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Microencapsulation by means of step-wise adsorption of polyelectrolytes.

Step-wise adsorption of polyelectrolytes is used for the fabrication of micro- and nanocapsules with determined size, capsule wall composition and thickness. The capsule walls made of polyelectrolyte multilayers exclude high molecular weight compounds. Assembling of lipid layers onto these polyelectrolyte capsules prevents the permeation of small dyes. Encapsulation of magnetite nanoparticles is demonstrated and the features of these novel capsules are discussed.

Adsorption↗

Treatment of effluents of poultry slaughterhouse with aluminum salts and natural polyelectrolytes.

A mixture of aluminum salts and natural polyelectrolytes, extracted from the cactus Opuntia ficus indica, has been used for cleaning of wastewater from poultry slaughterhouse. The aggregation and settling properties of colloids and complex organics such as oil, grease, fats, proteins, and suspended solids, was increased if compared with conventional methods of wastewater treatment using only aluminum or iron sulfate. A mixture of aluminum salt in a concentration range of 300 to 600 mg l(-1) and natural polyelectrolytes of 0.6 to 0.8 mg l(-1) was used for flocculation and coagulation. The combination of coagulant and natural polyelectrolytes was able to remove chemical oxygen demand (86%), oil and grease (93%), turbidity (89%), and suspended solids (93%). Methanization activity was also investigated for the effluents in natura.

Abattoirs↗

Immune response to 17 beta-estradiol in polyelectrolyte complex: antigen specificity and affinity of hybridoma clones.

Complex formation between synthetic polyelectrolytes (PE) [poly-4-vinyl-N-ethyl (cetyl), pyridine bromides-PVP(R2, R16)], bovine serum albumin (BSA), or 17 beta-estradiol-BSA conjugate (BSA.E) was studied in neutral water. Weakly water-soluble (colloidal) complex was formed upon addition of BSA.E to PVP (R2, R16) solution at pH 7. A nonrandom distribution of the protein molecules between the coils of polycations and self-assembly in the nonstochiometric polycomplex particles took place. The immunogenic properties of PVP (R2, R16)-BSA.E polycomplex were investigated and the specificities of produced antibodies analyzed. 17 beta-Estradiol introduced in polyelectrolyte complexes (PE-BSA) was found to invoke considerable increases in the steroid-specific immunoresponse. However, a comparative study of immunogenic activity of polycomplexes versus BSA.E+incomplete Freund's adjuvant (IFA) mixtures revealed some differences in regards to the specificity of antibody production. In contrast to IFA+BSA.E systems, polycomplexes were able to generate estradiol-as well as BSA-specific antibodies. Such a carrier-directed response may be determined by increase in immunogenicity of weak antigenic determinants and/or by the exposure of internally located determinants upon complex formation with polyelectrolytes. Fusions following the two different immunization procedures resulted in the growth of comparable numbers of estradiol-specific monoclonal antibodies with apparently similar antigen affinities. Thus, immunizations using antigens in PEC appear to provide an efficient alternative to IFA.

Animals↗

Effects of a polyelectrolyte additive on the selective dialysis membrane permeability for low-molecular-weight proteins.

BACKGROUND: Improving the sieving characteristics of dialysis membranes enhances the clearance of low-molecular-weight (LMW) proteins and may have an impact on outcome in patients receiving haemodialysis. To approach this goal, a novel polyelectrolyte additive process was applied to a polyethersulphone (PES) membrane. METHODS: Polyelectrolyte-modified PES was characterized in vitro by measuring complement activation and sieving coefficients of cytochrome c and serum albumin. In a prospective, randomized, cross-over study, instantaneous plasma water clearances and reduction rates of LMW proteins [beta(2)-microglobulin (b2m), cystatin c, myoglobin, retinol binding protein] were determined in eight patients receiving dialysis treatment with PES in comparison with polysulphone (PSU). Biocompatibility was assessed by determination of transient leucopenia, plasma levels of complement C5a, thrombin-antithrombin III (TAT), myeloperoxidase (MPO) and elastase (ELT). RESULTS: PES showed a steeper sieving profile and lower complement activation in vitro compared with PSU. Instantaneous clearance (69 +/- 8 vs. 58 +/- 3 ml/min; P < 0.001) and reduction rate (72.3 +/- 1 5% vs 66.2 +/- 6.1%; P < 0.001) of b2m were significantly higher with PES as compared with PSU. With higher molecular weight of proteins, differences in the solute removal between PES and PSU further increased, whereas albumin loss remained low (PES, 0.53 +/- 0.17 vs PSU, <0.22 g/dialysis). MPO, ELT and TAT did not differ between the two membranes. In contrast, leucopenia was less pronounced and C5a generation was significantly lower during dialysis with PES. CONCLUSIONS: Polyelectrolyte modification of PES results in a higher LMW protein removal and in optimized biocompatibility. Whether these findings translate into better outcome of patients receiving haemodialysis requires further studies.

