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Tsetska Radeva

Publications and source records attributed to Tsetska Radeva.

6 recordsLinked to original sources

Counterion release from adsorbed highly charged polyelectrolyte: an electrooptical study.

The adsorption of sodium poly(4-styrene sulfonate) on oppositely charged beta-FeOOH particles is studied by electrooptics. The focus of this paper is on the release of condensed counterions from adsorbed polyelectrolyte upon surface charge overcompensation. The fraction of condensed Na+ counterions on the adsorbed polyion surface is estimated according to the theory of Sens and Joanny and it is compared with the fraction of condensed counterions on nonadsorbed polyelectrolyte. The relaxation frequency of the electrooptical effect from the polymer-coated particle is found to depend on the polyelectrolyte molecular weight. This is attributed to polarization of the layer from condensed counterions on the polyion surface, being responsible for creation of the effect from particles covered with highly charged polyelectrolyte. The number of the adsorbed chains is calculated also assuming counterion condensation on the adsorbed polyelectrolyte and semiquantative agreement is found with the result obtained from the condensed counterion polarizability of the polymer-coated particle. Our findings are in line with theoretical predictions that the fraction of condensed counterions remains unchanged due to the adsorption of highly charged polyelectrolyte onto weakly charged substrate.

Journal Article↗

Formation of polyelectrolyte multilayers from polysaccharides at low ionic strength.

Layer-by-layer deposition of sodium carboxymethylcellulose (NaCMC) and chitosan (CHI) was used to create polyelectrolyte multilayers on ellipsoidal beta-FeOOH particles at low ionic strength. Using electro-optics, we investigated the formation of films in dependence on the polyelectrolyte charge density by controlling pH of the dipping solutions. We found out a linear growth of the CMC/CHI films when they are constructed from highly charged CHI (at pH 4.0) and weakly charged NaCMC (at pH 4.0 and 5.5). The hydrodynamic thickness of the film constructed at pH 4.0/4.0 is unusually large for a linearly growing film (ca. 220 nm after deposition of 8 bilayers), but it strongly decreases (ca. 4 times) with increasing ionization of NaCMC (at pH 5.5). In both cases, the multilayer buildup proceeded through a series of adsorption-desorption steps. This was explained by a partial loss of CHI from the film surface on exposure to the solution of longer NaCMC molecules. The irregular film growth correlated quite well with the variations in the electrical polarizability of the polymer-coated particles. This correlation enabled us to conclude that the adsorption of both polymers occurs only on the film surface, with no diffusion in and out of the film bulk during deposition of each CMC/CHI bilayer.

Adsorption↗

Electro-optics of colloid-polyelectrolyte complexes: counterion release from adsorbed macromolecules.

Complexation between sodium carboxymethylcellulose (NaCMC) and ellipsoidal particles of oppositely charged beta-FeOOH is studied using electric light scattering and electrophoresis. We focus on the complex behavior for overcharging of the particle surface. In this case, the fraction of condensed counterions on NaCMC is found to remain unchanged during polymer adsorption onto a weakly charged particle surface. Using the theory of Sens and Joanny, we evaluate the fraction of condensed counterions and compare it with results for nonadsorbed NaCMC. The polarization of condensed counterions along the chain of the adsorbed macromolecule is proved to create the electro-optical effect in suspensions stabilized by NaCMC adsorption.

Journal Article↗

In situ determination of thickness and electrical properties of multilayers from weak polyelectrolytes.

An electro-optical study of the role that the outermost layer plays in the behavior of a multilayer film of the weak polyelectrolytes poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) was carried out. The film surface was enriched with the chains of the last adsorbed polyelectrolyte when a fully ionized polymer was combined with nearly fully charged chains of the other polyelectrolyte. A distinct influence of the chain length on the critical frequency of relaxation of the electro-optical effect was demonstrated, indicating that polarization of condensed counterions of the last adsorbed polymer governs the behavior of the whole film. The multilayer growth, which was found to proceed via a series of adsorption-desorption steps, correlated well with the changes in the electro-optical effect. No indication was found, however, for participation of small ions from the film bulk in creation of the electro-optical effect.

Journal Article↗

Electrical properties of multilayers from low- and high-molecular-weight polyelectrolytes.

The formation of stable multilayer films by using as constituents sodium poly(4-styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (PVP) was studied by electrooptics. A strong increase in basicity of the pyridine rings in the electrical field of the oppositely charged PSS chains was suggested to be the driving force for multilayer film formation. A linear increase in the film thickness was registered after deposition of the first three layers, with no dependence on the polyelectrolyte molecular weight. The electrooptical effect was found to increase with increasing area of each next layer, but depended on the molecular weights of both polymers. Polarization of "condensed" counterions along the chains of the last-adsorbed layer was suggested to explain this dependence. Following the counterion dynamics, we come to the conclusion that the electrical properties of the top layer govern the electrooptical behavior of the PSS/PVP film.

Electric Conductivity↗

Electro-optics of colloids coated with multilayers from strong polyelectrolytes:surface charge relaxation.

The electrical properties and structure of polyelectrolyte multilayers prepared by layer-by-layer deposition of poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) on ellipsoidal beta-ferric hydrous oxide particles are examined in situ using the electric light scattering method. In the initial nonlinear growth regime, the electro-optical effect is found to increase almost in the same manner as the thickness of the multilayer film. This reveals an increase in the multilayer surface charge due to the nonlinear increase in polyelectrolyte adsorption. Above five deposition cycles, the electro-optical effect reaches a plateau and the thickness increment per layer becomes constant, indicating regular film growth. Evidence is given that the concentration of small residual ions incorporated into the PSS/PDADMAC film is negligible. Polarization of counterions, bound near to the surface of the last-adsorbed polyion, is assumed to explain the relaxation of the electro-optical effect in the frequency range 10(3)-10(5) Hz.

Journal Article↗