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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 A. 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 x 10(-5) M ) 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.

Journal Article↗

2H NMR and polyelectrolyte-induced domains in lipid bilayers.

2H NMR studies of polyelectrolyte-induced domain formation in lipid bilayer membranes are reviewed. The 2H NMR spectrum of choline-deuterated phosphatidylcholine (PC) reports on any and all sources of lipid bilayer surface charge, since these produce a conformation change in the choline head group of PC, manifest as a change in the 2H NMR quadrupolar splitting. In addition, homogeneous and inhomogeneous surface charge distributions are differentiated. Adding polyelectrolytes to lipid bilayers consisting of mixtures of oppositely charged and zwitterionic lipids produces 2H NMR spectra which are superpositions of two Pake sub-spectra: one corresponding to a polyelectrolyte-bound lipid population and the other to a polyelectrolyte-free lipid population. Quantitative analysis of the quadrupolar splittings and spectral intensities of the two sub-spectra indicate that the polyelectrolyte-bound populations is enriched with oppositely charged lipid, while the polyelectrolyte-free lipid population is correspondingly depleted. The same domain-segregation effect is produced whether cationic polyelectrolytes are added to anionic lipid bilayers or anionic polyelectrolytes are added to cationic lipid bilayers. The 2H NMR spectra permit a complete characterization of domain composition and size. The anion:cation ratio within the domains is always stoichiometric, as expected for a process driven by Coulombic interactions. The zwitterionic lipid content of the domains is always statistical, reflecting the systems tendency to minimize the entropic cost of demixing charged lipids into domains. Domain formation is observed even with rather short polyelectrolytes, suggesting that individual polyelectrolyte chains aggregate at the surface to form "superdomains". Overall, the polyelectrolyte bound at the lipid bilayer surface appears to lie flat along the surface and to be essentially immobilized through its multiple electrostatic contacts.

Antigens, Polyomavirus Transforming↗

Domains in cationic lipid plus polyelectrolyte bilayer membranes: detection and characterization via 2H nuclear magnetic resonance.

2H nuclear magnetic resonance (NMR) spectroscopy of choline-deuterolabeled 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC-alpha-d2 and POPC-beta-d2) has been used to detect and quantify domain formation induced in cationic lipid-containing bilayers upon the addition of anionic polyelectrolytes. Three different polyelectrolytes, poly(sodium 4-styrenesulfonate) or PSSS, poly(sodium acrylate) or PACA, and poly(sodium glutamate) or PGLU, were added to POPC lipid bilayers containing 1,2-dioleoyl-3-(dimethylamino)propane (DODAP) as the cationic amphiphile. All three polyelectrolytes produced two-component 2H NMR spectra, consistent with two populations of POPC, one polyelectrolyte-bound and another polyelectrolyte-free. The relative intensities of the two spectral components provided the relative amounts of the two POPC populations. The 2H NMR quadrupolar splitting from either spectral component provided the DODAP content of the particular POPC population. The two POPC populations differed in that the polyelectrolyte-bound population contained a stoichiometric polyelectrolyte anion:DODAP cation ratio leading to enrichment with respect to DODAP, while the polyelectrolyte-free population was depleted of DODAP. Estimates of the size of a polyelectrolyte-defined domain revealed a constant number of bound DODAP but a flexible number of bound POPC, which increased in proportion to the global POPC content. The most compact domains were formed by the most hydrophobic polyelectrolyte, PSSS, while the most expansive domains were formed by the most hydrophilic polyelectrolyte, PGLU.

Acrylates↗

A Monte Carlo study of spherical electrical double layer of macroions-polyelectrolytes systems in salt free solutions.

A canonical Monte Carlo simulation is performed to investigate the microstructure and the electrical double layer (EDL) of polyelectrolytes around macroions in the bulk systems based on the primitive model. We explore the influences of particles size, chain length, and charge density of polyelectrolytes on the microscopic behavior of the macroions-polyelectrolytes systems. The simulation results show that the surface charge density and the chain length of the polyelectrolytes are two key factors that affect the microstructure of polyelectrolytes around the macroions and potential of mean force between the macroions as well as the zeta potential of the spherical EDL constructed by polyelectrolytes. The high surface charge density of a polyelectrolyte leads to the polyelectrolyte acting as a bridge for the aggregation of macroions, causing the presence of the attraction between macroions. The polyelectrolytes with a long chain length present a cooperativity effect for the adsorption of the polyelectrolytes on the surface of the macroions. Furthermore, the two key factors both induce the overcharge of the macroions. The longer the chain length and the higher surface charge density of the polyelectrolytes, the stronger is the overcharge.

