Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

Anomalous low-frequency electro-optic behavior of ferric oxide particles in the presence of poly(ethylene oxide)

Electro-optic techniques were used to investigate the influence of poly(ethylene oxide) (PEO) on the surface electric state of positively charged oxide particles. The variations in particle electrophoretic mobility of beta-FeOOH particles in the presence of PEO indicate significant changes in the surface electric state of the particles in the concentration interval of PEO 10(-2)-10(-1) g dm(-3). The electro-optic results for the same conditions were unexpected: no significant difference is observed in the value and the relaxation frequency of particle electric polarizability in the frequency domain of the alpha-relaxation (detected in the kilohertz range); particle rotational relaxation time also remains unchanged; considerable changes are detected only in the relaxation interval of particle rotation (detected in the hertz range). The obtained results reject the possibility of the formation on the particle surface of a thick polymer layer. A thin adsorption layer cannot explain the significant decrease in particle electrophoretic mobility. The variations in electrophoretic mobility are well correlated with the effects in the domain of particle rotation. A possible explanation of the observed effects is proposed, based on our previous investigations of the effects in the low-frequency domain. The presented results demonstrate that the important information on the electrokinetic charge distribution is not found in the domain of the alpha-dispersion, but in the domain of particle rotation.     

Relevance of electrokinetic theory for "soft" particles to bacterial cells: implications for bacterial adhesion

Bacterial cells and other biological particles carry charged macromolecules on their surface that form a "soft" ion-permeable layer. In this paper, we test the applicability of an electrokinetic theory for soft particles to characterize the electrophoretic mobility (EPM) and adhesion kinetics of bacterial cells. The theory allows the calculation of two parameters--the electrophoretic softness and the fixed charged density--that define the characteristics of the polyelectrolyte layer at the soft particle surface. The theory also allows the calculation of an outer-surface potential that may better predict the electrostatic interaction of soft particles with solid surfaces. To verify its relevance for bacterial cells, the theory was applied to EPM measurements of two well-characterized Escherichia coli K12 mutants having lipopolysaccharide (LPS) layers of different lengths and molecular compositions. Results showed that the obtained softness and fixed charge density were not directly related to the known characteristics of the LPS of the selected strains. Interaction energy profiles calculated from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory were used to interpret bacterial deposition (adhesion) rates on a pure quartz surface. The outer surface potential failed to predict the low attachment efficiencies of the two bacterial strains. The lack of success in the application of the theory for soft particles to bacterial cells is attributed to chemical and physical heterogeneities of the polyelectrolyte layer at the cell surface.     

Analysis of the interfacial properties of fibrillated and nonfibrillated oral streptococcal strains from electrophoretic mobility and titration measurements: evidence for the shortcomings of the 'classical soft-particle approach'

Chemical and structural intricacies of bacterial cells complicate the quantitative evaluation of the physicochemical properties pertaining to the cell surface. The presence of various types of cell surface appendages has a large impact on those properties and therefore on various interfacial phenomena, such as aggregation and adhesion. In this paper, an advanced analysis of the electrophoretic mobilities of fibrillated and nonfibrillated strains (Streptococcus salivarius HB and Streptococcus salivarius HB-C12, respectively) is performed over a wide range of pH and ionic strength conditions on the basis of a recent electrokinetic theory for soft particles. The latter extends the approximate formalism originally developed by Ohshima by solving rigorously the fundamental electrokinetic equations without restrictions on the bacterial size, charge, and double layer thickness. It further allows (i) a straightforward implementation of the dissociation characteristics, as evaluated from titration experiments, of the ionogenic charged groups distributed throughout the bacterial cell wall and/or the surrounding exopolymer layer and (ii) the inclusion of possible specific interactions between the charged groups and ions from the background electrolyte other than charge-determining ions. The theory also enables an estimation of possible swelling/shrinking processes operating on the outer polymeric layer of the bacterium. Application of the electrokinetic model to HB and HB-C12 clearly shows a significant discrepancy between the amount of surface charges probed by electrophoresis and by protolytic titration. This is ascribed to the specific adsorption of cations onto pristine charged sites in the cell wall. Physicochemical parameters pertaining to the hydrodynamics (softness degree) and electrostatics of the bacterial cell wall (HB-C12) and soft polymeric layer (HB) are quantitatively derived.     

