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At least 19 recordsLinked to original sources
PubMed1989

Adhesion mechanism of polyelectrolyte cements to tooth structure--polyelectrolyte behavior of the cement polymers obtained by potentiometric titration in the presence of calcium ion.

Potentiomeric titration of aqueous solutions of polyacrylic acid and commercial polyelectrolyte cement polymers with sodium hydroxide solution was carried out in the presence of different concentrations of Ca2+. Polyelectrolytes all behave as weak acids without the coexisting Ca2+. However, in the presence of Ca2+, in amounts over one-half of the equivalent amount to the carboxyl group in the polymer, they have a strong acid-like behavior. This means that the carboxyl groups in the polymer chain tend to react strongly with coexisting Ca2+ as they are partially neutralized by the alkaline solution. This is also strong evidence supporting polyelectrolyte cement as an adhesion mechanism to tooth structure during cementation.

Acrylic Resins↗
PubMed1976

Polyelectrolyte effects in gel chromatography.

When polyelectrolytes (i.e., lignosulfonates) are eluted from Sepfected by steric exclusion, polyelectrolyte expansion, ion exclusion, and ion inclusion effects. The last-mentioned effect arises from the interaction of charged sites in the high-MW macroions, which are more or less excluded from the gel phase with charged sites in more permeable macroions. The ion inclusion effect depends on the counterion in such a way that the fractionation of polyelectrolytes with a univalent counterion is affected to a greater extent than is the fractionation of polyelectrolytes with a divalent counterion. This is attributable to the existence of a higher density of free charges in the former case, since univalent counterions have a lesser tendency to form ion pairs with the charged sites of the macroion than have divalent counter-ions. The ion inclusion effect may have a favorable influence on the resolution of components of relatively equal molar volume, but of different charge densities. Polyelectrolyte effects are suppressed if the elution is carried oe polyelectrolyte behaves as a nonionic polymer. However, since the separation effected by differences in charge densities is eliminated (swamped out), resolution may deteriorate; nevertheless, the fractionation order is independent of the composition of the sample, the concentration of sample solution, and other fractionation variables. If one wishes to acquire a general picture of the composition of a certain polyelectrolyte, a solution of a simple electrolyte may be the most appropriate eluent. However, if polyelectrolyte components with small differences in hydrodynamic volume are to be separated, an eluent comprising a solution of a high-MW polyelectrolyte, completely excluded by the gel (e.g., dextran sulfate), can be used.

Chemical Fractionation↗
PubMed1985

Chemiluminescence and superoxide generation by leukocytes stimulated by polyelectrolyte-opsonized bacteria. Role of histones, polyarginine, polylysine, polyhistidine, cytochalasins, and inflammatory exudates as modulators of oxygen burst.

Human blood leukocytes generate intense luminol-dependent chemiluminescence (LDCL) following stimulation by streptococci and by Gram negative rods which had been preopsonized by cationic polyelectrolytes (histone, poly L-arginine-PARG, poly L-histidine-PHSTD). Streptococci but not Gram negative rods or hyaluronic acid-rich streptococci (group C) also induced intense LDCL following opsonization with the anionic polyelectrolytes-dextran sulfate or polyanethole sulfonate (liquoid) suggesting that the outer surfaces of different bacteria bound anionic polyelectrolytes to different extents. Both normal and immune serum, synovial fluids and pooled human saliva inhibited the LDCL responses induced by streptococci preopsonized with poly cations. On the other hand, bacteria which had been first preopsonized by the various body fluids and then subjected to a second opsonization by cationic ligands ("sandwiches"), induced a very intense LDCL response in leukocytes. Streptococci which had been preopsonized by PARG, histone or by PHSTD also triggered superoxide generation by blood leukocytes, which was markedly enhanced by a series of cytochalasins. PHSTD alone induced the formation of very large amounts of superoxide. Paradoxically, the same concentrations of cytochalasins B or C which markedly boosted the generation of superoxide following stimulation of leukocytes with soluble or particulate ligands, had a strong inhibitory effect on the generation of LDCL. On the other hand cycochalasins failed to inhibit LDCL which had been induced by phorbol myristate acetate (PMA). Peritoneal macrophages which had been harvested from C. parvum-stimulated mice, generated more LDCL and superoxide following stimulation by PARG than macrophages obtained from proteose peptone-stimulated mice. Macrophages which had been activated either by proteose peptone or by C. parvum and cultivated for 2 hours on teflon surfaces, generated much more LDCL than macrophages which had been cultivated for 24 hours on teflon surfaces. Both cationic and anionic polyelectrolytes mimic the effects of antibodies as activators of the oxygen burst in blood leukocytes and in macrophages. Such polyelectrolytes can serve as models to further study leukocyte-bacteria interactions in infectious and inflammatory sites.

