Adsorption of cationic polyelectrolyte onto a model carboxylic latex and the influence of adsorbed polycation on the charge regulation at the latex surface

 Adsorption of a well-characterized cationic polyacrylamide (CPAM) onto the surface of a model colloid (monodisperse polystyrene latex with carboxylic functional groups) was studied over a wide range of pH (4–9) and KCl concentration (c _s =10^-3–0.3 M). The surface charge density of the latex particles with and without adsorbed CPAM was also measured over the same range of electrolyte compositions. The adsorbed amount of CPAM increases with increase in c _s and pH. The polyelectrolyte adsorption alters substantially the surface charge density of the latex particles as compared to the polymer-free case. A large overcompensation of the surface charge by the adsorbed polyelectrolyte is established at high c _s and low pH. A qualitative explanation of the observed features is put forward. Received: 3 December 1996 Accepted: 20 January 1997     

Dextran stabilized poly(methyl methacrylate) latex particles and their potential application for affinity purification of lectins

 Stable poly(methyl methacrylate) latex particles (220–360 nm in diameter) using dextran as the protective colloid were prepared and characterized in this study. Such an emulsion polymerization system follows Smith–Ewart Case III kinetics (i.e., the average number of free radicals per particle is greater than 0.5) due to the relatively large latex particle size. The carbohydrate content of these dextran modified emulsion polymers shows a maximum around 5% dextran based on total monomer weight. The latex stability during polymerization is closely related to the carbohydrate content of these latex particles, and it is controlled by the ratio of the thickness of the dextran adsorption layer to that of the electric double layer of the latex particles. The critical flocculation concentration (CFC) of the latex products correlates well with the latex stability during polymerization. The greater the total scrap produced during polymerization (i.e., the stronger the bridging flocculation), the lower is the CFC of the latex products. The affinity precipitation of concanavalin A (a model lectin used in this study) by the dextran modified PMMA latex particles is also illustrated in this study. The specifically adsorbed concanavalin A increases with the carbohydrate content of the dextran modified latex particles. Received: 9 December 1996 Accepted: 8 April 1997     

Interaction of bacterial endotoxine (lipopolysaccharide) with latex particles: application to latex agglutination immunoassays

The latex agglutination immunoassay technique uses polymer colloids as carriers for antibodies or antigens to enhance the immunological reaction. In this work, the interaction of a lipopolysaccharide (LPS) of Brucella Melitensis with two conventional latexes has been studied. Some experiments on the physical adsorption of the LPS onto these polystyrene beads have been performed and several complexes with different coverage degrees were obtained by modifying the incubation conditions. Regarding the application in the development of diagnostic test systems, it is advisable to study the latex-LPS complexes from an electrokinetic and colloidal stability point of view. The complexes were electrokinetically characterized by measuring the electrophoretic mobility under different redispersion conditions. The colloidal stability was determined by simple turbidity measurements. Experimental and theoretical data have been employed to study the molecular disposition of the LPS in the latex particle surface to compare with the outer membrane of bacterial cells. Latex complexes covered by different LPS amounts showed high colloidal stability and adequate immunoreactivity that remains for a long time period.     

On the adsorption of IgG onto polystyrene particles: electrophoretic mobility and critical coagulation concentration

An experimental investigation on the adsorption of immuno -globulin molecules on polystyrene microspheres is described. Three different IgG samples were adsorbed on latex particles. One was of polyclonal nature with a broad range of isoelectric points (6.1–8.7), whereas the other samples were of monoclonal nature, Mab 1 and Mab 2 with i.e.p. of (5.65±0.15) and (7.7±0.1), respectively. Adsorption isotherms at different ionic strengths and pH were performed. Most of the adsorption isotherms showed well-defined plateaus. Because of instability in solution of Mab 2 in the pH values of 7 and 8, no plateau values were found in the adsorption isotherms at both pH-values. Maximum protein adsorption was found around the i.e.p. of the protein. According to the findings, the IgG adsorption on polystyrene surface is strongly irreversible with respect to pH changes. The ionic-strength changes, however, exert a pronounced effect on the adsorption-desorption processes of IgG on negatively charged polystyrene surface. Also, electrophoresis experiments were performed to gain information on the electrostatic interaction between the IgG molecules and the PS latex. With increasing the adsorbed amount of IgG the absolute value of mobility decreases to reach a plateau value. The isoelectric pH of the IgG-PS complex is always smaller than the i.e.p. of the dissolved IgG, indicating that the PS surface charge must partly compensate the positive charge on the protein. Finally, the colloidal stability of the rabbit IgG/PS complex is always very low, whereas the Mab/PS complexes are very stable when the charge electrokinetically mobilized by these systems is very large.     