Animals↗

Size, flexibility, and scattering functions of semiflexible polyelectrolytes with excluded volume effects: monte carlo simulations and neutron scattering experiments

We present a systematic Monte Carlo study of the scattering function S(q) of semiflexible polyelectrolytes at infinite dilution, in solutions with different concentrations of added salt. In the spirit of a theoretical description of polyelectrolytes in terms of the equivalent parameters, namely, persistence length and excluded volume interactions, we used a modified wormlike chain model, in which the monomers are represented by charged hard spheres placed at distance a. The electrostatic interactions are approximated by a Debye-Huckel potential. We show that the scattering function is quantitatively described by that of uncharged wormlike chains with excluded volume effects provided that an electrostatic contribution is added to the persistence length. In addition we have studied the expansion of the radius of gyration and of the end-to-end distance. The results are in agreement with the picture outlined in the Odijk-Skolnick-Fixman theory, in which the behavior of charged polymers is described only in terms of increasing local rigidity and excluded volume effects. Moreover, the Monte Carlo data are found to be in very good agreement with experimental scattering measurements with equilibrium polyelectrolytes, i.e., giant wormlike micelles formed in mixtures of nonionic and ionic surfactants in dilute aqueous solution, with added salt.

Journal Article↗

Electrical conductivity of aqueous polyelectrolyte solutions in the presence of counterion condensation: the scaling approach revisited.

The conductometric properties of aqueous polyelectrolyte solutions in the absence of added salt are reviewed in the light of the dynamic scaling description of the polymer conformation in different concentration regimes, recently proposed by Dobrynin and Rubinstein [Macromolecules 28, 1859 (1995); 32, 915 (1999)]. The scaling approach to the transport properties of polyelectrolyte solutions allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to the dilute and semidilute regimes. Moreover, the quality of the solvent, influencing the polyion-counterion interactions, can be properly taken into account. The electrical conductivity predicted by this scaling approach compares reasonably well with the observed values for a model polyelectrolyte (polyacrylate sodium salt in aqueous solutions, good solvent condition) over an extended concentration range from the dilute to the semidilute regime.

Journal Article↗

Interaction of proteins with spherical polyelectrolyte brushes in solution as studied by small-angle x-ray scattering.

We use small-angle x-ray scattering (SAXS) as a tool to study the binding of proteins to spherical polyelectrolyte brushes (SPB) in situ. The SPB consists of a solid core of approximately 100 nm diam onto which long polyelectrolyte chains [poly(styrene sulfonic acid, PSS) and poly(acrylic acid, PAA)] have been densely grafted. The proteins used in this investigation, Bovine Serum Albumine (BSA) and Bovine Pancreatic Ribonuclease A (RNase A), adsorb strongly to these SPB if the ionic strength is low despite their negative charge. Virtually no adsorption takes place at high ionic strength. SAXS demonstrates that both proteins are distributed within the brush. The findings reported here give further evidence that the strong adsorption of proteins to SPB is due to the "counterions release forces": The patches of positive charge on the surface of the proteins become multivalent counterions of the polyelectrolyte chains. Thus, a concomitant number of co- and counterions is thereby released and the entropy of the entire system is increased. The repulsive Coulombic interaction as well as the steric repulsion between the proteins and the brush layer are counterbalanced by this effect. The data discussed here demonstrate that the adsorption of proteins in SPB presents a new principle for the immobilization of proteins.

Adsorption↗

Polyelectrolyte adsorption: chemical and electrostatic interactions.

