Electrophoresis of soft particles with charged rigid core coated with pH-regulated polyelectrolyte layer

We present a theoretical study on the electrophoresis of a soft particle with a dielectric charged rigid core grafted with a charge-regulated polyelectrolyte layer. The polyelectrolyte layer possesses either an acidic or a basic functional group and the charge dissociation depends on the local pH and ionic concentration of the electrolyte. The dielectric rigid core is considered to possess a uniform volumetric charge density. The electric potential distribution is determined by computing the Poisson-Boltzmann equation outside the core coupled with a Poisson equation inside the impermeable core along with suitable matching conditions at the core-shell interface. The computed electric field is used to determine the mobility of the particle through an existing analytic expression based on the Debye-Huckel approximation. Our results are found to be in good agreement with the existing solutions for the limiting cases. The influence of the core charge density, ionic concentration, and pH of the electrolyte on the particle mobility is studied for different choice of hydrodynamic penetration length of the polyelectrolyte and dissociation constant of the functional group. The critical value of the pH required to achieve zero mobility is estimated. We find that in a monovalent electrolyte solution, the soft particle with a net negative (positive) charge can have positive (negative) mobility.     

Diffusiophoresis of a highly charged soft particle normal to a conducting plane

Diffusiophoresis of a soft particle in electrolyte solutions normal to a conducting solid plane is investigated theoretically in this study, focusing on the highly charged particle in particular. A pseudo-spectral method based on Chebyshev polynomial is adopted to solve the resultant governing electrokinetic equations. It was found, among other things, that the closer the soft particle is to the plane, the faster it moves in general, provided only the chemiphoresis component of the diffusiophoresis is involved, i.e., no diffusion potential is present. The presence of the conducting plane is found to have three effects upon the particle motion nearby: the geometric boundary confinement effect, the electrostatic mirror-image force analog effect, and the hydrodynamic retarding effect. The enhancement of the double layer polarization by the first two effects leads to the seeming intriguing observation mentioned above. The particle always moves away from the plane in chemiphoresis. If a diffusion potential is present, however, then it is possible to drive the particle toward the plane. The results have potential applications in drug delivery.     

Electrophoresis of a concentrated dispersion of spherical particles covered by an ion-penetrable membrane layer

The electrophoretic behavior of a concentrated dispersion of soft spherical particles is investigated theoretically, taking the effects of double-layer overlapping and double-layer polarization into account. Here, a particle comprises a rigid core and an ion-penetrable layer containing fixed charge, which mimics biocolloids and particles covered by artificial membrane layers. A cell model is adopted to simulate the system under consideration, and a pseudo-spectral method based on Chebyshev polynomials is chosen for the resolution of the governing electrokinetic equations. The influence of the key parameters, including the thickness of the double layer, the concentration of particles, the surface potential of the rigid core of a particle, and the thickness, the amount of fixed charge, and the friction coefficient of the membrane layer of a particle on the electrophoretic behavior of the system under consideration is discussed. We show that while the result for the case of a dispersion containing rigid particles can be recovered as the limiting case of a dispersion containing soft particles, qualitative behaviors that are not present in the former are observed in the latter.     

Diffusiophoresis in suspensions of highly charged soft particles

Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery.     

Electric double layer and electrostatic interaction of hydrophobic particles

An hypothesis regarding the impact of water density near hydrophobic surfaces on the electrostatic component of their interaction was offered. A theoretical model of the electric double layer and the interparticle interaction under conditions of the variable density and, consequently, variable dielectric permittivity of water has been developed. It was shown that reduction of the dielectric permittivity near interfaces determined by their hydrophobicity resulted in compression of double electrical layers and weakening of their overlapping. This, in its turn, results in reduction of the electrostatic repulsion of hydrophobic disperse particles as compared with nonhydrophobic ones.     

Mass transfer of a neutral solute in polyelectrolyte grafted soft nanochannel with porous wall

A soft nanochannel involves a soft interface that contains a polyelectrolyte layer (PEL) sandwiched between a rigid surface and a bulk electrolyte solution. Mass transfer of a neutral solute in a combined electroosmotic and pressure driven flow through a polyelectrolyte grafted charged nanochannel with porous wall is presented in this work. Assuming the PEL as fixed charged layer and PEL-electrolyte interface as a semi-penetrable membrane, analytical solutions were obtained for potential distributions (for small wall potential). Velocity profiles were also derived in the same domains, for both inside and outside the PEL. Convective-diffusive species balance equation was semi-analytically solved inside the PEL. Expression of length averaged Sherwood number was also obtained and effects of different parameters, namely, drag parameter (α), Debye parameter , and PEL thickness were studied in detail. The variation of permeate concentration and permeation flux across the porous wall was obtained.     

Electrophoresis of large colloidal particles with surface charge layers. Position of the slipping plane and surface layer thickness

A theory is proposed for the electrophoresis of a large colloidal particle with a surface charge layer. The slipping plane is assumed to be located within the surface layer but may not be located at the boundary between the surface layer and the particle core. In previous studies, the depth of the slipping plane is assumed to coincide with the surface layer thickness. The present theory makes it possible to examine the separate dependence of the electrophoretic mobility on the position of the slipping plane and on the surface layer thickness. It is shown that, at constant amount of particle-fixed charges in the surface layer, the mobility increases as the depth of the slipping plane (d _s ) increases, while it decreases as the surface layer thickness (d _c ) increases, causing a mobility maximum in some cases ifd _s =d _c . Several approximate analytic expressions for the mobility are presented.     