Adsorption of Bovine Serum Albumin onto Polystyrene Latex Particles Bearing Saccharidic Moieties

The adsorption of bovine serum albumin (BSA) onto polystyrene latexes bearing various amounts of sugar moieties has been investigated as a function of pH and ionic strength and the results were compared to those for bare polystyrene latexes having negative surface charges. The functionalized latexes were produced by seeded copolymerization of (0.3 μm) liposaccharidic monomer onto polystyrene particles obtained by soap-free emulsion polymerization of styrene using potassium persulfate as initiator. At first, the electrophoretic mobility behavior of the various latexes was examined as a function of pH: a significant decrease was observed in the case of saccharide-containing latex particles compared to the bare particles. The adsorption of BSA onto these latexes exhibited a reduced amount of adsorbed BSA for those latex particles bearing saccharide groups. This adsorbed amount depends on the yield of saccharidic monomer incorporated onto the surfaces of the latex particles.     

Electrostatic interactions between amphoteric latex particles and proteins

The electrostatic interactions between amphoteric polymethyl methacrylate latex particles and proteins with different pI values were investigated. These latex particles possess a net positive charge at low pH, but they become negatively charged at high pH. The nature and degree of interactions between these polymer particles and proteins are primarily controlled by the electrostatic characteristics of the particles and proteins under the experimental conditions. The self-promoting adsorption process from the charge neutralization of latex particles by the proteins, which have the opposite net charge to that of the particles, leads to a rapid reduction in the zeta potential of the particles (in other words colloidal stability), and so strong flocculation occurs. On the other hand, the electrostatic repulsion forces between similarly charged latex particles and the proteins retard the adsorption of protein molecules onto the surfaces of the particles. Therefore, latex particles exhibit excellent colloidal stability over a wide range of protein concentrations. A transition from net negative charge to net positive charge, and vice versa (charge reversal), was observed when the particle surface charge density was not high enough to be predominant in the protein adsorption process.     

Electrochemical properties and stability of emulsifier-free polystyrene latexes in 1: 1 electrolyte solutions

The electrokinetic and adsorption characteristics of monodisperse emulsifier-free latexes of polystyrene (particle sizes of 0.25–0.40 μm) with surface carboxyl and sulfo groups are comprehensively studied depending on pH and the concentration of background NaCl solutions. The constants of surface carboxyl group dissociation and surface complexation, as well as the adsorption potentials of OH^? and Na⁺ ions, are calculated. The stability of latex suspensions is investigated and the coagulating concentrations of NaCl and HCl solutions are determined. An analysis of the curves plotted for the pair interaction between latex particles at different concentrations of NaCl solutions suggests that the system possesses an additional stability factor, which is probably associated with polymer chains that protrude over the particle surface into a solution.     

Latex Immunoagglutination Assays

Latex immunoagglutination assays continue to be widely used in biology and medicine for the detection of small quantities of an antibody or antigen of interest in fluid test samples. Main characteristics of preparation and use of these assays are examined here. Physical adsorption of proteins onto latex particles surface, with special relevance to immunoglobulins, is analyzed with major attention to those factors that influence adsorption: medium conditions such as pH and ionic strength, surface characteristics as type and amount of charge, or hydrophobicity. Different functionalized latexes for covalent linking are also presented, as well as the corresponding chemical reactions. Techniques for the detection and quantification of the immunoreaction are briefly summarized, including visual observation, light scattering, turbidimetry, nephelometry, and angular anisotropy. Finally, some problems of colloidal stability of these latex assays are analyzed, as well as the different solutions applied by scientists to solve them.     

Changes in electrokinetic properties of natural rubber latex after surface chemical modifications

High-ammonia latex concentrate prepared from doubly-concentrifuged fieldHevea latex was exhaustively dialyzed to remove any residual water-soluble non-rubber constituents. The specially purified latex was then treated with specific chemical reagents to modify the surface ionogenic groupings originally present on the latex particle surface. The electrophoretic mobility of the modified latexes was investigated as a function of pH. The change in electrokinetic properties of the surface-modified latex was explained in terms of chemical modification to the ionogenic groups of the adsorbed layer of proteins and long chain fatty acid soaps on the latex particle surface, the negative charges of which are primarily responsible for the colloidal stability of the latex. For comparison direct extraction of the long-chain fatty acid soaps from the specially purified latex by solvent was also carried out. Present results indicate that the number of carboxyl groups from the adsorbed long-chain fatty acid soaps plays a major role in the stabilization of the latex concentrate. In comparison the contribution of negative charges from the adsorbed proteins towards the stability of the latex is of less importance.     

