Solid-state magnetic resonance studies of polyaniline as a radical scavenger

The first detailed study of polyaniline (PANI) and reduced PANI (R-PANI) before and after reaction with the stable organic free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) by using solid-state C-13 CP MAS (cross-polarization magic-angle spinning), NQS (nonquaternary suppressed) and CPPI (cross-polarization phase inversion) nuclear magnetic resonance techniques is reported. These techniques reveal relatively subtle structural changes that occur upon reaction with DPPH free radicals and confirm the radical scavenging ability of PANI. The integrated intensity of the PANI CP MAS spectrum after reaction with DPPH is about 8% larger than that of PANI and this cannot be explained by an oxidation process alone. The increase is attributed to a decrease in the polaron concentration in the polymer, which is consistent with electron paramagnetic resonance (EPR) data that show a decrease of the EPR signal intensity after reaction of chemically synthesized PANI with DPPH.