Monte Carlo simulations of charged dendrimer-linear polyelectrolyte complexes and explicit counterions

We study complexes composed of one dendrimer of generation G = 4 (G4 dendrimer) with N-t = 32 charged terminal groups and an oppositely charged linear polyelectrolyte accompanied by neutralizing counterions in an athermal solvent using Monte Carlo simulations based on the bond fluctuation model. In our study both the full Coulomb potential and the excluded volume interactions are taken into account explicitly with the reduced temperature tau and the chain length N-ch as the main simulation parameters. Our calculations indicate that there exist three temperature ranges that determine the behavior of such complexes. At tau(complex) stable charged dendrimer-linear polyelectrolyte complexes are formed first, which are subsequently accompanied by selective counterion localization within the complex interior at tau(loc) <= tau(complex), and counterion condensation as temperature is further decreased below tau(cond) < tau(loc). In particular, we observe that condensation takes place exclusively on the excess charges in the complex and thus no condensation is observed at the compensation point (N-ch = N-t), irrespective of tau. For N-ch not equal N-t the complex is overally charged. Furthermore, we discuss the size and structure of the dendrimer and the linear polyelectrolyte within the complex, as well as spatial distributions of monomers and counterions. Conformations of the chain in the bound state are analysed in terms of loops, trains, and tails. (C) 2011 American Institute of Physics. [doi:10.1063/1.3592558]