Mean-field theory is used to model polyelectrolyte adsorption and the possibility of overcompensation of charged surfaces. For charged surfaces that are also chemically attractive, the overcharging is large in high salt conditions, amounting to 20-40 % of the bare surface charge. However, full charge inversion is not obtained in thermodynamical equilibrium for physical values of the parameters. The overcharging increases with addition of salt, but does not have a simple scaling form with the bare surface charge. Our results indicate that a more evolved explanation is needed in order to understand polyelectrolyte multilayer buildup. For strong polymer-repulsive surfaces, we derive simple scaling laws for the polyelectrolyte adsorption and overcharging. We show that the overcharging scales linearly with the bare surface charge, but its magnitude is very small in comparison to the surface charge. In contrast with the attractive surface, here the overcharging is found to decrease substantially with addition of salt. In the intermediate range of weak repulsive surfaces, the behavior with addition of salt crosses over from increasing overcharging (at low ionic strength) to a decreasing one (at high ionic strength). Our results for all types of surfaces are supported by full numerical solutions of the mean-field equations.

Journal Article↗

Equilibrium bundle size of rodlike polyelectrolytes with counterion-induced attractive interactions.

Multivalent counterions can induce an effective attraction between like-charged rodlike polyelectrolytes, leading to the formation of polyelectrolyte bundles. In this paper, we calculate the equilibrium bundle size using a simple model in which the attraction between polyelectrolytes (assumed to be pairwise additive) is treated phenomenologically. If the counterions are pointlike, they almost completely neutralize the charge of the bundle, and the equilibrium bundle size diverges. When the counterions are large, however, steric and short-range electrostatic interactions prevent charge neutralization of the bundle, thus forcing the equilibrium bundle size to be finite. We also show that if the attractive interactions between the rods become frustrated as the bundle grows, finite-size bundles can be obtained with pointlike counterions.

Journal Article↗

Scaling theory of polyelectrolyte adsorption on a repulsive charged surface.

We studied the problem of many-polyelectrolyte adsorption on a repulsive charged surface by scaling analysis. According to ratio of the dielectric constant between the medium and the substrate, the phase diagrams of the adsorbed layer are divided into two classes. Their phase diagrams are qualitatively different. The polyelectrolytes of low (high) f Z2 are adsorbed for low (high) dielectric ratio, where f is the fraction of charged monomers and Z is the polyelectrolyte valency.

Journal Article↗

Nonlinear elasticity of single collapsed polyelectrolytes.

Nonlinear elastic responses of short and stiff polyelectrolytes are investigated by dynamic simulations on a single-molecule level. When a polyelectrolyte condensate undergoes a mechanical unfolding, two types of force-extension curves--i.e., a force plateau and a stick-release pattern--are observed depending on the strength of the electrostatic interaction. We provide a physical interpretation of such force-extension behavior in terms of intramolecular structures of the condensates. We also describe charge distributions of counterions condensed onto a polyelectrolyte, which clarify formation of one-dimensional strongly correlated liquid at large Coulomb coupling regime. These findings may provide significant insights into the relationship between a molecular elasticity and a molecular mechanism of like-charge attractions observed in a wide range of charged biopolymer systems.

Journal Article↗

Self-consistent field theory of protein adsorption in a non-Gaussian polyelectrolyte brush.

To describe adsorption of globular protein molecules in a polyelectrolyte brush we use the strong-stretching approximation of the Edwards self-consistent field equation, combined with corrections for a non-Gaussian brush. To describe chemical potentials in this mixture of (globular) species of widely varying sizes (ions, brush polyelectrolyte segments, globular protein molecules), we use the Boublik-Mansoori-Carnahan-Starling-Leland equation of state derived for polydisperse mixtures of spherical particles. The polyelectrolyte chain is described in this approach as a string of beads with the beads of a size related to the chain diameter. We use the one-dimensional Poisson equation to describe the electrostatic field and include the ionizable character of both the brush polyions and the protein molecules. This model explains the experimental observation of high amounts of protein adsorption in a polyacid brush for values above the isoelectric point of the protein as being due to charge reversal of the protein molecules upon entry in the brush. We find a distinct minimum in protein concentration near the edge of the brush. With increasing this barrier to protein transfer becomes larger, but much less so when we increase the ionic strength, a difference that might relate to an experimentally observed difference in the protein release rate in these two cases. A free energy analysis shows that the release of small ions from the brush and the increase of brush ionization are the two driving forces for protein adsorption in a like-charged brush.

Journal Article↗

Monte carlo study of coulombic criticality in polyelectrolytes.

The role of charges in determining the water solubility of polyelectrolytes, a question of considerable relevance to biology, is currently unresolved. We use computer simulations to study the purely Coulombic phase separation of flexible polyelectrolytes with monovalent counterions in an athermal solvent. In agreement with recent theories we find that the critical temperature for this transition increases with chain length, but that the critical density remains unchanged. We therefore stress that the phase behavior of polyelectrolytes is qualitatively different from uncharged polymers, where the critical density decreases towards zero for long chains.

