Interactions between Adsorbed Layers of a Low Charge Density Cationic Polyelectrolyte on Mica in the Absence and Presence of Anionic Surfactant

Interactions between two negatively charged mica surfaces across aqueous solutions containing various amounts of a 10% charged cationic polyelectrolyte have been studied. It is found that the mica surface charge is neutralized when the polyelectrolyte is adsorbed from a 10–50 ppm aqueous solution. Consequently no electrostatic double-layer force is observed. Instead an attractive force acts between the surfaces in the distance regime 250–100 Å. We suggest that this attraction is caused by bridging. Additional adsorption takes place when the polyelectrolyte concentration is increased to 100 and 300 ppm, and a long-range repulsion develops. This repulsive force is both of electrostatic and steric origin. The polyelectrolyte layer adsorbed from a 50 ppm solution does not desorb when the polyelectrolyte solution is replaced with an aqueous polyelectrolyte-free solution. Injection of sodium dodecyl sulfate (SDS) into the measuring chamber to a concentration of about 0.01 CMC (8.3 × 10⁻⁵M) does not affect the adsorbed layers or the interaction forces. However, when the SDS concentration is increased to 0.02 CMC (0.166 mM) the adsorbed layer expands dramatically due to adsorption of SDS to the polyelectrolyte chains. The sudden swelling suggests a cooperative adsorption of SDS to the preadsorbed polyelectrolyte layer and that the critical aggregation concentration between the polyelectrolyte and SDS at the surface is about 0.02 CMC. The flocculation behavior of the polyelectrolyte in solution upon addition of SDS was also examined. It was found that 0.16–0.32 mol SDS/mol charged segments on the polyelectrolyte is enough to make the solution slightly turbid.     

Electrostatic Interactions and Stability of Poly-l-lysine Covered Polystyrene Latex Particles Investigated by Dynamic Light Scattering

Adsorption isotherms of the pH dependent positively charged polyelectrolyte poly-l-lysine (PLL) on negatively and positively charged polystyrene latices are determined. With photon correlation spectrometry (PCS) the influence of the fluctuating PLL domaines in solution on the diffusion coefficient is observed at low salt concentrationsc_NaBr< 10⁻³M with λ =c_PE/c_NaBr< 0.1 (c_PE= concentration of the polyelectrolyte units). Screening of the charged layer by increasing electrolyte concentration results in large adsorbed amounts and layer thicknesses. At low molar mass of PLL the suspensions become unstable and the state and kinetic of flocculation is followed by the decreasing diffusion coefficient. PLL of higher molar mass (M_w≥ 100 000) stabilizes the particles sterically and the adsorbed layer thicknesses can be determined. The conclusions drawn from PCS features are confirmed directly by raster electron micrographs of the filtered particles.     

Interaction of cellulose-based cationic polyelectrolytes with mucin

Mucoadhesivity of water-soluble polymers is an important factor, when testing their suitability for controlled drug delivery systems. For this purpose, the interaction of new cationic cellulose polyelectrolytes with lyophilized mucin was investigated by means of turbidimetric titration, microscopy and measurement of zeta potential and particle size changes in the system. Results show that the cellulose derivatives interact with mucin. This interaction became stronger if cellulose macromolecules contained positively charged groups and an electrostatic interaction with the negatively charged mucin particles occurred. Under certain conditions flocculation of mucin particles by the cellulose polyelectrolyte was observed.     

Charge-driven flocculation of poly(L-lysine)-gold nanoparticle assemblies leading to hollow microspheres

An unusual aggregation phenomenon that involves positively charged poly(L-lysine) (PLL) and negatively charged gold nanoparticles (Au NPs) is reported. Discrete, submicrometer-sized spherical aggregates are found to form immediately upon combining a PLL solution with gold sol (diameter approximately 14 nm). These PLL-Au NP assemblies grow in size with time, according to light scattering experiments, which indicates a dynamic flocculation process. Water-filled, silica hollow microspheres (outer diameter approximately microns) are obtained upon the addition of negatively charged SiO2 NPs (diameter approximately 13 nm) to a suspension of the PLL-Au NP assemblies, around which the SiO2 NPs form a shell. Structural analysis through confocal microscopy indicates the PLL (tagged with a fluorescent dye) is located in the interior of the hollow sphere, and mostly within the silica shell wall. The hollow spheres are theorized to form through flocculation, in which the charge-driven aggregation of Au NPs by PLL provides the critical first step in the two-step synthesis process ("flocculation assembly"). The SiO2 shell can be removed and re-formed by decreasing and increasing the suspension pH about the point-of-zero charge of SiO2, respectively.     