Electrokinetic behavior and colloidal stability of polystyrene latex coated with ionic surfactants

This work is focused on analyzing the electrokinetic behavior and colloidal stability of latex dispersions having different amounts of adsorbed ionic surfactants. The effects of the surface charge sign and value, and the type of ionic surfactant were examined. The analysis of the electrophoretic mobility (mu(e)) versus the electrolyte concentration up to really high amounts of salt, much higher than in usual studies, supports the colloidal stability results. In addition, useful information to understand the adsorption isotherms was obtained by studying mu(e) versus the amount of the adsorbed surfactant. Aggregation studies were carried out using a low-angle light scattering technique. The critical coagulation concentrations (ccc) of the particles were obtained for different surfactant coverage. For latex particles covered by ionic surfactants, the electrostatic repulsion was, in general, the main contribution to the colloidal stability of the system; however, steric effects played an important role in some cases. For latices with not very high colloidal stability, the adsorption of ionic surfactants always improved the colloidal stability of the dispersion above certain coverage, independently of the sign of both, latex and surfactant charge. This was in agreement with higher mobility values. Several theoretical models have been applied to the electrophoretic mobility data in order to obtain different interfacial properties of the complexes (i.e., zeta potential and density charge of the surface charged layer).     

On the General Expression for the Electrophoretic Mobility of a Soft Particle

Electrokinetic equations for electrophoresis of a soft particle (that is, a hard particle covered with a layer of polyelectrolytes) have been solved previously under the conditions that the net force acting on the soft particle as a whole (the particle core plus the polyelectrolyte layer) must be zero and that the electrical force acting on the polymer segment is balanced with a frictional force exerted by the liquid flow (J. Colloid Interface Sci. 163, 474 (1994)). In the present work we replaced the latter condition by the alternative and more appropriate condition that pressure is continuous at the boundary between the surface layer and the surrounding electrolyte solution to solve the electrokinetic equations and obtained the general mobility expression for the electrophoretic mobility of a spherical soft particle. It is found that the general mobility expression thus obtained reproduces all of the approximate mobility expressions derived previously and, in addition, that the continuous pressure condition leads to the correct limiting behavior of the electrophoretic mobility in the case where the frictional coefficient tends to zero (this behavior cannot be derived from the force balance condition for the polyelectrolyte layer). Copyright 2000 Academic Press.     

A new generalization of the standard electrokinetic model

We present a new generalization of the standard electrokinetic model based on the assumption that there is a thin layer surrounding the suspended particle where the equilibrium ion density is not determined by the Gouy-Chapman distribution, while the standard model applies outside this layer. Our approach differs from existing models in that we consider that the surface layer is made both of free ions (mostly counterions) and of the fixed ions that constitute the charge of the particle. Furthermore, the free ion density is determined by appropriate boundary conditions without considering any adsorption isotherms. Finally, the fluid is allowed to freely flow inside the layer, only hindered by the presence of the fixed charges and the adhesion condition on the surface of the particle. We show that this generalization leads to results that qualitatively differ from those obtained using existing models: instead of always decreasing, the electrophoretic mobility can actually increase with the anomalous surface conductivity. This could make it possible to use our model for the interpretation of a broader set of experimental data, including those cases when the measured mobility is higher than predicted by the standard model.     

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.     