The Influence of Leucanol on the Aggregative Stability of Synthetic Latexes

On the example of model systems (polystyrene latexes and copolymers of styrene with polar monomers, acrylonitrile and ethoxyethyl acrylate), the effect of sodium naphthyl formaldehyde sulfonate on the aggregative stability of synthetic latexes was analyzed. Upon reaching the limit conversion, these latexes during storage spontaneously transfer to a solid gel having a periodic colloidal crystal-like structure. It is shown that the gelation process obeys the Smoluchowski law for coagulation. An increase in the molecular weight of the polymer and in the size of the latex particles during the formation of the gel was recorded. The introduction of a NF dispersing agent neutralizes the gel effect, stabilizes the system, prevents gelation and leads to a slight increase in the molecular weight of the polymer and the degree of polydispersity of the polymers obtained. It has been suggested that stable macroradicals accumulating from the gel-effect stage and remaining in the system after completion of polymerization can be one of the reasons for the loss of aggregative stability of latexes, and incorporating the dispersing agent into the adsorption layer of polymer-monomer particles leads to the recombination of these radicals within the particle and the stabilization of latexes in the polymerization process.     

Synthesis and characterization of core–shell polyacrylate latex containing fluorine/silicone in the shell and the self-stratification film

A series of core–shell polyacrylate latexes with different fluorine/silicone monomer concentrations were prepared successfully by seeded emulsion polymerization. Dodecafluoroheptyl methacrylate and perfluorooctyl methacrylate with different fluorinated side chains were employed as fluorinated monomers, and γ-methacryloxypropyl triisopropoxidesilane (MAPTIPS) was used as a silicone-containing monomer as well as a self-cross-linking agent. The morphology and chemical structure of the latexes were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry, and the self-stratification properties of the latex film were verified by X-ray photoelectron spectroscopy and static contact angle measurement. The results showed that the fluorine/silicone-containing polyacrylate latexes presented a uniformly spherical core–shell structure, and the latex films displayed a preferential distribution of fluorinated composition near the surface, which was more remarkable with the synergism effect between the fluorine monomer and MAPTIPS. Additionally, the hydrophobicity and oleophobicity of the latex films exhibited high relevance with the fluorine/silicone monomer concentrations as well as the fluorinated side-chain structure.     

Controlled adsorption-desorption of cationic polymers on the surface of anionic latex particles

The complexation of anionic latex particles with two series of cationic copolymers is studied. The copolymers of the first series contain cationic and electroneutral (zwitter ion) hydrophilic units. The electrostatic adsorption of these copolymers on the surface of latex particles is accompanied by the formation of multiple salt bridges between cationic copolymer units and surface anionic groups. The dependence of ultimate adsorption on the molar fraction of cationic groups in copolymer α is described by a bell-shaped curve with a maximum at α = 0.05−0.10 and a long horizontal portion at α > 0.24. In terms of the adsorption theory of polyampholytes, such a pattern of the adsorption curve results from the compromise between the attraction of polymer chains to the surface induced by their polarization in the electric field of particles and the repulsion of like charged macromolecular units. The stability of complexes with the copolymers of the first series in water-salt media increases with an increase in α. The copolymers of the second series contain cationic and hydrophobic units. In this case, an increase in α is accompanied by a decrease in the amount of the adsorbed polymer throughout the studied α range (0.24–1). The complexes are stabilized not only via electrostatic interactions but also via hydrophobic interactions. A decrease in α decreases the role of electrostatics in stabilization of the complexes; however, this effect is compensated for by an increase in the number of hydrophobic contacts. This allows the stability of complexes to be preserved in concentrated water-salt solutions. The results of this study indicate that the stability of interfacial layers with the participation of cationic copolymers can be changed in a wide range by varying the ratio of ionic and electroneutral (hydrophilic or hydrophobic) comonomers in macromolecules.     