Kinetics of polyelectrolyte adsorption onto polystyrene latex particle studied using electrophoresis: effects of molecular weight and ionic strength

The kinetics of the adsorption of a cationic polymer flocculant onto negatively charged polystyrene latex (PSL) particles were measured by means of electrophoresis as a function of the molecular weight of the polyelectrolyte and the ionic strength of the solution. In the experiment, the dispersion of bare PSL particles was mixed with a polyelectrolyte solution by means of end-over-end rotation in which the mixing intensity was evaluated in terms of the collision frequency between the colloidal particles. The rate of electrophoretic mobility of a PSL particle, which remained as a singlet, was measured against the mixing steps, which was equivalent to the time elapsed after the onset of flocculation. The shape of the kinetic curves is typical: a linear increase for a short period followed by a plateau, implying the saturation of the colloidal surface by the adsorbed polyelectrolyte. In the case of low ionic strength, the plateau value was dependent on the molecular weight of the polyelectrolyte. That is, a lower plateau value was detected when the molecular weight of the polyelectrolyte was smaller and its concentration was lower. However, the amount of adsorption was kinetically controlled only for the case of higher molecular weight. In the case of high ionic strength, the plateau value of electrophoresis was constant, regardless of the polyelectrolyte concentration and molecular weight. These data will ultimately be useful in further analysis of the flocculation behavior of colloidal particles with a polyelectrolyte.     

Depletion Interactions Produced by Nonadsorbing Charged and Uncharged Spheroids

The effect of macromolecule shape on the depletion attraction between two hard spherical particles in a solution with nonadsorbing hard spheroidal macromolecules of arbitrary size and aspect ratio was investigated using a modified form of the force-balance model of J. Y. Walz and A. Sharma (1994, J. Colloid Interface Sci. 168, 495). The macromolecules were represented as general spheroids, which could be either charged or uncharged. For the uncharged case, a set of analytical expressions describing the depletion attraction, valid for particles much larger than the characteristic macromolecule size, was developed. Comparisons with the case of spherical macromolecules were made under the condition of either constant macromolecule number density, rho(b), or constant volume fraction, phi. It was found that increasing the spheroidal macromolecule aspect ratio (major axis length/minor axis length) decreases the depletion attraction at constant rho(b), but increases the interaction at constant phi. In the latter case, the interaction produced by prolate macromolecules is greater than that produced by oblate macromolecules of equal axis lengths, while the opposite is true at constant rho(b). A simple scaling analysis is used to explain these trends. Surface charge is found to increase both the range and the magnitude of the depletion attraction; however, the general trends are the same as those found in the uncharged systems. Finally, the effect of the depletion attraction produced by spherical and spheroidal macromolecules on the stability of a dispersion of charged particles was examined. It was found that charged spheroids at concentrations of order 1% volume can produce secondary energy wells of sufficient magnitude to induce flocculation in a dispersion of charged spherical particles. Copyright 2000 Academic Press.     

Coagulation and flocculation measurements by photon correlation spectroscopy — colloidal SiO2 bare and covered by polyethylene oxide

With photon correlation spectrometry (PCS) the diffusion coefficients, average diameters and polydispersities of colloidal particles can be determined in dilute aqueous suspensions. In this study PCS is used to follow the coagulation and flocculation of silica particles. Electrolyte solution added to suspensions of bare particles and of particles covered with adsorbed polyethylene oxide layers induces aggregation. The rate constants of aggregation are evaluated by the second-order Smoluchowski theory with the assumptions of spherical aggregated particles and volume proportional light-scattering amplitude. Adsorbed PEO layers of molar mass lower thanM _w=160000 decrease the critical flocculation concentration and the flocculation states and rate constants for bare and covered particles are the same at high electrolyte concentrations. Polymer layers of high molar mass (M _w=325000, 900000) reducved at full coverage the rate constants and stabilize the suspensions even at high electrolyte concentrations. At low coverage adsorption of high molar mass polymers results in the same values as of low molar mass PEO. The correlation between rate constants and hydrodynamic PEO layer thicknesses demonstrates the steric influence of the tails of the adsorbed macromolecules on stability and flocculation.Dedicated to Prof. Dr. Joachim Klein on the occasion of his 60th birthday     

The effect of pretreatment of calcite dispersions with anionic sodium polyacrylate on their flocculation behavior induced by cationic starch