Significance of cell electrokinetic properties determined by soft-particle analysis in bacterial adhesion onto a solid surface

The influence of extracellular polymeric substances (EPSs) on bacterial cell electrokinetic properties and on cell adhesion onto glass beads in connection with bacterial cell electrokinetic properties was investigated using 12 heterotrophic bacterial strains. Bacterial cell surface properties such as the softness 1/lambda and charge density ZN were determined by Ohshima's soft-particle analysis using the measured electrophoretic mobility as a function of ionic strength. In 10 of 12 strains, when EPSs covering the cell surface were removed, the softness of the cell decreased, indicating that EPS adsorption enhanced the ease of liquid fluid in the ion-penetrable layer on the cell surface. On the other hand, the negative charge density of the cell surface increased for 9 of 12 strains, suggesting that EPSs covering the cell surface decreased the negative charge density of the cell surface layer. In addition, the characteristics of bacterial cell adhesion onto glass beads were evaluated by the packed-bed method and the data were interpreted to indicate cell adhesiveness. As a result, the efficiency of cell adhesion onto glass beads increased as negative cell surface potential psi0 decreased, whereas there seemed to be no correlation between zeta potential and cell adhesiveness. Cell surface potential psi0, which was derived by taking the bacterial polymer layer with EPSs into consideration, provided a more detailed understanding of the electrokinetic properties of bacterial cells.     

Ion size effects on the electrokinetics of salt-free concentrated suspensions in ac fields

We analyze the influence of finite ion size effects in the response of a salt-free concentrated suspension of spherical particles to an oscillating electric field. Salt-free suspensions are just composed of charged colloidal particles and the added counterions released by the particles to the solution that counterbalance their surface charge. In the frequency domain, we study the dynamic electrophoretic mobility of the particles and the dielectric response of the suspension. We find that the Maxwell-Wagner-O’Konski process associated with the counterions condensation layer is enhanced for moderate to high particle charges, yielding an increment of the mobility for such frequencies. We also find that the increment of the mobility grows with ion size and particle charge. All these facts show the importance of including ion size effects in any extension attempting to improve standard electrokinetic models.     

Electrohydrodynamics of spherical polyampholyte‐grafted nanoparticles: Multiscale simulations by coupling of molecular dynamics and lattice‐boltzmann method

We perform multiscale simulations based on the coupling of molecular dynamics and lattice‐Boltzmann (LB) method to study the electrohydrodynamics of a polyampholyte‐grafted spherical nanoparticle. The long‐range hydrodynamic interactions are modeled by coupling the movement of particles to a LB fluid. Our results indicate that the net‐neutral soft particle moves with a nonzero mobility under applied electric fields. We systematically explore the effects of different parameters, including the chain length, grafting density, electric field, and charge sequence, on the structures of the polymer layer and the electrophoretic mobility of the soft particle. It shows that the mobility of nanoparticles has remarkable dependence on these parameters. We find that the deformation of the polyampholyte chains and the ion distribution play dominant roles in modulating the electrokinetic behavior of the polyampholyte‐grafted particle. The enhancement or reduction in the accumulation of counterions around monomers can be attributed to the polymer layer structure and the conformational transition of the chains in the electric field. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1435–1447     

Examination of the atypical electrophoretic mobility behavior of charged colloids in the low salt region using the O’Brian-White theory

 Polystyrene microspheres having roughly the same size but different negative surface charge densities were prepared by emulsion polymerization. The amount of sulfate groups on the surface of the particles was controlled by variation of the amount and the decomposition rate of the initiator used, potassium, persulfate. After the cleaning process involving dialysis and extensive ultrafiltration the surface-charge density of the samples was determined and their electrokinetic behavior was studied. A simple model based on the Gouy–Chapman theory and the O’Brian–White approach allows the calculation of the dependence of the electrophoretic mobility on salt concentration. Comparison of the theoretical and experimental curves showed that they were in good agreement in a number of qualitative features. Moreover, the model revealed that a monotonously increasing zeta potential with falling electrolyte concentration results in a mobility maximum, and that this so-called atypical behavior is in accordance with the standard electrokinetic theory. No ion adsorption mechanism or the existence of a charged hairy layer, current standard explanations for this anomality, had to be invoked. Received: 13 February 1997 Accepted: 2 June 1997     

Parameter identifiability in application of soft particle electrokinetic theory to determine polymer and polyelectrolyte coating thicknesses on colloids

