Fluorescence observations on complex formation between linear and hyperbranched polyelectrolytes in dilute aqueous solutions

The complexation between poly(ethylene imine) (PEI) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) or AMPS copolymers was investigated with the relative excimer emission intensity IE/IM of a cationic probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl), fluorescence nonradiative energy transfer (NRET) IPy/INp of naphthalene to pyrene labels, the fluorescence anisotropy r and IE/IM of pyrene labels. PEI was a hyperbranched weak polycation in acid solution, which formed complex with anionic polyelectrolytes due to the electrostatic attraction. The IE/IM of PyMeA · HCl probe decreased to zero, the intra-, intermolecular NRET IPy/INp and IE/IM of pyrene labels on the AMPS copolymers reached their maxima when χ was increased from 0 to 2.4, which was defined as the mole ratio of the amino group in PEI to the AMPS group in the polyanion. These facts indicated the formation of nonstoichiometric complex of the oppositely charged polyelectrolytes when χ = 2.4 at the concentration much lower than their overlap concentrations. The intermolecular aggregate appeared as indicated by an increase in the intermolecular IPy/INp and r with χ up to 2.4 due to neutralizing and hydrophobizing the polyelectrolytes and the bridging effect of the PEI chain bound on different polyanion chains. At high pH, PEI became a neutral polymer and did not bind with the AMPS anion to form the complex as illustrated by the constant value of r for the pyrene labels attached to the AMPS polyanion as that without addition of PEI. The amino group in PEI quenched pyrene and naphthalene emission, resulting a decrease in both INp and IPy.