The flocculation performance of cationic starches on calcite pretreated with anionic sodium polyacrylate (NaPA) was investigated by measuring the mean particle size and the dynamic mobility of the calcite dispersions. Cationic starches of different molecular weight and degree of substitution were used. By varying the amount of anionic sodium polyacrylate, which has a strong affinity to the calcium carbonate surface, one is able to anionically modify the particles and reverse the charge character of the originally cationic calcium carbonate. By such modification of the charge character of the calcium carbonate dispersion, it is possible to approach the mechanisms of flocculation caused by cationic macromolecules like starch. The importance of different mechanisms of flocculation, such as bridging, charge neutralization, and flocculation induced by polyelectrolyte complexes (PEC), was further investigated in this work. It was found that when the NaPA is completely absorbed at the calcite surfaces the mechanism of the flocculation induced by the starch is mainly bridging flocculation. Excess NaPA in the calcium carbonate dispersion will result in polyelectrolyte complexes formed between the non-absorbed NaPA and the oppositely charged starch polymers. These complexes will in most cases strongly enhance the flocculation due to mainly charge neutralization. Depending on the ratio of non-absorbed NaPA and the starch in the aqueous phase, the calcite dispersion is either re-stabilized or more strongly flocculated due to the formed polyelectrolyte complexes. Both the mobility and the particle size measurements support the mechanisms described. It was further demonstrated that the molecular weight and degree of substitution of the starches might be adjusted to control the flocculation behavior.     

The role of complex formation in the flocculation of negatively charged sols with anionic polyelectrolytes

Summary Flocculation of negatively charged colloids by anionic polyelectrolytes, resulting from the adsorption of polymers on the colloid surface and from bridging of polymer chains between solid particles, is only possible if an appropriate concentration of electrolyte is present in the solution. Complex formation in the immediate vicinity of the sol surface between the counter cation and the functional groups of the polyelectrolyte plays a major role in the attachment of anionic polyelectrolytes to negative hydrophobic sols.Stability constants for Cu(II) polyacrylate and for the Ca complexes of a polyacrylic acid, hydrolyzed polyacrylamide and polystyrene sulfonate have been determined, and the effect of solution variables upon flocculation of AgBr/Br^– sols by anionic polyelectrolytes have been investigated. Ca⁺² ions affect the adsorption of polystyrenesulfonate on a negatively polarized mercury surface, as reflected in measurements of the differential capacitance; the presence of complex bound functional groups apparently changes the structure and orientation ability of the adsorbed polymer.With 5 figures in 10 details and 2 tables     

Design and characterization of randomly speckled spheres

We use the "particle lithography" technique to fabricate randomly speckled spheres. Parts of positively charged 3.3 microm polystyrene microspheres were masked off with negatively charged 0.9 microm silica particles, and the remaining portion was covered with negatively charged 60 nm polystyrene nanoparticles. The masking particles were then removed to leave speckles on the larger core particle. Images from electron microscope and confocal microscope show that the diameter of the circular speckles is predictable and reliable, following an estimate from simple geometry, and that the number of speckles formed on a particle can be altered by changing the concentration of silica particle masks. The process described in this paper can be adapted to a wide variety of materials, opening the door for applications where size-controlled patches of one chemistry can appear on core particles of another chemistry and where the precise placement of patches is of little importance.     

Macroporous ZrO2 ceramics prepared from colloidally stable nanoparticles building blocks and organic templates

ZrO2 macroporous materials with well-ordered structures were prepared using nano-ZrO2 particles as the building materials and polystyrene spheres as the organic templates. A well-dispersed nano-ZrO2 suspension with a narrow particle size distribution was prepared by deagglomeration of as-received nano-ZrO2 powders via ultrasonication, and then centrifugation was performed to remove agglomerated bigger particles. Negatively charged polystyrene spheres were uniformly coated with positively charged nano-ZrO2 particles by means of electrostatic attraction at pH 4. Green samples were prepared by slip casting from colloidally stable suspension of nano-ZrO2 coated polystyrene spheres. ZrO2 macroporous materials with well-ordered microstructure derived from the nano-ZrO2 coated polystyrene spheres.     

Direct measurement of depletion and structural forces in polydisperse, charged systems

The effect of polydispersity in macromolecule size or surface potential on the depletion interaction between a spherical silica particle and a silica flat in solutions containing two different types of nonadsorbing charged spherical macromolecules was studied with an atomic force microscope (AFM). The macromolecules used here were negatively charged nanospheres of either polystyrene or silica. To investigate the effect of size polydispersity, experiments were performed under the condition of either constant macromolecule number density or constant volume fraction as the relative proportions of smaller and larger polystyrene nanospheres in the suspension were varied. Similarly, for the experiments with surface potential polydispersity, the suspensions contained varying fractions of more highly charged (polystyrene) and less highly charged (Ludox silica) nanospheres at constant number density. The experimental results were compared to the predictions of the modified force-balance model of Piech and Walz and semiquantitative agreement was found. In particular, the maximum attraction and repulsion observed in the measured force profiles were found to agree with the predicted trends as the makeup of the macromolecules was varied. The trend in the maximum attraction was also consistent with predictions made using a simple "scaling" analysis derived using the equation for hard-sphere interactions.     