Electrolytes↗

Electrosteric Stabilization of Al(2)O(3), ZrO(2), and 3Y-ZrO(2) Suspensions: Effect of Dissociation and Type of Polyelectrolyte.

The mechanisms of eight anionic polyelectrolytes stabilizing colloidal sized alpha-Al(2)O(3), pure ZrO(2), and Y(2)O(3)-doped ZrO(2) particles in aqueous solution are discussed. The polyelectrolytes studied were the Na(+) and NH(4)(+) salts of polyacrylic acid and polymethacrylic acid having different molecular weights. The particle-dispersant interactions were studied by measuring adsorption isotherms, particle size, thickness of adsorbed layer, and zeta potentials by elektrokinetic sonic analysis at different powder volume fractions (straight phi=0.01-0.3), pH, and electrolyte (KCl) content. The dissociation of the polyelectrolytes was studied by potentiometric titrations. The dissociation constant of the polymethacrylates was found to be 0.6 pH unit higher than that for the polyacrylates. High-affinity adsorption isotherms were observed over the pH range when the polyelectrolytes were fully ionized. The results show good correlation between adsorption isotherms and zeta potential data in systems of dispersed, dilute alumina particles. When particles and polymers were of equal charge (the same sign of charge) the polymer shell was thicker. At higher volume fractions (straight phi=0.3), and when alumina particles/added ammonium polyelectrolyte were of equal charge, a maximum in the absolute value of zeta potential resulted. Due to adsorption all the anionic polyelectrolytes studied provided electrosteric stabilization of the alpha-Al(2)O(3), and Y(2)O(3)-doped ZrO(2) suspensions by enhancing the zeta potential to 40 mV or over and by shifting the isoelectric point to lower pH, the low-molecular-weight polyelectrolytes decreasing the isoelectric point more than the polyelectrolytes having higher molecular weight. The polyelectrolytes studied failed to stabilize pure monoclinic ZrO(2) particles. Due to the shortness of the chain of polyelectrolytes studied, no bridging was observed between oppositely charged polyelectrolyte/alumina particles. Copyright 2000 Academic Press.

Journal Article↗

Polyelectrolytes as adhesion modifiers.

Adsorbed layers of polyelectrolytes have been studied with atomic force microscopy (AFM) and the interferometric surface force apparatus (SFA). Particular emphasis was put on determining the effect of the polyelectrolyte charge density on surface topography, and the effect of the polyelectrolyte coating on the adhesive properties. The AFM was employed to image individual polymer chains at low adsorption densities and to characterize the layer topography and coverage at higher adsorption densities. The adhesive properties between two polyelectrolyte-coated surfaces in air were determined as a function of the number of contacts made at any given spot. The data provide evidence for formation of electrostatic bridges, particularly when highly charged polyelectrolytes are used. Further, material transport between the surfaces is observed when the polyelectrolyte is either highly charged or have a very low charge density. For intermediate charge densities we could not observe any indication of material transfer. The adhesion between one polyelectrolyte-coated surface and one bare surface was initially higher than that between two polyelectrolyte-coated surfaces. However, due to material transfer between the two surfaces the adhesion decreased significantly with the number of times that the surfaces were driven into contact. For the polyelectrolytes of the lowest charge density the results suggest that entanglement effects contribute to the adhesive interaction. The modification of the adhesion by polyelectrolytes in practical systems such as in the case of dry-strength additives to improve paper resistance is also considered.

Adsorption↗

Molecular dynamics simulations of polyelectrolyte-polyampholyte complexes. Effect of solvent quality and salt concentration.

