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

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    Research Article

    Films of Manganese Oxide Nanoparticles with Polycations or Myoglobin from Alternate-Layer Adsorption†
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    Institute for Micromanufacturing, Louisiana Tech University, Ruston, Louisiana 71272, and Department of Chemistry, Box U-60, University of Connecticut, Storrs, Connecticut 06269-3060, and Faculty of Engineering, Kyushu University, Fukuoka 812, Japan
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    Cite this: Langmuir 2000, 16, 23, 8850–8857
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    https://doi.org/10.1021/la000110j
    Published June 13, 2000
    Copyright © 2000 American Chemical Society
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    Abstract

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    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 MnO2 and PDDA and for SiO2 nanoparticles and Mb. Scanning electron microscopy of MnO2/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 MnO2 reflected a competition for adsorption of the protein by the film surface and dispersed MnO2 nanoparticles. Nevertheless, films of Mb and MnO2 up to 30 nm thick on rough pyrolytic graphite electrodes could be constructed. These novel films featured reversible interconversion of the protein's heme FeIII/FeII 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 FeII, BET specific areas, and electrochemically driven catalytic reduction of oxygen suggest that the Mb/MnO2 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.

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    †

     Part of the Special Issue “Colloid Science Matured, Four Colloid Scientists Turn 60 at the Millennium”.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    ‡

     Louisiana Tech University.

    §

     University of Connecticut.

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     Kyushu University.

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    Cite this: Langmuir 2000, 16, 23, 8850–8857
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