Lateral Distribution of Charged Species along a Polyelectrolyte Probed with a Fluorescence Blob Model

The distribution of metal counterions binding onto the oppositely charged surface of a model polyelectrolyte, namely DNA, was characterized by conducting fluorescence quenching experiments. In these experiments, DNA was used as a molecular ruler to measure the average distance (dblob) over which electron transfer takes place between DNA intercalated ethidium bromide (DNA-EB) and the electrostatically bound divalent metal cations Ni2+ and Cu2+. Analysis of the fluorescence decays of DNA-EB quenched by Cu2+ and Ni2+ with the Fluorescence Blob Model showed that dblob equaled the Debye length (?-1). This surprisingly simple result considering the overall complexity of the system under study led to the straightforward proposal that counterions bind to a polyelectrolyte by distributing themselves randomly into an array of self-defined subdomains of dimension ?-1. In turn, this insight can be utilized to rationalize the complex behavior of polyelectrolytes in aqueous solution.