Soft particle electrokinetic models have been used to determine adsorbed nonionic polymer and polyelectrolyte layer properties on nanoparticles or colloids by fitting electrophoretic mobility data. Ohshima first established the formalism for these models and provided analytical approximations ( Ohshima, H. Adv. Colloid Interface Sci.1995, 62, 189 ). More recently, exact numerical solutions have been developed, which account for polarization and relaxation effects and require fewer assumptions on the particle and soft layer properties. This paper characterizes statistical uncertainty in the polyelectrolyte layer charge density, layer thickness, and permeability (Brinkman screening length) obtained from fitting data to either the analytical or numerical electrokinetic models. Various combinations of particle core and polymer layer properties are investigated to determine the range of systems for which this analysis can provide a solution with reasonably small uncertainty bounds, particularly for layer thickness. Identifiability of layer thickness in the analytical model ranges from poor confidence for cases with thick, highly charged coatings, to good confidence for cases with thin, low-charged coatings. Identifiability is similar for the numerical model, except that sensitivity is improved at very high charge and permeability, where polarization and relaxation effects are significant. For some poorly identifiable cases, parameter reduction can reduce collinearity to improve identifiability. Analysis of experimental data yielded results consistent with expectations from the simulated theoretical cases. Identifiability of layer charge density and permeability is also evaluated. Guidelines are suggested for evaluation of statistical confidence in polymer and polyelectrolyte layer parameters determined by application of the soft particle electrokinetic theory.     

Influence of membrane layer properties on the electrophoretic behavior of a soft particle

The influence of the physical properties of the membrane layer of a soft particle, which comprises a rigid core and a porous membrane layer, on its electrophoretic behavior, is investigated. Because that influence was almost always neglected in the previous studies, the corresponding results can be unrealistic. The applicability of the model proposed is verified by the available theoretical and experimental results. The electrophoretic mobility of the particle under various conditions is simulated through varying the dielectric constant, the thickness, and the drag coefficient of the membrane layer, and the bulk ionic concentration. We show that under typical conditions, the deviation in the electrophoretic mobility arising from assuming that the dielectric constant of the membrane layer is the same as that of the bulk liquid phase can be in the order of 50%. In addition, the thicker the membrane layer and/or the higher the bulk ionic concentration, the larger the deviation. If the surface of the core of the particle is charged, as in the case of inorganic particles covered by an artificial membrane layer, the deviation at constant core surface potential is larger than that under other types of charged conditions. However, if the surface of the core is uncharged, as in the case of biocolloids, then that deviation becomes negligible. These findings are of fundamental significance to theoreticians in their analysis on the electrokinetic behaviors of soft particles, and to experimentalists in the interpretation of their data.     

Single particle analysis using fluidic, optical and electrophoretic force balance in a microfluidic system

A unique microfluidic system is developed which enables the interrogation of a single particle by using multiple force balances from a combination of optical force, hydrodynamic drag force, and electrophoretic force. Two types of polystyrene (PS) particles with almost identical size and refractive index (plain polystyrene (PS) particle - mean diameter: 2.06 μm, refractive index: 1.59; carboxylated polystyrene (PS-COOH) particles - mean diameter: 2.07 μm, refractive index: 1.60), which could not be distinguished by optical chromatography, reveal different electrokinetic behaviors resulting from the difference in their surface charge densities. The PS-COOH particles, despite their higher surface charge density when compared to the PS particles, experience a lower electrophoretic force, regardless of ionic strength. This phenomenon can be understood when the more prominent polarization of the counter ion cloud surrounding the PS-COOH particles is considered. The surface roughness of the carboxylated particles also plays an important role in the observed electrokinetic behavior.     