Colloidal stability of sulfonated polystyrene model colloids. Correlation with electrokinetic data

In this work we describe the colloid stability of functionalized latexes: two sulfonated polystyrene model colloids with the same particle size and different surface charge densities. The critical coagulation concentration (ccc) was determined in the presence of two electrolytes (11 and 22), being around 0.75 M and 0.075 M, respectively. By the DLVO theory the electrokinetic and colloid stability data were correlated to calculate the Hamaker constant at both experimental conditions. By comparing the experimental and theoretical values of the Hamaker constant, it is possible to get more information about the colloidal stabilization mechanism of functionalized latexes. In the case of sulfonated latexes, the electrostatic and seric contributions occur, with different influence for each latex depending of their surface electric charge.     

New polycationic polynorbornene latexes bearing an amphiphilic sugar corona of counterions: synthesis and complexation with DNA

A new family of polycationic polynorbornene with ω-gluconamidoalkanoates and ω-lactobionamidoalkanoates as amphiphilic counterions has been prepared. These polymers spontaneously form stable latexes in water with an amphiphilic sugar corona around the particles. With these counterions, the sugar moieties are separated from the surface of latex particles by the aminoalkanoic acid residue and consequently are remote from the surface of such latexes. Such location of sugar may promote their stronger interaction with cell receptors. These original amphiphilic compartmentalized surface polycationic latexes are able to bind and efficiently complex DNA in very small complexes. Furthermore, because of the effect of the sugar corona on the formation of the complexes, there is only a slight influence of the hydrophobicity of the counterions on DNA packing.     

Study of the adsorption of F(ab')2 onto polystyrene latex beads

An experimental investigation on the adsorption of F(ab')₂ from rabbit IgG onto polystyrene (PS) latex beads is described. All adsorption isotherms were of high affinity and showed well-defined plateaus. Maximum protein adsorption was found around the average isoelectric point (IEP) of the dissolved protein. According to the findings, the F(ab')₂ adsorption on the polystyrene surface is strongly irreversible with respect to ionic strength changes. The pH changes, however, exert a certain effect on the adsorption-desorption process of F(ab')₂ on negatively charged polystyrene surfaces. In order to determine the role played by the electrostatic forces in the F(ab')₂ adsorption onto negatively charged latex particles, an electrokinetic study of the protein-latex complexes has also been carried out. The isoelectric pH of the F(ab')₂-PS complexes is always smaller than the IEP of the dissolved F(ab')₂, indicating that the PS surface charge must partly compensate the positive charge on the protein. Finally, a comprehensive study on the colloidal stability of the sensitized latex beads was performed.     

Cationic amino-containing N-isopropyl- acrylamide-styrene copolymer particles: 2-surface and colloidal characteristics

 In a previous paper [1], the synthesis of various polystyrene– poly[NIPAM] core–shell latexes bearing cationic amidino and/or amino charges has been described. Several colloidal properties of these cationic latexes have been charac-terized such as: particle size, surface charge density, electrophoretic mobility and finally colloidal stability. Due to the poly[NIPAM]-rich layer in the shell, it was found that temperature played a significant role on all these properties, a LCST around 33 °C being exhibited. In addition, ionic strength was also found to affect the colloidal behavior of these latexes, the largest effect being observed with latexes having both amidino and amino surface charges. The critical coagulation concentra-tions (CCC) of the various latexes above and below the LCST were determined, highlighting the contribution of electrostatic and steric repulsive forces to the stability of these particles. Received: 20 January 1998 Accepted: 8 June 1998     

Kinetics of sodium dodecyl benzene sulfonate adsorption on hematite and its interaction with polyacrylamide

This article describes the adsorption of sodium dodecyl benzene sulfonate, an anionic surfactant, on a hematite surface and that when the surface is preadsorbed with polyacrylamide. The adsorption of surfactant on a hematite surface has been studied through equilibration and during kinetics measurements at three pH levels, viz. 4.0, 7.0, 8.9. The surfactant adsorbs strongly on the hematite surface. The adsorption density at equilibrium as well as the rate of adsorption are dependent on the suspension pH. The maximum adsorption density has been observed at pH 4, which reflects strong adsorption of negatively charged sulfonate ions on the oppositely charged Fe₂O₃ surface (point of zero charge, 6.4). The adsorption density reaches its equilibrium value sooner in the case of an alkaline suspension and later in the case of acidic pH. The polymer surfactant interaction has been noticed in the present study and is also a function of pH. The hematite mineral when preadsorbed with the polymer draws fewer of the surfactant molecules at lower surface coverage (during the initial period of the kinetics measurement) irrespective of the pH. When the adsorption of the surfactant reaches a value which is near the equilibrium one, the pH effect is evident. In the case of acidic pH, the surfactant adsorbs more on the hematite surface when preadsorbed with the polymer compared to the bare surface. In the case of neutral or alkaline pH, however, the density of surfactant adsorption remains lower throughout the kinetics measurement when the surface is preadsorbed with the flocculant compared to the bare surface. The particles also remain flocculated till the end of the experiment, whereas at pH 4 the particles are deflocculated. In addition to pH, the electrostatic nature of the adsorbent and the presence of anionic surfactant have an influence on the flocculation–deflocculation phenomena. The polymer–surfactant interaction has been schematically represented. The surfactant is bound with polymeric chains as a combination of its monomeric form as well as in the form of association in the case of acidic media and in competition with polymer in the case of alkaline media. Received: 18 April 2000/Accepted: 2 August 2000     