Prediction and measurement of the interparticle depletion interaction next to a flat wall

A theoretical and experimental study was performed to investigate the depletion interaction between two colloidal particles next to a solid wall in a solution of nonadsorbing macromolecules. By calculating the change in free volume available to the macromolecules upon approach of the two particles, a relatively simple expression was developed for the interparticle depletion attraction in hard sphere systems as a function of the particle-particle and particle-plate spacing. Perhaps the most useful result obtained from this analysis was that the wall has no effect whenever the ratio of the particle radius to the macromolecule radius is greater than four. (In charged systems, this ratio would apply to the effective particle and macromolecule sizes.) A series of experiments was then performed in which the hydrodynamic force balance (HFB) apparatus was used to measure the shear force needed to separate a colloidal doublet consisting of two particles trapped in a secondary energy well formed by a repulsive electrostatic force and an attractive depletion force. The macromolecules used here were small, nanometer-sized spheres of either silica or polystyrene. Agreement between the measured separation forces and those predicted using the force balance model of J. Y. Walz and A. Sharma (J. Colloid Interface Sci. 168, 485 (1994)) was within a factor of 1.3 using no adjustable parameters and accounting for polydispersity and uncertainty in the macromolecule size. It is shown that this remaining discrepancy could be caused by the Brownian (stochastic) nature of the doublet breakup process.     

Strong and weak adsorptions of polyelectrolyte chains onto oppositely charged spheres

We investigate the complexation of long thin polyelectrolyte (PE) chains with oppositely charged spheres. In the limit of strong adsorption, when strongly charged PE chains adapt a definite wrapped conformation on the sphere surface, we analytically solve the linear Poisson-Boltzmann equation and calculate the electrostatic potential and the energy of the complex. We discuss some biological applications of the obtained results. For weak adsorption, when a flexible weakly charged PE chain is localized next to the sphere in solution, we solve the Edwards equation for PE conformations in the Hulthen potential, which is used as an approximation for the screened Debye-Huckel potential of the sphere. We predict the critical conditions for PE adsorption. We find that the critical sphere charge density exhibits a distinctively different dependence on the Debye screening length than for PE adsorption onto a flat surface. We compare our findings with experimental measurements on complexation of various PEs with oppositely charged colloidal particles. We also present some numerical results of the coupled Poisson-Boltzmann and self-consistent field equation for PE adsorption in an assembly of oppositely charged spheres.     

Probe diffusion from dilute to concentrated in polyelectrolyte solution: salt effect

The adsorption behaviors between a positively charged poly(allyamine) hydrochloride (PAH) matrix and negatively charged sulfate polystyrene (PS) particle probe were investigated using dynamic light scattering (DLS) and fluorescence photobleaching recovery (FPR) with reference to the matrix and salt concentration. The system experienced a steep decrease of diffusion (flocculation) under dilute conditions and a gradual decrease above semidilute concentrations. The fluorescence photobleaching recovery and viscometry experiments revealed that the probe behaviors in the polyelectrolyte solution were strongly affected by the coil overlap concentration (0.5 g/L poly(allyamine) hydrochloride). Near the coil overlap concentration, the hydrodynamic radius representing the entanglement dimension of the matrix was approximately 30 nm; however, at higher concentrations the radius gradually decreased, suggesting a transition toward a network structure. In this system, the salt performed two roles: (1) reinforcing the electrostatic interaction, and (2) preventing electrostatic interaction between the probe and the matrix.     

Electrochemical Properties of a Boron‐Doped Diamond Electrode Modified with Gold/Polyelectrolyte Hollow Spheres

Oppositely charged polyelectrolyte (poly(allyamine hydrochloride) (PAH) and poly(sodium 4‐styrene‐sulfonate) (PSS)), and negatively charged gold nanoparticles (Au) were assembled alternately on polystyrene (PS) spheres via layer‐by‐layer technique, and the different PAH/(PSS/PAH)_n/(Au/PAH)_m/Au composite hollow spheres were derived by dissolving PS core. These hollow spheres were used to modify boron‐doped diamond (BDD) electrodes for electrochemical sensors. The cyclic voltammetric results for dopamine (DA) detection demonstrated that hollow‐sphere‐modified BDD exhibited better electrocatalytic activity than did bare BDD. Influence of the wall thickness and composition of hollow spheres on electrochemical properties were investigated. The results showed that the oxidative peak potential of DA and the peak current varied with different PSS/PAH and Au/PAH layers. The optimized wall structure of hollows spheres was PAH/(PSS/PAH)₇/(Au/PAH)₅/Au.     

