Polyelectrolyte, interactions between

The parameter n reflects the measure of deviation of the system from the behavior of the monomeric acid where n = 1, i.e., it characterizes the degree of interaction between the neighboring functional groups of the macroion. The value of n depends on the structure of the polyelectrolyte and the nature of the counterion pK = pK0 — log (1 — a)/a is the negative decadic logarithm of the effective dissociation constant of the carboxylic CP depending on a. 

Interaction between Crosslinked Polyelectrolytes and Dipolar Ions... 

High sorption capacities with respect to protein macromolecules are observed when highly permeable macro- and heteroreticular polyelectrolytes (biosorbents) are used. In buffer solutions a typical picture of interaction between ions with opposite charges fixed on CP and counterions in solution is observed. As shown in Fig. 13, in the acid range proteins are not bonded by carboxylic CP because the ionization of their ionogenic groups is suppressed. The amount of bound protein decreases at high pH values of the solution because dipolar ions proteins are transformed into polyanions and electrostatic repulsion is operative. The sorption maximum is either near the isoelectric point of the protein or depends on the ratio of the pi of the protein to the pKa=0 5 of the carboxylic polyelectrolyte [63]. It should be noted that this picture may be profoundly affected by the mechanism of interaction between CP and dipolar ions similar to that describedby Eq. (3.7). 

The interpretation of the relationships obtained here is based on the same principles of polyfunctional interaction between CP and organic ions which are considered in sections 3.1-3.3. The dispersion of CP grains to a certain size (1-10 pm) yields particles retaining the ability of polyfunctional interaction with organic ions. Simultaneously with increasing dispersion, the mobility of elements of the crosslinked structure also increases, which favors additional interaction. Further dispersion of CP (d 0.1 pm) gives so weak networks that the spatial effect of polyfunctional interaction with organic ions drastically decreases similar to linear polyelectrolytes [64]. 

The swelling pressure of polyelectrolyte gels is usually considered as a sum of the network (jtnct) and ionic contributions (nion) [4, 99, 101, 113, 114]. The former describes the uncharged gel while taking into account the interaction between the polymer segments and the solvent as well as the network elasticity [4] ... 

Hayama et al.132 discussed the catalytic effects of silver ion-polyacrylic add systems toward the hydrolyses of 2,4-dinitrophenylvinylacetate 84 (DNPVA) by using the weak nudeophilicity of carboxylic groups and the change-transfer interactions between olefinie esters and silver ions133Metal complexes of basic polyelectrolytes are also stimulating as esterase models. Hatano etal. 34, 13S) reported that some copper(II)-poly-L-lysine complexes were active for the hydrolyses of amino acid esters, such as D- and L-phenylalanine methyl ester 85 (PAM). They... 

The precise nature of the adhesion of the polyelectrolyte cements to untreated dental enamel and dentine has yet to be established. The earliest theory was due to Smith (1968) who speculated that the polyacrylate chains of the cement formed a chelate with calcium ions contained in the hydroxyapatite-like mineral in enamel and dentine. Beech (1973) considered this unhkely since it involved the formation of an eight-membered ring. Beech studied the interaction between PAA and hydroxyapatite, identified the formation of polyacrylate and so considered that adsorption was due to ionic attraction. 

In this paper we briefly describe the apparatus and experimental method, then consider the interactions between i) layers of polystyrene in cyclohexane under poor-solvent and ii) 0 - solvent conditions,iii) the interactions between adsorbed PEO layers in a good (aqueous) solvent and iv) the surface forces between layers of adsorbed poly-L-lysine, a cationic polyelectrolyte, in aqueous salt solutions. We consider briefly the implications of our results for the current theoretical understanding. 

The interactions between bare mica surfaces in 10 and 10 M KNO solutions were determined at pH = 3.5. In both cases an exponential type relation F(D) = 0-lcD was indicated, with decay lengths 1/k = 1.4 nm and 8 nm for the two salt concentrations, respectively, but with an effective surface potential tp = 40 mV, considerably lower than its value at the higher pH used in the PEO experiments (figure 6a, curve (a)). The lower value of p is probably the result of a lower net degre of ionization of the mica surface in the presence of the large H1" concentration (the low pH was used to ensure full ionization and polyelectrolyte). 

In scenario (c) corresponding to semidilute solutions, polyelectrolyte chains interpenetrate. Under these circumstances, there are three kinds of screening. The electrostatic interaction, excluded volume interaction, and the hydro-dynamic interaction between any two segments of a labeled polyelectrolyte chain are all screened by interpenetrating chains. Each of these three interactions is associated with a screening length, namely, and These screening... 

This value of kn is actually low by an order of magnitude for dilute suspensions of charged spheres of radius Rg. This is due to the neglect of interchain correlations for c < c in the structure factor used in the derivation of Eqs. (295)-(298). If the repulsive interaction between polyelectrolyte chains dominates, as expected in salt-free solutions, the virial expansion for viscosity may be valid over considerable range of concentrations where the average distance between chains scales as. This virial series may be approxi-... 

In 1991 Decher and coworkers introduced a new method to prepare multilayered thin films by electrostatic interaction between oppositely charged polyelectrolytes [3, 62, 63]. In this fashion, thin molecular films comprised of charged polymers. 

The measurement of the surface tension of SDS solutions at constant polymer additions was performed to investigate any possible interactions between SDS and the polymers used in these experiments. The results, shown in Figure 2, indicate no interaction between SDS and either PAA or PAM. Interactions between similarly charged surfactant and polyelectrolyte are not common as electrical effects frequently dominate to prevent any hydro-phobic or hydrogen bonding interaction. The hydrophilic nature of the amide dipole of polyacrylamides has been suggested (11) as a possible factor in preventing interaction with sodium dodecylsulfate,... 

Analysis by XPS after incorporation of the linear or dendritic cationic polymers showed an increase in the atom % N consistent with incorporation of an N-rich polycation. The polyvalent interactions between the cationic polyelectrolytes and the poly(sodium acrylate)graftson PE were stable to Soxhlet extraction with 95% ethanol, repeated acid/base treatment, and soaking or sonication in isopropanol and THE However, in these cases, simple acid treatment did not release the cationic polymer as was the case with PAA/Au grafts even though grafting in both cases was reportedly ionic and not covalent. 

For polyelectrolytes, electrostatic interactions provide the driving force for their salient features and have to be included in any theoretical description. The reduced electrostatic interaction between two point-like charges can be written as qiq2v r) where... 

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