Efficient polymerization of the aniline dimer p-Aminodiphenylamine (PADPA) with Trametes versicolor laccase/O2 as catalyst and oxidant and AOT vesicles as templates

The aniline dimer PADPA (= p-aminodiphenylamine = N-phenyl-1,4-phenylenediamine) was polymerized to poly(PADPA) at 25 °C with Trametes versicolor laccase (TvL)/O2 as catalyst and oxidant and in the presence of vesicles formed from sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as templates. In comparison to the previously studied polymerization of aniline with the same type of enzyme–vesicle system, the polymerization of PADPA is much faster, and considerably fewer enzymes are required for complete monomer conversion. Turbidity measurements indicate that PADPA strongly binds to the vesicle surface before oxidation and polymerization are initiated. Such binding is confirmed by molecular dynamics (MD) simulations, supporting the assumption that the reactions which lead to poly(PADPA) are localized on the vesicle surface. The poly(PADPA) obtained resembles the emeraldine salt form of polyaniline (PANI-ES) in its polaron state with a high content of unpaired electrons, as judged from UV/vis/NIR, EPR, and FTIR ...