the collision efficiency increases with particle size, their dependence on the latter is different because of the various assumptions and hydrodynamic conditions used in each model. Collision efficiencies of quartz particles with single bubbles have been obtained from experimental flotation experiments under conditions where the attachment and stability efficiencies were at, or near, unity. These collision efficiencies were then used to test various collision models. Good agreement between the experimental and calculated collision efficiencies was only obtained with the Generalised Sutherland Equation. The differences in collision efficiencies obtained between the various models were mainly explained in terms of, firstly, the degree of mobility of the bubble surface and, secondly, a consideration of the inertial forces acting on the particles.
Keywords: Flotation; Collision efficiency; Inertial forces;

Many proteins exhibit both a water-soluble and a membrane-bound state. The proteins in the membrane-bound state obtain a distinct structure from that in the bulk, which exists in many important biological processes. In the present paper we would stress that the variation of the physical chemistry properties of the microenvironment adjacent to the membrane-surface region play an important role in the process of the membrane-induced conformational changes of the proteins.
Keywords: Lipid protein interaction; Protein conformation; Membrane insertion; Protein adsorption;

Book review (269-271).