Separation and detection of individual submicron particles by capillary electrophoresis with laser-light-scattering detection

Separation and detection of individual submicron polystyrene spheres using capillary electrophoresis with laser-light-scattering detection has been demonstrated. Electrophoretically separated particles were passed through a focused laser beam and light scattered from individual particles was collected at 90 degrees. Each diameter of polystyrene spheres injected (from 110 to 992 nm) resulted in the observation of a well-defined migration window containing multiple peaks, each arising from the light scattered by an individual particle. The migration time window for individual particles of a particular size corresponded well to the migration time of a peak from a population of particles of the same size detected using a UV absorbance detector. The electrophoretic mobility and scattered light intensity were determined for each particle detected. The average scattered light intensity for each particle size was consistent with Mie scattering theory. Particles as small as 110 nm in diameter were detected individually using this method, but particles with a diameter of 57 nm could not be individually detected. The number of single particle scattering events was counted and compared to the theoretical number of particles injected electrokinetically, and the detection efficiency determined ranged from 38 to 57% for polystyrene spheres of different sizes. The laser-light-scattering detection method was directly compared to laser-induced fluorescence detection using fluorescent polystyrene microspheres. The number of particles detected individually by each method was in agreement.     

Peculiarities of the formation of polyacrylamide compound-based polyelectrolyte complexes in the course of the flocculation of clay-salt dispersions

Peculiarities of the formation of polyelectrolyte complexes based on cationic and anionic copolymers of acrylamide having different macromolecule charge densities on the surfaces of kaolin particles in highly concentrated salt solution are investigated. The interactions of the copolymers with the clay particle surface and with each other are studied by electrokinetic and IR spectroscopy methods. The rheological properties of kaolin suspensions are investigated in a salt solution in the presence of the polyelectrolytes. The flocculation ability of the polyelectrolytes and their binary mixtures with respect to clay-salt dispersion is estimated. The mechanism for the formation of polyelectrolyte complexes on the surface of clay particles is discussed. It is shown that the complexation of oppositely charged polyelectrolytes on the surfaces of clay particles intensifies the flocculation of clay-salt dispersions.     

Adsorption of poly(vinyl formamide-co-vinyl amine) onto silica particle surfaces and stability of the formed hybrid materials

In order to produce silica/polyelectrolyte hybrid materials the adsorption of the polyelectrolyte poly(vinyl formamide-co-vinyl amine), P(VFA-co-VAm) was investigated. The adsorption of the P(VFA-co-VAm) from an aqueous solution onto silica surface is strongly influenced by the pH value and ionic strength of the aqueous solution, as well as the concentration of polyelectrolyte. The adsorption of the positively charged P(VFA-co-VAm) molecules on the negatively charged silica particles offers a way to control the surface charge properties of the formed hybrid material. Changes in surface charges during the polyelectrolyte adsorption were studied by potentiometric titration and electrokinetic measurements. X-ray photoelectron spectroscopy (XPS) was employed to obtain information about the amount of the adsorbed polyelectrolyte and its chemical structure. The stability of the adsorbed P(VFA-co-VAm) was investigated by extraction experiments and streaming potential measurements. It was shown, that polyelectrolyte layer is instable in an acidic environment. At a low pH value a high number of amino groups are protonated that increases the solubility of the polyelectrolyte chains. The solvatation process is able to overcompensate the attractive electrostatic forces fixing the polyelectrolyte molecules on the substrate material surface. Hence, the polyelectrolyte layer partially undergoes dissolving process.     

Heteroaggregation, repeptization and stability in mixtures of oppositely charged colloids

We report a study of mixtures of initially oppositely charged particles with similar size. Dispersions of silica spheres (negatively charged) and alumina-coated silica spheres (positively charged) at low ionic strength, mixed at various volume ratios, exhibited a surprising stability up to compositions of 50% negative colloids as well as spontaneous repeptization of particles from the early-stage formed aggregates. The other mixtures were found to contain large heteroaggregates, which were imaged using cryogenic electron microscopy. Electrophoretic mobility, electrical conductivity, static and dynamic light scattering and sedimentation were studied as a function of volume fraction of the mixed dispersions to investigate particle interactions and elucidate the repeptization phenomenon.