Collect. Czech. Chem. Commun. 2008, 73, 439-458

Charge Distribution and Conformations of Weak Polyelectrolyte Chains in Poor Solvents

Peter Košovan, Zuzana Limpouchová and Karel Procházka*

Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University, Hlavova 8, 128 43 Prague, Czech Republic


In this work we study the effect of mobility of charges in annealed polyelectrolytes on their conformational behavior in poor solvents. A combination of molecular dynamics and Monte Carlo simulation techniques was used to take the dissociation into account. We investigated the relation between the conformation of the polyelectrolyte and the distribution of charges along the chain. The results suggest that in sufficiently poor solvents the local degree of charging differs significantly from the average. When a pearl-necklace conformation is formed, the degree of charging of the pearls is significantly lower than that of the strings. The redistribution of charges stabilizes the pearl-necklace conformation and enables the formation of asymmetric conformations with a single pearl at one chain end and a string at the other end.

Keywords: Annealed polyelectrolytes; Molecular dynamics; Monte Carlo; Simulation; Polymers; Pearl-necklace; Poor solvent; Conformation.

References: 26 live references.