Pai-Yi Hsiao | PubMed Health

PubMed2006

Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes.

We study the salt-dependent conformations of dilute flexible polyelectrolytes in solution via computer simulations. Low concentrations of multivalent salt induce the known conformational collapse of individual polyelectrolyte chains, but as the salt concentration is increased further this is followed by a reexpansion. We explicitly demonstrate that multivalent counterions can overcompensate the bare charge of the chain in the reexpansion regime. Both the degree of reexpansion and the occurrence of overcharging sensitively depend on ion size. Our findings are relevant for a wide range of salt-induced complexation phenomena.

Computer Simulation↗

PubMed2006

Linear polyelectrolytes in tetravalent salt solutions.

The effect of adding tetravalent salt of different sizes to a solution of linear and flexible polyelectrolytes is investigated by molecular dynamics simulations. Upon the addition of salt, a chain reexpansion takes place, following a well-known collapsed conformation. The degrees of collapse and reexpansion increase with ion size. In the solution, tetravalent counterions replace monovalent ones and condense onto the chains. The condensation for small ions displays a profile different from that for large ones. In a high-salt region, ions can form layering orders around a polyelectrolyte and locally overcompensate the charge inside. Consequently, the integrated charge distribution reveals an oscillatory behavior away from a chain. By studying the radial distribution function between monomers on different polyelectrolytes, like-charge attraction between chains is demonstrated. This attraction is a prerequisite to chain aggregation or precipitation. The results show a strong dependence of salt concentration and ion size on the properties of polyelectrolyte solutions.

Journal Article↗