Production of soft core/hard shell composite polymer particles by the stepwise heterocoagulation method with heat treatment

Soft core/hard shell composite polymer particle was prepared by the stepwise heterocoagulation, which was proposed by authors in 1990, of many cationic hard small polymer particles (SPs) onto an anionic soft large polymer particle (LP). The powder was obtained by freeze-drying at 0 ^°C which was higher than glass transition temperature of LP (−7 ^°C) and lower than that of SP (90 ^°C). Received: 9 December 1997 Accepted: 12 May 1998     

Electrophoresis of hydrophilic/hydrophobic rigid colloid with effects of relaxation and ion size

This article deals with a semi‐analytical study on the electrophoresis of charged spherical rigid colloid by considering the effects of relaxation and ion size. The particle surface is taken to be either hydrophilic or hydrophobic in nature. In order to consider the ion size effect we have invoked the Carnahan and Starling model (J. Chem. Phys. 1969, 51, 635‐636). The mathematical model is based on Stokes equation for fluid flow, modified Boltzmann equation for spatial distribution of ionic species and Poisson equation for electric potential. We adopt a linear perturbation technique under a weak electric field assumption. An iterative numerical technique in employed to solve the coupled set of perturbed equations. We have validated the numerically obtained electrophoretic mobility with the corresponding analytical solution derived under low potential limit. Going beyond the widely employed Debye‐Hückel linearization, we have presented the results for a wide range of surface charge density, electrolyte concentration, and slip length to Debye length ratio. We have also identified several interesting features including occurrence of local maxima and minima in the mobility for critical choice of pertinent parameters.     

Comparison of treecodes for computing electrostatic potentials in charged particle systems with disjoint targets and sources

In molecular simulations, it is sometimes necessary to compute the electrostatic potential at M target sites due to a disjoint set of N charged source particles. Direct summation requires O(MN) operations, which is prohibitively expensive when M and N are large. Here, we consider two alternative tree‐based methods that reduce the cost. The standard particle‐cluster treecode partitions the N sources into an octree and applies a far‐field approximation, whereas a recently developed cluster‐particle treecode instead partitions the M targets into an octree and applies a near‐field approximation. We compare the two treecodes with direct summation and document their accuracy, CPU run time, and memory usage. We find that the particle‐cluster treecode is faster when N > M, that is, when the sources outnumber the targets, and conversely, the cluster‐particle treecode is faster when M > N, that is, when the targets outnumber the sources. Hence, the two treecodes provide useful tools for computing electrostatic potentials in charged particle systems with disjoint targets and sources. © 2013 Wiley Periodicals, Inc.     

Stability of capillaries coated with highly charged polyelectrolyte monolayers and multilayers under various analytical conditions--application to protein analysis

The stability of capillaries coated with highly charged polyelectrolytes under various analytical conditions was studied, as well as their performance for the analysis of proteins by Capillary Electrophoreis (CE) over a wide range of pH (2.5-9.3). In this study, fused silica capillaries were modified either with a poly(diallyldimethylammonium) chloride (PDADMAC) monolayer or PDADMAC/poly(sodium 4-styrenesulfonate) (PSS) multilayer coatings, using optimal coating conditions previously determined. Results show that the coated capillaries are remarkably stable and efficient to limit protein adsorption under a variety of extreme electrophoretic conditions even in the absence of the coating agent in the background electrolyte which is exceptional for non-covalent coatings. Monolayer coated capillaries were demonstrated for the first time to be stable to acidic rinses and to organic solvents which proves that the stability of the capillaries is highly dependent on the coating procedure used. In addition, PDADMAC/PSS multilayer coatings were found to be stable to alkaline treatments. PDADMAC/PSS coated capillaries gave excellent performances for the analysis of proteins covering a large range of pI (4-11) and of molecular weight (14-65 kDa) over a wide pH range (i.e. 2.5-9.3). Even at high pH 9.3, protein analysis was possible with very good repeatabilities (RSD(tm)<1% and RSD(CPA)<2.6% (n ≥ 8)) and high peak efficiencies in the order of 700,000.     

Synthesis and characterization of a novel fluorine-containing polymer emulsion with core/shell structure

A novel fluorine-containing polymer emulsion 4 with core/shell structure was synthesized in water phase by a two-stage emulsion polymerization technique using monomer 3 (i.e., 2-methacryloyloxyethyl perfluorooctanoate (MAEF)) reacting with the monomers such as butyl acrylate (BA), acrylic acid (AA) and styrene (ST). The monomer 3 was synthesized from the intermediate 2 (pentadecafluoro-octanoyl chloride) reacting with β-hydroxyethyl methacrylate (HEMA). Polymer film were prepared by coating emulsion 4 directly on a cleaned glass plate and allowed to dry at room temperature. Moreover, the characteristics of polymer film such as hydrophobicity, chemical resistance, surface composition, thermal stability, emulsion particle morphology, as well as the film-forming property were also studied.     

Self-organization of polymer particles on hydrophobic solid substrates in aqueous media. II. Self-organization of cationic polymer particles on polymer films and wettability control with particle monolayers

Self-organization of cationic polymer particles through hydrophobic interaction on polymer films in aqueous system and characteristic properties of the resulting particle monolayers were investigated. Cationic polymer particles bearing quaternary ammonium groups on their surfaces effectively self-organized on polymer films. With an increase of the particle surface charge density, the surface coverage and average aggregate size (N _a) decreased. The surface coverage control was accomplished by tuning the ionic strength of the media. The wettability of polymer films for water was imparted by the formation of particle monolayers on them. Annealing of the particle monolayers resulted in the increase of the adhesive strength, while the wettability for water was lost. Further improvements of both wettability and adhesive strength of particle monolayers were achieved by the immobilization of silica colloids on the particle monolayers. This method would be effective for the hydrophilization of polymer films.