Adult↗
PubMed1991

Polyelectrolyte effects on 9-aminoacridine-DNA binding.

The 9-aminoacridine-DNA binding curve is analyzed in two ways: with polyelectrolyte effects neglected and with polyelectrolyte effects included. It is found that the analysis which includes polyelectrolyte effects is consistent with the violation of neighbor exclusion displayed by diacridine complexes as observed by Atwell et al. and by Zimmerman and coworkers. However the analysis which neglects polyelectrolyte effects is inconsistent with the diacridine results. This comparison supports the necessity of including polyelectrolyte effects in the analysis of drug-DNA binding curves.

Aminacrine↗
PubMed1977

Limiting laws and counterion condensation in polyelectrolyte solutions. IV. The approach to the limit and the extraordinary stability of the charge fraction.

The limiting laws for polyelectrolyte solutions developed in previous papers of this series have been amply confirmed by measurement. A surprising result of the accumulated data is that the limiting polyelectrolyte charge fraction (fraction of fixed charges uncompensated by condensed counterions in the limit of zero concentration), persists up to concentrations of 0.1 M or even higher. Here the theory is extended in a simple manner to finite concentrations, and the stability of the charge fraction is found to be firmly based on consequences of the long-range polyelectrolyte field. The associated counterions are assumed to translate freely in a region centered on the contour axis of the polyion. The numerical value of the free volume is determined self-consistently from the axial charge density of the polyelectrolyte and is used as the general framework within which specific binding effects are treated.

Calcium Chloride↗
PubMed1989

Cationic polyelectrolytes: potent opsonic agents which activate the respiratory burst in leukocytes.

Bacteria and yeasts which are "opsonized" with cationic polyelectrolytes (poly-L-arginine, poly-L-histidine and arginine-rich histone) are avidly endocytosed by both "professional" and "non-professional" phagocytes. The cationized particles also strongly activate the respiratory burst in neutrophils and in macrophages leading to the generation of chemiluminescence, superoxide and hydrogen peroxide. On the other hand, lysine and ornithine-rich polymers are poor opsonic agents. Poly L-arginine is unique in its capacity to act synergistically with lectins, with chemotactic peptides and with cytochalasin B to generate large amounts of chemiluminescence and superoxide in human neutrophils. Unlike polyarginine, polyhistidine, in the absence of carrier particles, is one of the most potent stimulators of superoxide generations, known. Neutrophils treated with cetyltrimethylammonium bromide fail to generate superoxide, but generate strong luminol-dependent chemiluminescence which is totally inhibited by sodium azide and by thiourea. Neutrophils injured by cytolytic agents (saponin, digitonin, lysolecithin) lose their chemiluminescence and superoxide-generating capacities upon stimulation by a variety of ligands. These activities are however regained by the addition of NADPH. Lysolecithin can replace polyarginine in a "cocktail" also containing lectins and cytochalasin B, which strongly activate the respiratory burst. This suggests that polyarginine acts both as a cytolytic agent and as a ligand. Arginine and histidine-rich polyelectrolytes enhance the pathogenic effects of immune complexes in vivo (reversed Arthus phenomenon) presumably by "glueing" them to tissues. Polyhistidine complexed to catalase or to superoxide dismutase, markedly enhances their efficiency as antioxidants. On the other hand polyhistidine complexed to glucose oxidase markedly enhances injury to endothelial cells suggesting that the close association of the cationized enzyme with the plasma membrane facilitates the interaction of hydrogen peroxide with the targets. A variety of cationic agents (histone, polyarginine, polyhistidine, polymyxin B) and membrane-active agents (lysophosphatides, microbial hemolysins) act synergistically with glucose oxidase or with reagent hydrogen peroxide to kill target cells. The mechanisms by which arginine- and histidine-rich polyelectrolytes activate the respiratory burst in neutrophils might involve interaction with G-proteins, the activation of arachidonic acid metabolism and phospholipase A2, or the interaction with myeloperoxidase. Naturally-occurring cationic proteins might modulate several important functions of leukocytes and the course and outcome of the inflammatory process.