Well-Characterized Monodisperse Latexes as Model Colloids

Monodisperse polystyrene latexes prepared with persulfate-ion initiator can be ion exchanged to remove the adsorbed emulsifier and solute electrolyte. Rigorous purification of the ion-exchange'resins is necessary to avoid contamination with leached polyelectrolytes. These ion-exchanged latexes are stabilized with the residual sulfate end-groups of the polymer molecules, the number of which is determined by conductoroetric titration. The result is a dispersion of monodisperse spheres with-a constant and known surface charge due to chemically-bound strong-acid groups. These latexes are ideal models for colloidal studies. Preliminary experiments of stability, adsorption, sedimentation, viscosity, interference colors, and conductance give consistent results, e.g., the particle double-layer interactions determined by viscosity are in accord -with the particle spacings estimated from interference colors, the double-layer parameters estimated from conductometric titration and conductance measurements account for the measured decrease in sedimentation rate due to double-layer interactions, and the molecular area of sodium dodecyl sulfate measured by adsorption in latex is in agreement with literature values.     

Hydrophilic magnetic polymer latexes. 1. Adsorption of magnetic iron oxide nanoparticles onto various cationic latexes

With a view to preparing monosized hydrophilic functional magnetic latex particles based on a two-step strategy using anionic iron oxide and cationic polymer latexes, the adsorption step was systematically investigated for a better control of the subsequent encapsulation step. The iron oxide nanoparticles were first obtained according to the classical precipitation method of ferric and ferrous chloride salt using a concentrated sodium hydroxide solution, whereas the polystyrene (PS), P(S/N-isopropylacrylamide (NIPAM)) core–shell and PNIPAM latexes were produced via emulsion and precipitation polymerizations, respectively. The polymer and inorganic colloids were then characterised. The adsorption of iron oxide nanoparticles onto the three types of polymer latexes via electrostatic interaction was studied as a function of iron oxide particle concentration, charge density and the cross-linking density of the hydrophilic layer. The maximum amounts of magnetic nanoparticles adsorbed onto the various latexes were found to increase in the following order: PS < P(S/NIPAM) < P(NIPAM). This significant difference is discussed by taking into account the charge distribution in the hydrogel layer and diffusion phenomena inside the cross-linked hydrophilic shell. Received: 28 December 1998 Accepted in revised form: 15 April 1999     

Electrokinetic characterization of polystyrene–non-ionic surfactant complexes

An experimental study on the electrophoretic mobility (μ_e) of polystyrene particles after the adsorption of non-ionic surfactants with different chain lengths is described. Two sulphate latexes with relatively low surface charge densities (3.2 and 4.8 μC cm⁻²) were used as solid substrate for the adsorption of four non-ionic surfactants, Triton X-100, Triton X-165, Triton X-305 and Triton X-405, each one with 9–10, 16, 30 and 40 molecules of ethylene oxide (EO), respectively. The electrophoretic mobility of the polystyrene–non-ionic surfactant complexes was studied versus the amount of adsorbed surfactant (Γ). The presence of non-ionic surfactant onto particles surface seems to produce a slight shifting of the slipping plane because the mobilities of the different complexes display a very small decreasing. The increase in the number of EO chains in the surfactant molecule seems to operate as a steric impediment which decreases the number of adsorbed large surfactant molecules. The electrophoretic mobilities of the latex–surfactant complexes with maximum adsorption were measured versus the pH and ionic strength of the dispersion. While the different complexes showed a similar qualitative behaviour compared with that of the bare latex against the pH, the adsorption of the surfactant reduces the typical maximum in the μ_e−log[electrolyte].