Complexation between polyelectrolyte and polyampholyte chains in poor solvent conditions for the polyelectrolyte backbone has been studied by molecular dynamics simulations. In a poor solvent a polyelectrolyte forms a necklace-like structure consisting of polymeric globules (beads) connected by strings of monomers. The simulation results can be explained by assuming the existence of two different mechanisms leading to the necklace formation. In the case of weak electrostatic interactions, the necklace formation is driven by optimization of short-range monomer-monomer attraction and electrostatic repulsion between charged monomers on the polymer backbone. In the case of strong electrostatic interactions, the necklace structure appears as a result of counterion condensation. While the short-range attractions between monomers are still important, the correlation-induced attraction between condensed counterions and charged monomers and electrostatic repulsion between uncompensated charges provide significant contribution to optimization of the necklace structure. Upon forming a complex with both random and diblock polyampholytes, a polyelectrolyte chain changes its necklace conformation by forming one huge bead. The collapse of the polyelectrolyte chain occurs due to the neutralization of the polyelectrolyte charge by polyampholytes. In the case of the random polyampholyte, the more positively charged sections of the chain mix with negatively charged polyelectrolyte forming the globular bead while more negatively charged chain sections form loops surrounding the collapsed core of the aggregate. In the case of diblock polyampholyte, the positively charged block, a part of the negatively charged block, and a polyelectrolyte chain form a core of the aggregate with a substantial section of the negatively charged block sticking out from the collapsed core of the aggregate. In both cases the core of the aggregate has a layered structure that is characterized by the variations in the excess of concentration of monomers belonging to polyampholyte and polyelectrolyte chains throughout the core radius. These structures appear as a result of optimization of the net electrostatic energy of the complex and short-range attractive interactions between monomers of the polyelectrolyte chain.

Computer Simulation↗

Human serum albumin self-assembly on weak polyelectrolyte multilayer films structurally modified by pH changes.

Adsorption of proteins onto film surfaces built up layer by layer from oppositely charged polyelectrolytes is a complex phenomenon, governed by electrostatic forces, hydrogen bonds, and hydrophobic interactions. The amounts of the interacting charges, however, both in polyelectrolytes and in proteins adsorbed on such films are a function of the pH of the solution. In addition, the number and the accessibility of free charges in proteins depend on the secondary structure of the protein. The subtle interplay of all these factors determines the adsorption of the proteins onto the polyelectrolyte film surfaces. We investigated the effect of these parameters for polyelectrolyte films built up from weak "protein-like" polyelectrolytes (i.e., polypeptides), poly(L-lysine) (PLL), and poly(glutamic acid) (PGA) and for the adsorption of human serum albumin (HSA) onto these films in the pH range 3.0-10.5. It was found that the buildup of the polyelectrolyte films is not a simple function of the pure charges of the individual polyelectrolytes, as estimated from their respective pKa values. The adsorption of HSA onto (PLL/PGA)n films depended strongly on the polyelectrolyte terminating the film. For PLL-terminated polyelectrolyte films, at low pH, repulsion, as expected, is limiting the adsorption of HSA (having net positive charge below pH 4.6) since PLL is also positively charged here. At high pH values, an unexpected HSA uptake was found on the PGA-ending films, even when both PGA and HSA were negatively charged. It is suggested that the higher surface rugosity and the decrease of the alpha-helix content at basic pH values (making accessible certain charged groups of the protein for interactions with the polyelectrolyte film) could explain this behavior.

Absorption↗

The interaction of humic substances with cationic polyelectrolytes.

The anionic charge carried by aquatic humic substances plays a major part in their interaction with metal ions and other cationic species. Removal of such substances by coagulation and flocculation can be, at least partly, determined by charge neutralisation. In this work, the charge densities of a commercial humic acid and an aquatic humic extract have been investigated by studying their interactions with a series of synthetic cationic polyelectrolytes. These covered a range of charge densities and molecular weights. The techniques used were colloid titration by spectrophotometry and streaming current detection, and flocculation determined by colour removal and by an optical monitoring method. For a given cationic polyelectrolyte, all four methods gave charge densities for humic substances which were in good agreement. However, systematic differences in the apparent humic charge density were found, depending on the charge density of the cationic polyelectrolyte used. With low charge density polyelectrolytes, the apparent anionic charge of the humic substances was found to be low. With higher polyelectrolyte charge densities, the apparent humic substance charge density increases and reaches a limiting value when the polyelectrolyte charge is greater than about 3 meq/g. This indicates a non-stoichiometric interaction between the anionic sites of the humic substances and the cationic charges of the low-charge polyelectrolytes. Optimum flocculation of humics occurred with less cationic charge in the case of low-charge polyelectrolytes than those with higher charge density. However, the degree of removal was considerably better in the latter case. In all cases, the molecular weight of the cationic polyelectrolytes (over a range from about 50,000 to 15 million) appeared to have no effect on the results.

Cations↗

Nanoblossoms: light-induced conformational changes of cationic polyelectrolyte stars in the presence of multivalent counterions.