Animals↗
PubMed1986

Phenotype correction of Ir-genic control of immune response to (T,G)-A-L conjugated to synthetic polyelectrolytes.

Experiments in CBA (H-2k) and C57BL/6 (H-2b) strains of mice have shown (T,G)-A-L covalently bound to synthetic polyelectrolytes possessing immunoadjuvant effect to induce a pronounced antibody and cell-mediated immune response irrespective of murine genotype. When conjugated to the polyelectrolytes (T,G)-A-L was also found to acquire the properties of a highly immunogenic thymus-independent antigen. Thus, (T,G)-A-L-synthetic polyelectrolytes conjugates manifested the effects of highly immunogenic thymus-independent antigens inducing a potent Ir-1-independent immune response. It provided for the transformation of genetically low responder individuals into high responder ones.

Animals↗
PubMed1991

Polyelectrolytes at the endothelial cell surface.

It is recalled that the tension in a stretched polyelectrolyte chain mechanically compensates both the coulomb interaction and the hydrostatic pressure increase around the chain in a compromise which minimises the free energy and keeps water chemical potential constant throughout. Stretching strongly favors parallel cylinder nematic order in polyelectrolyte brushes on a surface or in the slit between two surfaces when the polyelectrolyte chains function as bridges. Strong, stiffly stretched chains result when the molarity of the fixed charge distribution is larger than the molarity of the neutral salt solution with which the brushes are in equilibrium. The relevance of these two systems to the endothelial cells which cover the walls of blood vessels is discussed.

Cell Membrane↗
PubMed1972

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↗
PubMed1985

Persistence of staphylococcal cell-wall components in inflammatory sites may be due to the modulation by sulphated polyelectrolytes of autolytic wall enzymes: a working hypothesis.

The interaction of leucocytes with Staphylococcus aureus results in killing of the bacterial cells, but large portions of the bacterial cell walls persist apparently phagocytic cells for long periods. The mechanisms of biodegradation of staphylococci by leucocyte factors have shown that degradation of cell walls in vitro may be the result of the activation, by leucocyte kationic proteins, of the bacterial autolytic wall enzymes that are responsible for degrading the cell walls from within. This process is markedly inhibited by sulphated polysaccharides like dextran sulphate, by heparin, or by polyanetholesulfonate (liquoid). These anionic polyelectrolytes have also been shown to inhibit the lysis of staphylococci treated with bacteriolytic concentrations of penicillin G. Staphylococci injected intraarticularly into the knee joint of rats underwent massive plasmolysis, but structures compatible with cell walls (peptidoglycan) persisted within macrophages in the inflammatory sites, for long periods. It is postulated that the inability of leucocytes to degrade staphylococcal cell-wall components may be the result of the interference, by anionic polyelectrolytes likely to accumulate in the inflammatory sites, with the activation of the autolytic systems. Alternatively, anionic polyelectrolytes may coat the bacterial cells and interfere with the binding of the autolytic enzymes with their corresponding substrates.

