Correlation length of hydrophobic polyelectrolyte solutions

Abstract

The combination of two techniques (Small Angle X-ray Scattering and Atomic Force Microscopy) has allowed us to measure in reciprocal and real space the correlation length $\xi$ of salt-free aqueous solutions of highly charged hydrophobic polyelectrolyte as a function of the polymer concentration $C_p$, charge fraction $f$ and chain length $N$. Contrary to the classical behaviour of hydrophilic polyelectrolytes in the strong coupling limit, $\xi$ is strongly dependent on $f$. In particular a continuous transition has been observed from $\xi \sim C_p^{-1/2}$ to $\xi\sim C_p^{-1/3}$ when $f$ decreased from 100% to 35%. We interpret this unusual behaviour as the consequence of the two features characterising the hydrophobic polyelectrolytes: the pearl necklace conformation of the chains and the anomalously strong reduction of the effective charge fraction.