Probing the Inhomogeneous Charge Distribution on Annealed Polyelectrolyte Star Polymers in Dilute Aqueous Solutions

The conformational structure of a polyelectrolyte chain in dilute aqueous solution is strongly coupled with its surrounding electrostatic environment. With the introduction of branched topology, the distribution of counterions in the vicinity of a polyelectrolyte chain becomes highly inhomogeneous, giving rise to complex structures of branched polyelectrolytes in dilute aqueous solution. To directly probe the local electrostatic conditions near a branched polyelectrolyte in aqueous solutions, star-shaped poly(2-vinylpyridine) (P2VP) polymers with precise labeling of one single fluorophore at different locations, for example, the star center or the terminal group of one arm, were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization of vinyl-terminated P2VP macromonomers. Using fluorescence correlation spectroscopy (FCS) combined with photon counting histogram (PCH) analysis, the conformational structures and local electric potential of P2VP star polyelectrolytes were investigated in dilute aqueous solutions of varied pH at a single molecule level. Despite the same hydrodynamic radius of P2VP stars, pH-sensitive fluorophores labeled at different locations sensitively differentiated the higher electric potential at the star center from the lower electric potential at the periphery in dilute aqueous solutions.