Animals↗
PubMed1985

Novel method for the preparation of controlled-release theophylline granules coated with a polyelectrolyte complex of sodium polyphosphate-chitosan.

A novel method for the preparation of theophylline granules coated with a polyelectrolyte complex of sodium tripolyphosphate and chitosan was developed. The theophylline granules containing sodium tripolyphosphate were stirred in an HCl solution of chitosan. During the mixing, the dissolved sodium tripolyphosphate in the granule moved to the surface and reacted with the chitosan, resulting in the formation of the polyelectrolyte complex film. The factors affecting the drug content, the particle size, and the coating-film thickness of the resultant coated granules were determined. The theophylline content in the coated granule decreased with increasing content ratio of sodium tripolyphosphate to theophylline in the original granule and with increasing chitosan concentration in the coating solution. The coated granule size increased with increasing chitosan concentration in the coating solution and with decreasing agitation speed. The coating-film thickness increased with an increase in the chitosan concentration, the pH of the coating solution, and the sodium tripolyphosphate to theophylline content ratio in the original granule. The drug-release pattern of the coated granules followed zero-order kinetics and the release rates were significantly reduced compared with that of the original granule.

Chemical Phenomena↗
PubMed1977

Dynamic properties of polyelectrolyte calcium membranes.

Shashoua observed spontaneous oscillations in a polyelectrolyte membrane formed by interfacial precipitates of polyacid and polybase. We have here undertaken experimental and theoretical studies of polyglutamic acid-Ca++ membrane in order to clarify the processes involved in this dynamic behavior. We find a region of distinct hysteresis in the voltage current curve for this system. A sharp transition from a state of low membrane resistance to one of high resistance occurs at a current density different from that of inverse transition. This membrane system is modeled as a two layer structure: a negatively charged layer alpha made of ionized polyelectrolyte in series with a neutral region beta in which the polymeric ionic sites are masked by calcium ion. This structure results in a difference in the transference number for the mobile ions, causing salt accumulation at the interfacial region during a current flow in the alpha to beta direction. This altered salt concentration induces a change of polymeric conformation, which in turn affects the membrane permeability and the rate of accumulation. Based upon nonequilibrium thermodynamic flow equations, and a two-state representation of membrane macromolecular conformation, this model displays a region of hysteresis in the current range of experimental observations.

Calcium↗
PubMed1987

Acetylcholinesterase as polyelectrolyte in reaction with cationic substrates.

It is shown that the salt effect in acetylcholinesterase-catalyzed hydrolysis of 2-(N-methylmorpholinium)-ethylacetate can be quantitatively described by the equation log(k2/KS) = log(k2/KS) degrees--psi log[M+Z] following from Manning's polyelectrolyte theory; the psi values for salts with univalent and bivalent cations at different pH values of the reaction medium were in accordance with the conclusions of the theory. Manning's polyelectrolyte theory seems to be a useful framework for studying salt effects in the reactions of charged substrates with enzymes as globular polyions.

Acetylcholinesterase↗
PubMed1990

Conformational transition and polyelectrolyte behaviour of a succinoglycan polysaccharide.

We report the chemical characterization and the relationship between the physicochemical properties and conformational change of a succinoglycan polysaccharide produced by Pseudomonas sp, NCIB 11592. The expected chemical structure is confirmed, with a ratio of D-glucose: D-galactose: pyruvate: succinate of 7:1:1:1. The molecular weight of the native form is 4.2 x 10(6) but after a single heating cycle through the disordered state the molecular weight is reduced to 3.0 x 10(6). The polymer has a polymolecularity index of 1.3 in both cases. The conformational change was studied by different methods which enabled us to define the exact nature of the ordered and disordered states. The conformational transition depends on the temperature, the ionic strength and the nature of the counterion. The polyelectrolyte behaviour is in favour of a single chain conformation with an intramolecular helix-coil transition. The enthalpy change during this transition is greater than that expected solely on the basis of the polyelectrolyte contribution. It may be associated with changes in solvation or a rearrangement of water molecules in close association with the polymer.