We analyze the structure of star-shaped polyelectrolytes in the presence of di- and trivalent counterions, and we use the gained knowledge to manipulate the polyelectrolyte's conformation by light. By applying dynamic light scattering and atomic force microscopy, we demonstrate that, at constant ionic strength, the arms of the cationic polyelectrolyte retract when adding multivalent counterions. Adding trivalent hexacyanocobaltate(III) ions leads to a collapse of the polyelectrolyte star even at low concentrations. This is shown by analysis of the star polyelectrolytes in solution as well as in the adsorbed state on mica surfaces. Considerably higher salt concentrations are necessary to obtain the same contraction of the polyelectrolyte star if the divalent tetracyanonickelate(II) ions are used. Sufficiently high multivalent counterion concentration leads finally to the precipitation of the polymer from the solution. We demonstrate that we can switch a polyelectrolyte star from the collapsed to the expanded state by transforming the trivalent hexacyanocobaltate(III) ions into a mixture of mono- and divalent ions by UV light. Thus, these collapsed stars react to light like "nanoblossoms". Moreover, polyelectrolyte stars precipitated through addition of the trivalent hexacyanocobaltate(III) ions can be redissolved by irradiation with light (photoinduced dissolution). Hence, the conformation and interaction of star polyelectrolytes can be switched by light. Possible applications of this novel way of manipulating polymers are discussed.

Cations↗

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↗

Inhibitory effect of polyelectrolytes on oligomeric enzymes.

The effect of polyelectrolytes on the stability and catalytic characteristics of oligomeric enzymes--pig muscle lactate dehydrogenase (LDH) and bovine liver glutamate dehydrogenase (GDH)--was studied by fluorescent spectroscopic and steady state kinetic methods. It was shown that the binding of negatively charged polyelectrolytes--polystyrene sulfonate, polymethacrylate, and polyphosphate--destroys the tertiary and partially the secondary structure of LDH and GDH, resulting in their complete inactivation at pH < 7. The concentrations of polyelectrolytes needed for inhibition of the enzymes were in this case by two or more orders of magnitude lower than the corresponding concentrations for monomers--toluene sulfonate, methacrylate, and phosphate. The affinity of the substrate (pyruvate) for LDH did not vary in the presence of the polyelectrolytes, but the inhibition was removed by excess of substrate. We propose that the oligomeric state of enzymes causes polyelectrolytes to act on them in a special manner, this special effect differing significantly from the effect of polyelectrolytes on monomeric enzymes. The effect consists in that polyelectrolytes cleave the oligomeric structure of the enzymes, this "cleaving" effect being higher the greater the hydrophobicity of the polyelectrolyte chain.

Animals↗

POLYELECTROLYTES AND THEIR BIOLOGICAL INTERACTIONS.

Polyelectrolytes are water-soluble electrically charged polymers. Their properties are determined by the interplay of the electrical forces, the Brownian motion of the macromolecular chain, and intermolecular Van der Waals forces. Charged polyacids or polybases are stretched by the electrostatic forces, as evidenced by increase in solution viscosity, or by the stretching of polyelectrolyte gels. The electrical field of the polyions is neutralized by a dense atmosphere of counter-ions. The counter-ion attraction to the polyions is expressed by a reduction of the osmotic activity of the polyion-the osmotic pressure being only 15 to 20 per cent of the ideal in highly charged polyelectrolytes neutralized by monovalent counter-ions, and as low as 1 to 3 per cent of the ideal for polyvalent counter-ions. Since the ionic atmosphere is only slightly dependent on added low molecular salt, the osmotic pressure of polyelectrolyte salt mixtures is approximately equal to the sum of the osmotic pressure of polyelectrolyte and salt alone. Acidic and basic polyelectrolytes interact electrostatically with precipitation at the point of polymeric electroneutrality. At higher salt concentrations the interaction is inhibited by the screening of polymeric fixed charges. The importance of these interactions in enzymatic processes is discussed. The electrical double layer is polarizable as may be deduced from dielectric and conductometric studies. The polarizability leads to strong dipole formation in an electrical field. These macromolecular dipoles may play a role in the adsorption of polyelectrolytes on charged surfaces. The final part of the paper is devoted to interactions of polyelectrolytes with cell membranes and the gluing of cells to higher aggregates by charged biocolloids.

Adsorption↗

Protein-polyelectrolyte cluster formation and redissolution: a Monte Carlo study.

Aqueous solutions of proteins and oppositely charged polyelectrolytes were studied at different polyelectrolyte chain length, ionic strength, and protein-protein interaction potential as a function of the polyelectrolyte concentration. One of the protein models used represented lysozyme in aqueous environment. The model systems were solved by Monte Carlo simulations, and their properties were analyzed in terms of radial distribution functions, structure factors, and cluster composition probabilities. In the system with the strongest electrostatic protein-polyelectrolyte interaction the largest clusters were formed near or at equivalent amount of net protein charge and polyelectrolyte charge, whereas in excess of polyelectrolyte a redissolution appeared. Shorter polyelectrolyte chains and increased ionic strength lead to weaker cluster formation. An inclusion of nonelectrostatic protein-protein attraction promoted the protein-polyelectrolyte cluster formation.

