ATP cap ͉ length diffusivity ͉ modeling ͉ critical concentration

Counterion condensation is a basic feature of 2D electrostatics exhibited by highly charged rodlike polymers such as DNA. In the framework of the Poisson Boltzmann equation with salt, we show that such a polymer of radius a attracts a condensate of thickness RM=A(axi)1/2 where xi is the Debye length and A depends weakly on the polymer charge density q0. To leading order in 1/ln(xi/a), we derive the condensate structure and show that free ions follow universal density profiles independent of a and q0. Generalizing this approach we calculate ion profiles for finite concentration solutions.

No abstract

The molecular conformation of two typical polyelectrolytes, sodium polystyrene sulfonate (NaPSS) and quarternized poly-4-vinylpyridine (QP4VP), was studied in aqueous solutions without salt addition at the single molecular level. By fluorescence correlation spectroscopy, the hydrodynamic radius (R) of NaPSS and QP4VP with the molecular weight ranging more than one order of magnitude was measured. The scaling analysis of R exhibits scaling exponent of 0.70 and 0.86 for NaPSS and QP4VP in solutions without added salts, respectively, showing the conformation is much more expanded than random coil. Numerical fittings using the model of diffusion of a rod molecule agree with the data well, indicating that the polyelectrolyte chains take the rod-like conformation under the condition without salt addition. Further investigations by determining the electric potential of single PSS chains using the photon counting histogram technique demonstrate the enhanced counterion adsorption to the charged chain at higher molecular weight.