Calcium Chloride↗
PubMed1991

Solution and gelling properties of polysaccharide polyelectrolytes.

Attention is focussed on the special class of polysaccharide polyelectrolytes belonging to the family of the microbial polysaccharides. But a few exceptions, these are high molecular weight water- soluble polycarboxylates with complex, regular structures. Complexity and regularity in primary structure--two features normally not shared by other polysaccharides of either vegetal or animal origin--quite naturally entail unique conformational propensities, special physico-chemical properties in bulk and in solution and, as a consequence, make these biopolymers of particular interest from both a basic research and an industrial standpoint. What is outlined in this presentation should demonstrate that for many exocellular microbial polycarboxylates the solution properties are, as expected, dictated by the conformation assumed by the polyelectrolytic chains which, in turn, are governed by several free energy terms in particular stemming from specific solvent-chain interactions, among which the coulombic contribution may play a minor role.

Circular Dichroism↗
PubMed1988

The use of polyelectrolytes as osmotic agents for peritoneal dialysis.

Various small and large molecules have been studied as osmotic agents to replace dextrose in peritoneal dialysis. Macromolecules are attractive because of their slow absorption from intraperitoneal solutions; however, it has been assumed that they are only marginally effective as osmotic agents unless they function as polyelectrolytes at physiological pH. In experimental exchanges conducted in rats we measured volume changes induced by Gelifundol (5.5% oxypolygelatin) and Ringers lactate to which was added either nothing, 4.25% dextrose, or 5% albumin. In the control exchanges using Ringers lactate, intraperitoneal fluid volume remained unchanged for eight hours. The volume changes induced by 4.25% dextrose were complete within two hours and resulted in a two-thirds increase over the amount of fluid administered. In both series in which polyelectrolytes were used volume transport was sustained throughout an eight hour dwell. With 5% albumin the total increase in fluid volume was about 40% of that installed, while Gelifundol caused fluid volume to double. Qualitatively similar results were obtained in transport studies conducted in vitro. Physical studies of the oxypolygelatin solutions indicated that the fixed charges per liter were comparable to those in the albumin solutions. Thus the different volume transport the two proteins induced could not be attributed to Donnan effects. However, since the molecular weight of albumin is triple that of Gelifundol the van't Hoff pressures of the two macromolecules can explain the observed differences in volume transport. These results suggest that neutral macromolecules deserve further study as potential osmotic agents for peritoneal dialysis.

Albumins↗
PubMed1988

Poliovirus retention in soil columns after application of chemical- and polyelectrolyte-conditioned dewatered sludges.

The transport of poliovirus type 1 (strain LSc) was studied in Red Bay sandy loam columns that were treated with chemical- or polyelectrolyte-conditioned dewatered sludges and then leached with natural rainwater under saturated flow conditions. Poliovirus was concentrated in the alum and ferric chloride sludges that were produced following the flocculation of virus-seeded raw sewage. Virtually complete inactivation of the virus was observed following the flocculation of raw sewage or the stabilization of alum and ferric chloride sludges with lime at pH 11.5. Poliovirus was also concentrated in polyelectrolyte-conditioned dewatered sludge that was produced from virus-seeded, anaerobically digested sludge. Despite the saturated flow conditions for a sustained period, no viruses were detected in the leachates of the soil columns that were treated with these chemical and chemically treated sludges. Since the viruses were mostly associated with the solids in these sludge samples, it is believed that they were immobilized along with the sludge solids in the top portion of the soil columns.

Hydrogen-Ion Concentration↗