Aggregation behavior of poly(N-isopropylacrylamide) microspheres

Electrophoretic mobility and aggregation in suspensions of three types of microspheres (Ms 1, Ms 2 and Ms 3) are studied at different pH, ionic strengths and temperatures of the medium. Here Ms 1 is a core particle composed of poly(N-isopropylacrylamide-co-styrene). Ms 2 is a core-shell microsphere consisting of Ms 1 as the particle core covered with a surface layer of poly(N-isopropylacrylamide) hydrogel. Ms 3 is also a core-shell microsphere composed of MS-1 covered with a surface layer of poly(N-isopropylacrylamide-co-acrylic acid) hydrogel. The charge density zN and the softness parameter 1/λ of the microspheres were obtained from the electrophoretic mobility data on the basis of an electrokinetic theory of soft particles. It is shown that when zN is large, suspensions of microspheres are always stable, showing no aggregation. When zN is small, the suspensions are stable for large 1/λ but show strong aggregation for small 1/λ.     

Electrophoretic mobility, zeta potential, and fixed charge density of bovine knee chondrocytes, methyl methacrylate-sulfopropyl methacrylate, polybutylcyanoacrylate, and solid lipid nanoparticles

The electrophoretic mobility and zeta potential of bovine knee chondrocytes (BKCs), methyl methacrylate-sulfopropyl methacrylate (MMA-SPM) nanoparticles (NPs), polybutylcyanoacrylate (PBCA) NPs, and solid lipid nanoparticles (SLNs) were investigated under the influences of Na+, K+, and Ca2+ with various ionic strengths. The fixed charge density in the surface layers of the four biocolloidal particles was estimated from the experimental mobility of capillary electrophoresis with a theory of soft charged colloids. The results revealed that, for a specific cationic species, the absolute values of the electrophoretic mobility, the zeta potential, and the fixed charge density decreased with an increase in ionic strength. For a constant ionic strength, the effect of ionic species on the reduction in the absolute values of the electrophoretic mobility, the zeta potential, and the fixed charge density followed the order Na+>K+>Ca2+ for the negatively charged BKCs, MMA-SPM NPs, and SLNs. The reverse order is true for the positively charged PBCA NPs.     

Electrostatics and electrophoresis of engineered nanoparticles and particulate environmental contaminants: Beyond zeta potential-based formulation

Colloidal nano/micro-(bio)particles carry an electrostatic charge in aqueous media, and this charge is critical in defining their stability, (bio)adhesion properties, or toxicity toward humans and biota. Determination of interfacial electrostatics of these particles is often performed from zeta potential estimation using the electrophoresis theory by Smoluchowski. The latter, however, strictly applies to the ideal case of hard particles defined by a surface charge distribution under the strict conditions of particle impermeability to electrolyte ions and to flow. Herein, we review sound theoretical alternatives for capturing electrokinetic and therewith electrostatic features of soft colloids of practical interest defined by a 3D distribution of their structural charges and by a finite permeability to ions and/or flow (e.g., bacteria, viruses, nanoplastics, (bio)functionalized particles or engineered nanoparticles). Reasons for the inadequacy of commonly adopted hard particle electrophoresis models when applied to soft particulate materials are motivated, and analytical expressions that properly capture their electrophoretic response are comprehensively reviewed.     

Adsorption of human serum albumin (HSA) onto colloidal TiO2 particles, Part I

The adsorption of human serum albumin (HSA) onto colloidal TiO2 (P25 Degussa) particles was studied in NaCl electrolyte at different solution pH and ionic strength. The HSA-TiO2 interactions were studied using adsorption isotherms and the electrokinetic properties of HSA-covered TiO2 particles were monitored by electrophoretic mobility measurements. The adsorption behavior shows a remarkable dependence of the maximum coverage degree on pH and was almost independent of the ionic strength. Other characteristic features such as maximum adsorption values at the protein isoelectric point (IEP approximately 4.7) and low-affinity isotherms that showed surface saturation even under unfavorable electrostatic conditions (at pH values far away from the HSA IEP and TiO2 PZC) were observed. Structural and electrostatic effects can explain the diminution of HSA adsorption under these conditions, assuming that protein molecules behave as soft particles. Adsorption reactions are discussed, taking into account acid-base functional groups of the protein and the surface oxide in different pH ranges, considering various types of interactions.