Computer Simulation↗

Ion multivalence and like-charge polyelectrolyte attraction.

It is known empirically that multivalent ions generate attractions between like-charged polyelectrolytes, with different valence requirements for different systems. How multivalent must an ion be before it can condense a given polyelectrolyte? Using charge-tunable M13 virus rods and a family of artificial homologous "dumbbell" divalent ions of different sizes, we have constructed a multivalent ion-polyelectrolyte phase diagram, and find an experimentally motivated general criterion for like-charged attraction based on the ion valence, ion size, and the Gouy-Chapman length.

Anions↗

Counterion-mediated attraction and kinks on loops of semiflexible polyelectrolyte bundles.

The formation of kinks in a loop of bundled polyelectrolyte filaments is analyzed in terms of the thermal fluctuations of charge density due to polyvalent counterions adsorbed on the polyelectrolyte filaments. It is found that the counterion-mediated attraction energy of filaments depends on their bending. By consideration of curvature elasticity energy and counterion-mediated attraction between polyelectrolyte filaments, the characteristic width of the kink and the number of kinks per loop is found to be in reasonable agreement with existing experimental data for rings of bundled actin filaments.

Actin Cytoskeleton↗

Cationic polyelectrolytes, liquoid and leukocyte extract modulate the binding of IgG to group A streptococcal Fc-receptors.

Various polyelectrolytes were investigated regarding their capacity to inhibit the binding of human IgG to Fc-receptors on group A streptococci, type M1. Of cationic substances, protamine and arginine-rich histone inhibited significantly, while lysine-rich histone, concanavalin A, lysozyme, polymyxin B, ribonuclease and tuftsin did not. Of anionic materials, liquoid was inhibitory, in contrast to chondroitin sulphate, dextran sulphate, DNA and heparin. Washing experiments showed that the inhibition was caused by binding of the polyelectrolytes to the streptococci. The finding that heated IgG inhibited the binding of histone to the streptococci also indicated a close relation between the binding sites for these compounds. Diffusion-in-gel experiments with alkaline extract of M1 demonstrated that the substances blocking the IgG Fc-receptor were bound to polyglycerophosphate, suggesting that the inhibition of the IgG uptake was due to interaction with lipoteichoic acid. Leukocyte and platelet extracts could modify the binding of IgG, probably by an enzymatic digestion of the receptors. The arginine-rich histone was also capable of inhibiting the binding of IgG to type M15 group A streptococci and to one group G strain. However, the polyelectrolytes had no effect on the binding of IgG to Staphylococcus aureus or of IgA to type 4 group A streptococci.

Anions↗

Algal flocculation with synthetic organic polyelectrolytes.

The feasibility of removing algae from water and wastewater by chemical flocculation techniques was investigated. Mixed cultures of algae were obtained from both continuous- and batch-fed laboratory reactors. Representative cationic, anionic, and nonionic synthetic organic polyelectrolytes were used as flocculants. Under the experimental conditions, chemically induced algal flocculation occurred with the addition of cationic polyelectrolyte, but not with anionic or nonionic polymers, although attachment of all polyelectrolyte species to the algal surface is shown. The mechanism of chemically induced algal flocculation is interpreted in terms of bridging phenomena between the discrete algal cells and the linearly extended polymer chains, forming a three-dimensional matrix that is capable of subsiding under quiescent conditions. The degree of flocculation is shown to be a direct function of the extent of polymer coverage of the active sites on the algal surface, although to induce flocculation by this method requires that the algal surface charge must concurrently be reduced to a level at which the extended polymers can bridge the minimal distance of separation imposed by electrostatic repulsion. The influence of pH, algal concentration, and algal growth phase on the requisite cationic flocculant dose is also reported.

Amides↗

Concentration and purification of influenza virus on insoluble polyelectrolytes.

A method for rapid concentration and purification of influenza virus by adsorption on and elution from an insoluble polyelectrolyte is described. To accomplish this task, influenza virus had to be rendered stable at pH 4 to 5, since viruses adsorb to the polyelectrolyte more efficiently at this pH range. A precipitate which forms in influenza harvests under acid conditions in the cold can be removed by ammonium sulfate at a concentration which traps the precipitate but not the virus. Thus, ammonium sulfate-treated influenza virus in allantoic fluid could be readily concentrated on the polyelectrolyte. Elution yielded a virus concentrate essentially free of nonviral proteins.

Adsorption↗