Cluster Analysis↗

Nanoparticle adsorption on a weak polyelectrolyte. Stiffness, pH, charge mobility, and ionic concentration effects investigated by Monte Carlo simulations.

Monte Carlo simulations have been used to study two different models for a weak linear polyelectrolyte in the presence of nanoparticles: (i) a rodlike and (ii) a flexible polyelectrolytes. The use of simulated annealing has made it possible to simulate a polyelectrolyte chain in the presence of several nanoparticles by improving conformation sampling and avoiding multiple minima problems when dense conformations are produced. Nanoparticle distributions along the polymer backbone were analyzed versus the ionic concentration, polyelectrolyte stiffness, and nanoparticle surface charge. Titration curves were calculated and the influences of the ionic concentration, solution pH, and number of adsorbed nanoparticles on the acid/base polyelectrolyte properties have been systematically investigated. The subtle balance of attractive and repulsive interactions has been discussed, and some characteristic conformations are presented. The comparison of the two limit models provides a good representation of the stiffness influence on the complex formation. In some conditions, overcharging was obtained and presented with respect to both the polyelectrolyte and nanoparticle as the central element. Finally, the charge mobility influence along the polyelectrolyte backbone was investigated by considering annealed and quenched polyelectrolyte chains.

Journal Article↗

Monte Carlo simulations of polyampholyte-polyelectrolyte complexes: effect of charge sequence and strength of electrostatic interactions.

We present the results of Monte Carlo simulations of complexation between polyampholyte and polyelectrolyte chains. Polymers are modeled as bead-spring chains of charged Lennard-Jones particles each consisting of 32 monomers. Formation of a polyampholyte-polyelectrolyte complex is driven by polarization-induced attractive interactions. The complex is usually formed at the end of the polyelectrolyte with the polyampholyte chain elongated and aligned along the polyelectrolyte backbone. This complex structure between the polarized polyampholyte chain and the polyelectrolyte leads to maximization of the attractive and minimization of the repulsive electrostatic interactions. The size of a polyampholyte in a complex is usually larger than that of an isolated polyampholyte chain. We also observed that initially collapsed polyampholytes undergo a coil-globule transition by forming a complex. The structure of a polyampholyte-polyelectrolyte complex was analyzed by tail and loop distribution functions. We have found that the number of loops increases while their sizes decrease with the strength of the electrostatic interactions. Polyampholytes with random charge sequence form stronger complexes with polyelectrolytes than those with alternating charge sequence. Polyampholytes with long blocky sequences form a double helix with a polyelectrolyte at sufficiently large values of the Bjerrum length.

Journal Article↗

Light scattering, CD, and ligand binding studies of ferrihemoglobin-polyelectrolyte complexes.

Quasi-elastic light scattering (QELS), electrophoretic light scattering (ELS), CD spectroscopy, and azide binding titrations were used to study the complexation at pH 6.8 between ferrihemoglobin and three polyelectrolytes that varied in charge density and sign. Both QELS and ELS show that the structure of the soluble complex formed between ferrihemoglobin and poly(diallyldimethylammonium chloride) [PDADMAC] varies with protein concentration. At fixed 1.0 mg/mL polyelectrolyte concentration, protein addition increases complex size and decreases complex mobility in a tightly correlated manner. At 1.0 mg/mL of greater protein concentration, a stable complex is formed between one polyelectrolyte chain and many protein molecules (i.e., an intrapolymer complex) with apparent diameter approximately 2.5 times that of the protein-free polyelectrolyte. Under conditions of excess polyelectrolyte, each of the three ferrihemoglobin-polyelectrolyte solutions exhibits a single diffusion mode in QELS, which indicates that all protein molecules are complexed. CD spectra suggest little or no structural disruption of ferrihemoglobin upon complexation. Azide binding to the ferrihemoglobin-poly(2-acrylamide-2-methylpropanesulfonate) [PAMPS] complex is substantially altered relative to the polyelectrolyte-free protein, but minimal change in induced by complexation with an AMPS-based copolymer of reduced linear charge density. The change in azide binding induced by PDADMAC is intermediate between that of PAMPS and its copolymer.

Animals↗