Fluorescence decay and quenching of pyrene labeled on sulfonate polyelectrolytes in salt-free aqueous solutions

Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacrylamide were observed in dilute salt-free aqueous solutions as a function of the mole fraction FAMPS of AMPS from 0 to 0.896. Monoexponential decay was found for the samples of FAMPS<0.35 and biexponential decay for the samples of FAMPS>0.35. The fast decay component is 80%, and the averaged lifetime 〈τ〉 and lifetime τ1 of the fast decay is decreased with increasing FAMPS. Quenching efficiency of Cu2+, I−, CH3NO2, and dinitrobenzene to the pyrene label was investigated in the framework of Stern–Volmer plot. With increasing FAMPS the quenching efficiency of Cu2+ is increased while that of I− decreased. For the neutral quenchers, the quenching rate constant kq increases when FAMPS<0.449 then decreases, showing a decline of accessibility to the pyrene label. These results were interpreted consistently with the counterion condensation concept, where condensed counterions caused the polyelectrolyte chains to aggregate. The existence of less-polar “temporal aggregated domain” in highly charged polyelectrolytes appears to lead to the slower decay and lower accessibility of the pyrene labels.