Films of Manganese Oxide Nanoparticles with Polycations or Myoglobin from Alternate-Layer Adsorption

Abstract

Alternate adsorption of manganese oxide nanoparticles with polycations poly(dimethyldiallylammonium) (PDDA) or myoglobin (Mb) onto silver, quartz, and rough pyrolytic graphite gave stable, porous, ultrathin films. Quartz crystal microbalance (QCM) and UV−vis absorbance revealed regular film growth at each adsorption step for MnO 2 and PDDA and for SiO 2 nanoparticles and Mb. Scanning electron microscopy of MnO 2 /PDDA films showed smooth surfaces on the 20 nm scale and cross sections consistent with individual nanoparticles. QCM during growth of films of Mb and MnO 2 reflected a competition for adsorption of the protein by the film surface and dispersed MnO 2 nanoparticles. Nevertheless, films of Mb and MnO 2 up to 30 nm thick on rough pyrolytic graphite electrodes could be constructed. These novel films featured reversible interconversion of the protein's heme Fe III /Fe II redox couple with 10 electroactive layers of protein, considerably more than for polyion−Mb films on smooth gold (ca. 1.3 electroactive layers), and coiled PSS/Mb films on rough graphite (7 electroactive layers). Shifts in redox potential caused by CO complexation of the heme Fe II, BET specific areas, and electrochemically driven catalytic reduction of oxygen suggest that the Mb/MnO 2 films are highly porous to gas molecules. To our knowledge, these films represent the first nanofabrication of inorganic particles with functional proteins by the layer-by-layer method.