Computer Simulations of Ionenes, Hydrophobic Ions with Unusual Solution Thermodynamic Properties. The Ion-Specific Effects

Ionenes are alkyl polymer chains in which different numbers of methylene groups separate quaternary ammonium groups. They are ideal molecules for studying the balance between hydrophobic and charge effects in water. Implicit-solvent models predict osmotic coefficients that are too high (too low water vapor pressures), compared to experiments. We present a molecular dynamics simulation, in explicit SPC/E water, of a solution of aliphatic 6,6 ionene oligocations with sodium co-ions and fluorine, chlorine, bromine, or iodine counterions. In the 6,6 ionene solution, the latter polyion, has more hydrophobic groups than its 3,3 counterpart, the waters are displaced more from the oligoion surface. Also, we find that the large ions, much as iodine, act like hydrophobic groups insofar as they bind to ionene's methylene groups. The water-mediated attraction between fluorine ions is enhanced in presence of weakly charged 6,6 ionene molecules. This effect may additionally reduce the osmotic pressure in such systems: Our results can explain some experimental trends in ionene solutions and weakly charged polyelectrolytes in general.