Polyelectrolyte macromolecules

Antonietti M., Briel A., Fosrster S. Quantitative Description of the Intrinsic Viscosity of Branched. Polyelectrolytes. Macromolecules 1997, 30, 2700-2704. 

By definition, in a solution all ions belong to the same phase, even though counterions may cluster more or less diffusely around the macroions. When significant amounts of a simple 1 1 electrolyte (such as KCl) are added to a polyelectrolyte solution, dissociation of the polyelectrolyte macromolecule is repressed in an extreme case the polyelectrolyte may be salted out. An undissociated polyacid may be precipitated by generous addition of a simple acid such as HCl. 

Gieselman, M. B. and Reynolds, J. R. 1992. Water-soluble polybenzimidazole-based polyelectrolytes. Macromolecules 25 4832-4834. 

K. Hayakawa, J.P. Santerre, and J.C.T. Kwak Study of Surfactant-Polyelectrolyte Interactions. Binding of Dodecyl-and Tetradecyltrimethylammonium Bromide by Some Carboxylic Polyelectrolytes. Macromolecules 16, 1642 (1983). 

Note 1 A polyelectrolyte network is sometimes called a cross-linked polyelectrolyte. Use of the latter term is not recommended unless the polyelectrolyte network is formed by the cross-linking of existing polyelectrolyte macromolecules rather than by nonlinear polymerization. (See the definition of a crosslink, definition 1.59, ref [4].)... 

We have investigated ultrafiltrated sodium lignosulfonate which is a three dimensional polyelectrolytic macromolecule. Rauma-Repola Corporation, Finland, produced ultrafiltrated sodium lignosulfonate in 95% purity, which contained only 5% impurities, mostly sugars. 

Kramarenko, E. Yu., Khokhlov, A.R. and Yoshikawa, K. (1997) Collapse of polyelectrolyte macromolecules revisited. 

Shiratori SS, Rubner MF (2000) pH-Dependent thickness behavior of sequentially adsorbed layers of weak polyelectrolytes. Macromolecules 33 4213—4219... 

D. Yoo, S.S. Shiratori, M.R Rubner, Controlling Bilayer Composition and Surface Wettability of Sequentially Adsorbed Multilayers of Weak Polyelectrolytes , Macromolecules, 31, 4309 (1998)... 

Grohn, F., and Antonietti, M. Intermolecular structure of spherical polyelectrolyte mi-crogels in salt-free solution. 1. quantification of the attraction between equally charged polyelectrolytes. Macromolecules, 2000,33, No. 16, p. 5938-5949. 

H. Schiessel and P. Pincus (1998) Counterion-condensation-induced collapse of highly charged polyelectrolytes. Macromolecules 31, pp. 7953-7959... 

Y. Morishima, M. Tsuji, M. Kamachi, and K. Hatada, Photochromic isomerization of azobenzene moieties compartmentalized in hydrophobic microdomains in a microphase structure of amphiphilic polyelectrolytes, Macromolecules 25, 4406-4410 (1992). 

Stevens MJ, Kremer K. Form factor of salt-free linear polyelectrolytes. Macromolecules 1993 26 4717-4721. 

Skolnick J, Fixman M. Electrostatic persistence length of a wormlike polyelectrolyte. Macromolecules 1977 10 944-948. 

Ray J, Manning GS. Counterion and coion distribution functions in the counterion condensation theory of polyelectrolytes. Macromolecules 1999 32 4588-4595. 

These two examples show that the theoretical description of conformational transition in polyelectrolyte macromolecules is of great importance. The study of conformational transition in polyelectrolyte molecules is also very important from the fundamental point of view. 

Analysis shows that the basic reason for the crucial increase of sharpness of coil-globule transition of polyelectrolyte macromolecules in comparison with the transition of electroneutral macromolecules is that the polyelectrolyte molecule in good solvent is much more expanded than the electroneutral macromolecule. It is interesting that the physical reason leading to the additional expansion of polyelectrolyte macromolecules in good solvent depends on the size of the macromolecules. 

In this paper we would like to discuss the theoretical approaches developed for the description of coil-globule transition of polyelectrolyte macromolecules in these two limiting situations and in the intermediate case when both of the contributions (due to the electrostatic repulsion and due to the translational entropy of counterions) are of the same order. We will discuss in detail mainly the theories constructed or developed by members of the Moscow group. 

Let us consider the conformation of polyelectrolyte macromolecules immersed in an infinite quantity of solvent. The counterions having high translational entropy are distributed over the whole volume of the solution their concentration in the vicinity of the macromolecules is extremely low, and their influence on the molecular conformation can be omitted completely. The conformation of the polyelectrolyte macromolecule is determined by rather strong unscreened repulsive interactions between charged groups attached to the chain. Due to this repulsion, the macromolecule assumes a strongly stretched conformation in the sense that its end-to-end distance R is a linear function of the degree of its polymerization m [14-18]. 

A similar presentation of the polyelectrolyte macromolecule as an extended sequence of blobs is valid also in the case of good solvent, when the interaction between neutral monomers has a repulsive character, and the polymer chain within the electrostatic blob has a conformation of the coil with the excluded volume interaction [15]. 

The collapse transition in the framework of the blob model of the polyelectrolyte macromolecule was considered in Ref. 17. It was proposed that the structure of the polyelectrolyte macromolecule as sequence of blobs remains valid also in poor solvent. However, in this case the space size D of... 

The collapse transition of polyelectrolyte macromolecules upon worsening of solvent quality was considered as a coil-globule transition of each of mflg blobs collapsed approximately as the chain of gif monomer units unperturbed by the Coulomb interaction [17]. It was shown that the collapse transition occurs somewhat below the 0-point. The corresponding relative temperature deviation... 

Let us consider now the intermediate case—the conformational transition in polyelectrolyte macromolecules of finite size dissolved in a solution of finite concentration. 

Winkler RG, Gold M, Reineker P. Collapse of polyelectrolyte macromolecules by counterion condensation and ion pair formation a molecular dynamics simulation study. Phys. Rev. Lett. 1998 80 3731-3734. 

Vasilevskaya VV, Khokhlov AR, Yoshikawa K. Single polyelectrolyte macromolecule in the salt solution effect of escaped counterions. Macromolecular Theory and Simulations 1999, submitted for publication. 

Pincus P. Colloid stabilization with grafted polyelectrolytes. Macromolecules 1991 24 2912-2919. 

Kokufuta E., Shimizu H., Nakamura I. Stoichiometric complexation of human serum albumin with strongly acidic and basic polyelectrolytes. Macromolecules 1982 15 1618-1621. 

Hayakawa K, Santerre JP, Kwak JCT. Study of surfactant-polyelectrolyte interactions. Binding of dodecyl- and tetradecylammonium bromide by some carboxylic polyelectrolytes. Macromolecules 1983 16 1642-1645. 

Hong J D, Jung B D, Kim CH, Kim K. 2000. Effects of spacer chain lengths on layered nanostructures assembled with main chain azobenzene ionenes and polyelectrolytes. Macromolecules 33(21) 7905 7911. 

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